Energy 207 (2020) 118289

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

Artificial neural network approach for co-pyrolysis of Chlorella vulgaris

and peanut shell binary mixtures using microalgae ash catalyst
Jang Tyng Bong a, Adrian Chun Minh Loy b, c, Bridgid Lai Fui Chin a, *, Man Kee Lam c, d,
Daniel Kuok Ho Tang a, Huei Yeong Lim c, d, Yee Ho Chai c, d, Suzana Yusup c, d
a
Department of Chemical Engineering, Faculty of Engineering and Science, Curtin University Malaysia, CDT 250, 98009, Miri, Sarawak, Malaysia
b
Department of Chemical Engineering, Monash University, Victoria, 3800, Australia
c
National HiCoE Thermochemical Conversion of Biomass Processing Lab, Centre for Biofuel and Biochemical Research, Institute of Sustainable Living,
Chemical Engineering Department, Universiti Teknologi PETRONAS, Seri Iskandar, Perak, 32610, Malaysia
d
Department of Chemical Engineering, Universiti Teknologi PETRONAS, 32610, Seri Iskandar, Perak, Malaysia

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

Article history: The catalytic pyrolysis of pure microalgae (M), peanut shell wastes (PS) and their binary mixtures were
Received 13 April 2020 analysed by introducing the microalgae ash (MA) as a catalyst. The pyrolysis processes were conducted at
Received in revised form different heating rates from 10 K/min-100 K/min to observe their thermal degradation behaviour.
23 June 2020
Additionally, Artificial Neural Network (ANN) was applied by feeding the heating rates and temperatures
Accepted 30 June 2020
to predict the weight loss of the samples. The kinetic and thermodynamic parameters were also
Available online 6 July 2020
determined through three different iso-conversional kinetic models: Friedman (FR), Kissinger-Akahira-
Sunose (KAS) and Flynn-Wall-Ozawa (FWO). Based on the kinetic results, FWO model achieved the
Keywords:
Catalytic pyrolysis
lowest deviation between the activation energies (Ea) from the experimental which aligned with the
Microalgae ANN predicted results. The finding also shows that the activation energy (Ea) of the catalytic pyrolysis of
Thermodynamic analysis binary mixtures was lower than the pure M and PS (Experimental: 142.56 kJ/mol; ANN forecast:
Kinetic analysis 131.37 kJ/mol).
Artificial neural network © 2020 Elsevier Ltd. All rights reserved.

1. Introduction Biomass feedstock is one of the potential fossil fuel alternatives

The demand of fossil fuels in the industry especially on trans-
portation, heating and electricity generation is escalating rapidly
due to the advantages of high energy output, high availability and
low cost; which have brought about the depletion of this resource.
According to Ediger [1]; 45 out of 87 countries that produce fossil
fuel used more than their yields, where the range of dependency on
it is from 32.1% to 100%. Besides, the U.S. Energy Information
Administration (2019) have predicted that the upraise in petroleum
and natural gas usage will continue until up the year of 2050. This
matter has prompted the discovery and development of renewable
energies such as wind, solar, biomass and thermal [2].
* Corresponding author.
E-mail addresses: 700016478@student.curtin.edu.my (J.T. Bong), adrian.loy@
monash.edu (A.C.M. Loy), bridgidchin@curtin.edu.my, bridgidchin@gmail.com
(B.L.F. Chin), lam.mankee@utp.edu.my (M.K. Lam), daniel.tang@curtin.edu.my
(D.K.H. Tang), limhueiyeong@gmail.com (H.Y. Lim), yeeho.chai@utp.edu.my
(Y.H. Chai), drsuzana_yusup@utp.edu.my (S. Yusup).
because of their abundant supply, biodegradability, affordability,
high concentration of volatile matters and low content of ashes [3].
According to Loy et al. [4] and Khan et al. [5]; biomass can be
transformed into useful products such as bio-char, syngas and bio-
oil via thermochemical conversion. It was observed that an
increasing current trend of industries are moving towards devel-
oping biomass conversion technologies for renewable energy re-
sources. Peanut shell wastes (PS) is one of the common biomass
produced in the world and considered as the main by-product
generated from peanut production. According to Perea-Moreno
et al. [6]; the quantity of peanuts production in 2016 is 43.9
million tons and are mainly grown in ASEAN countries with a 65.3%
global production rate. In the present researches, PS are mainly
used to produce activated carbon for adsorption of hexavalent
chromium, precursor to produce active elements of a hybrid so-
dium ion capacitor and bio-fillers of reinforced epoxy composite
[7e9]. Meanwhile, microalgae, a photosynthetic organism that in-
habits in places such as saltwater, freshwater, soil and marine
surroundings can utilize CO2 effectively, have high heating values

https://doi.org/10.1016/j.energy.2020.118289
0360-5442/© 2020 Elsevier Ltd. All rights reserved.
2 J.T. Bong et al. / Energy 207 (2020) 118289

Table 1 novel carbon-based solid acid catalyst from the MA through partial
Physiochemical properties of microalgae chlorella vulgaris (Pure M) and peanut hydrothermal carbonization and claimed that the addition of the
shells waste (Pure PS).
MA catalyst can induced a higher catalytic pyrolysis activity. In
Microalgae chlorella vulgaris (wt %) Peanut shell wastes (wt %) addition, MA has a high reusability in which the catalyst activity can
Proximate analysisa last for at least five cycles, indicating that MA is an effective catalyst
Moisture 6.20 7.23 in thermochemical conversion.
Protein 17.20 6.43 Researches on pyrolysis process of PS are predominantly
Fat 34.30 12.30
revolving around pure PS, pre-treated PS, and a combination of PS
Ash 42.30 19.98
Crude Fiber e 45.94 and catalyst, where the study on utilizing PS in co-pyrolysis process
with other biomass mixtures and MA as catalyst to produce syngas
Ultimate analysisa
have not been explored [15,16]. Hence, this research will focused on
Carbon 54.20 52.80 utilizing PS as the fuel source mixed with microalgae chlorella
Hydrogen 7.15 6.35
Nitrogen 10.25 0.85
vulgaris in the pyrolysis process with the presence of MA as catalyst
Sulphur 0.20 0.26 for the production of third generation biofuel. There are a few pa-
Oxygen 28.20 39.74 rameters such as feedstock composition, temperature, residence
time, catalyst, and gas flow rate can influence both quality and
a
Dry mass fraction basis. quantity of the pyrolysis products [17]. Higher heating rate in-
creases both the decomposition rates of feedstock and bio-oil yield
[18]. Furthermore, high heating rates from conventional pyrolysis
(HHV) and biofuel yields. Thus, the production of biofuel specif-
process can be obtained from the reduction of particle size. When
ically on biodiesel from microalgae is highly attractive and feasible.
the residence time of the vapour phase is extended during high
The only limitation of the process is 25e30% of the microalgae ash
temperatures, this provides a secondary decomposition vapour to
(MA) will be produced along with the biodiesel which reduces the
occur [18]. The vapour removal in bio-oil is important and can be
economical attractiveness of the process [10,11]. Among the
done by introducing a suitable carrier gas flow rate to the reactor
different varieties of microalgae, the microalgae chlorella vulgaris is
[18]. Hence, it can be concluded that fast heating rates, moderate
said to produce in high yield of bioenergy and has been cultivated in
temperatures and low residence time are favoured in bio-oil pro-
industrial scale [12]. In recent year, researchers have reported that
duction [19]. The presence of high oxygen content and oxygenated
the composition of biomass residues (e.g. cellulose, hemicellulose,
compounds leads to the reduction of higher heating values (HHVs)
lignin, lipid and proteins) can be used as the catalyst materials in
and increment of the viscosity of bio-oil during storage, respec-
the thermochemical conversion for bioenergy production [13]. For
tively [18]. The quality of the bio-oil can be improved through
instance Ref. [14], have reported that the addition of rice hull ash
upgrading process via physical and chemical methods [20].
can reduced the Ea of the rice husk pyrolytic system from 190.8 kJ/
Various studies on co-pyrolysis of various mixtures have been
mol to 152.6 kJ/mol. Whereas, Fu et al. (2013) have synthesized a

Table 2
Frequently used transfer functions in Artificial Neural Network (ANN) (Hudson et al., 1992; Yusri et al., 2018).

Transfer Function Formula Graphical Plot Properties

Linear (purelin) f ðuÞ ¼ u Output range: ve to þ ve infinity Input range: ve to þ ve infinity

 Output is calculated by returning the value passed to it.
 Not suitable to be used in hidden layers as it only provides linear separable solutions

Sigmoid or log-sigmoid (logsig) f ðuÞ ¼ Output range: 0 to 1

1 Input range: ve to þ ve infinity
1 þ eu  Can adjust weights to reduce error

Hyperbolic tangent sigmoid f ðuÞ ¼ Output range: 1 to 1

(tansig) eu  eu Input range: ve to þ ve infinity
eu þ eu  Can adjust weights to reduce error
 Derived from the logsig function
 Learns faster, has more analytical benefits compared to logsig (considers wider output
range)
 J.T. Bong et al. / Energy 207 (2020) 118289
Table 3
Artificial Neural Network (ANN) model development parameters.
Parameter
Number of inputs
Number of outputs
Number of hidden layers
Transfer functions
Number of neurons
Data division function
Learning algorithm
Data division (Training-Validation-Testing)
Data number
Training number
Performance function
Maximum training epochs
Validation checks
Fig. 1. ANN architecture developed for current study.
carried out in recent years. The combination mixtures include
peanut and cassava starch; sugarcane bagasse and Enteromorpha
prolifera (green algae); rubber seed shells and plastics [21] and
microalgae and plastics [22e24]. The products of co-pyrolysis
process have been reported as chemical solvents and fuel genera-
tion. For instance, the liquid bio-oil have a wider application on
heat, transport fuels, electricity and chemicals due to their ease of
transportation and its convenience on being added into an existing
system [25]. On the other hand, char collected from co-pyrolysis
processes can be mixed with other binder materials to be used to
fire a furnace whereas biogas can be used to substitute diesel [26].
Recently, researchers have reported that the accuracy of weight
loss data obtained through thermogravimetric analysis (TGA)
approach can be further confirmed using Artificial Neural Network
(ANN) model. ANN model works like the neural system of a human
brain where it is capable to suggest outputs even when the rela-
tionship is complicated, and the information is inadequate. This
unique model is not programmable, but it is trained to adapt and
recognize the trend of parameters introduced so that the desired
output can be classified and predicted accurately in a short time
3
Network Detail
2 (Heating rate, K/min; Temperature, K)
1 (Weight loss, wt %)
2
tansig-tansig (TT)/losig-tansig (LT)
1-12/1-12
Dividerand
Levenberg-Marquardt (TRAINLM)
70%-15%e15%
~ 5000
20
Mean squared error (MSE)
1000 epochs
6
[27,28]. Thus far, the available research studies on waste pyrolysis
related to the ANN application revolves around sewage sludge, rice
husks, cotton cocoon shell, tea waste, olive husks and pine sawdust
[29e32]. It was brought to attention that there is a lack of ANN
studies on the third generation of biofuel feedstocks published.
Therefore, in this research, MATLAB® R2017b will be used to run
the ANN model to study the catalytic biomass mixtures’ thermal
degradation behaviour prediction through the TG and DTG plot.
Both experimental and predicted results from TGA and ANN for
each feedstock mixtures under different heating rates will be
substituted into different iso-conversional kinetic models such as
Friedman (FR), Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-
Ozawa (FWO) to obtain the values of Ea, pre-exponential factor
(A) and order of reaction (n). Iso-conversional model is a robust
method to calculate the Ea of a pyrolysis process through the
investigation of different isothermal or dynamic measurements
[33,34]. Meanwhile, the kinetic parameters (Ea and A) obtained
from each model (FR, KAS, FWO and ANN) will be substituted into
the respective equations to obtain the thermodynamic parameters
(DH, DG and DS). The energy analysis equations are constructed by
4 J.T. Bong et al. / Energy 207 (2020) 118289

Fig. 2. DTG curves of (a) pure microalgae (Pure M), (b) pure microalgae ash (Pure MA), (c) pure peanut shell (Pure PS), (d) microalgae and microalgae ash mixtures (M/MA), and (e)
microalgae, microalgae ash and peanut shell mixtures (M/MA/PS).

abiding the second law of thermodynamics, where the entropy of a
system will vary until thermal equilibrium is achieved.
2. Materials and methods
2.1. Biomass preparation
The chlorella vulgaris microalgae biomass and MA ash catalyst
were provided by Dr. Lam Man Kee from Centre for Biofuel and
Biochemical Research, Universiti Teknologi PETRONAS (UTP),
Malaysia. The moisture content of the microalgae biomass and
catalyst was reduced through sun-drying for 24 h and then, sieved
to a particle size of ca. 100e200 mm. Meanwhile, the PS was ob-
tained from Ngan Yin Food Industries Sdn. Bhd and grounded to ca.
100e200 mm. The physiochemical properties of the biomasses used
in this study were shown in Table 1. The proximate analysis was
performed using gravimetric analysis method reported by Garcia
et al. [35] to determine the volatile matter, fixed carbon and ash
 J.T. Bong et al. / Energy 207 (2020) 118289 5

content. Whereas, the elemental composition of carbon, hydrogen,

nitrogen, oxygen, and sulphur of the feedstocks were determined
using LECO CHNS-932 elemental analyzer. Then, the co-pyrolysis
binary mixtures were mixed homogeneously with respect to the
pre-calculated ratio (e.g. mixture of microalgae and microalgae ash
mixtures (M/MA) ¼ weight of MA is 10% of the weight of M (9:1);
mixture of the microalgae, microalgae ashes and peanut shell
wastes (M/MA/PS) is in the ratio is 4.5:1: 4.5).

2.2. Thermogravimetric analyzer (TGA)

All the co-pyrolysis experiments were conducted by using a

Fig. 3. Average MSE of pure microalgae (Pure M) at transfer functions tansig-tansig
(TT) and logsig-tansig (LT).
thermogravimetric analysis (TGA) TGADSCI; 1600 (Mettler Toledo
(M) Sdn Bhd) coupled with mass spectrometer (MS) and quadru-
pole analyzer (Thermostar Prisma QMS 200, Pfeiffer Vacuum)
within the temperature from 300 K to 1180 K to investigate the
thermal decomposition of biomass [36]. Before the commencement
of the experiment, 100 mL/min of nitrogen gas was purged into the
TGA at 50  C for 20 min to avoid undesirable oxidation and to

Table 4
Minimum average MSE obtained from different samples with tansig-tansig (TT) and logsig-tansig (LT) transfer functions.

Minimum Average MSE

Sample Neuron Number TT Neuron Number LT

3
Pure M 9 2.36  10 11 4.98  103
Pure MA 10 2.03  102 12 3.83  103
Pure PS 12 9.36  102 12 6.09  102
M/MA 10 1.08  102 12 1.27  102
M/MA/PS 11 4.31  103 10 4.11  103

Fig. 4. ANN generated plot of pure microalgae (Pure M) at a heating rate of 10 K/min (HR10) and 9 neuron numbers (a) validation performance of MSE (b) error histogram, and (c) R-
squared value distribution.
6 J.T. Bong et al. / Energy 207 (2020) 118289
Fig. 4. (continued).
remove any possible trapped gas. Then, a total of 10 mg pure
sample or its mixtures were placed on a ceramic crucible with equal
portions in the analyzer. The experiments were performed at
different heating rates of 10, 20, 30, 50 and 100 K/min (known as
HR10, HR20, HR30, HR50 and HR100 respectively). Five sets of
samples which are pure M, pure MA, pure PS, M/MA mixture and
M/MA/PS mixture were tested. The results obtained from the TGA
(weight loss with respect to temperature and time) were collected
so that thermogravimetric (TG) curves and derivative thermog-
ravimetry (DTG) curves can be plotted to observe the variation of
feedstocks at different heating rates and temperatures.
2.3. Artificial Neural Network (ANN) topology
The structure of Artificial Neural Network (ANN) model imitated
the human neural system to predict the results for nonlinear and
complicated inputs. The transfer function in ANN model controls its
output and the frequently used transfer functions (purelin, logsig
and tansig), its formulae and the graphical plots are listed in Table 2.
For back-propagation algorithms, step function and non-monotonic
functions should be avoided to achieve a differentiable, smooth,
monotonic and bounded prediction [37]. Linear transfer functions
such as purelin should be avoided in the hidden layers as it provides
a linearly separable prediction. Generally, the tansig function has
more advantages as compared to the other two as it considers a
larger range of output (Yusri et al., 2018).
A summary of ANN details established in this study is presented
in Table 3 whereas its architecture is depicted in Fig. 1. The algo-
rithm chosen to build the model in MATLAB® R2017b software was
the feedforward Levenberg-Marquardt (LM) back-propagation al-
gorithm along with heating rates (K/min) and temperatures (K)
obtained from the experimental data as the inputs and the weight
loss (wt %) as the suggested output. Besides, two hidden layers were
involved where both tansig-tansig (TT) and logsig-tansig (LT)
transfer functions were used to predict the outcome. The TGA’s
input data division function ‘dividerand’ was used and the training,
testing and validation data was distributed into 70%, 15% and 15%
randomly so that the computational burden can be reduced. The
final set of data selected from the ANN predictions were deter-
mined by evaluating the mean square error (MSE) and the regres-
sion value (R2). The optimum set of values with a low MSE and high
R2 will be chosen as the data to be used to test the data precision as
it indicates a smaller cycle error and a higher proximity of the
predicted output as compared to the actual data. Lastly, the weight
loss percentage of feed predicted by the network will be extracted
to plot a TG curve, calculate the kinetic parameters by using
Friedman, KAS and FWO methods and thermodynamic parameters
to be compared with the experimental data.
 J.T. Bong et al. / Energy 207 (2020) 118289 7

Fig. 5. Comparison between experimental, tansig-tansig (TT) and logsig-tansig (LT) predicted TG curves of (a) pure microalgae (Pure M), (b) pure microalgae ash (Pure MA), (c) pure
peanut shell (Pure PS), (d) microalgae and microalgae ash mixtures (M/MA), and (e) microalgae, microalgae ash and peanut shell mixtures (M/MA/PS).

2.4. Kinetic analysis

k
Solid ðsÞ/Char ðsÞ þ VolatileðgÞ (1)
The identification of kinetic parameters such as activation en-
ergy (Ea), pre-exponential factor (A) and order of reaction (n) of the Ea
pyrolysis and co-pyrolysis processes are important as the param- k ¼ Ae RT (2)
eters that affect the composition of pyrolysis products, at the same
Besides, Eq. (3) shows the rate equation for solid state reaction
time acting as a reference for the design and optimization of re-
to produce volatiles from the feedstock with parameters such as a,
actors and the process conditions. The weight loss of feedstock
t, k(T) and f(a) which represents the extent of conversion, time (s),
obtained from the TGA and ANN was used to plot TG curves and
rate constant and reaction model, respectively. The extent of con-
DTG curves to determine the Ea, A and n along with the iso-
version (a) can be calculated by substituting the initial mass (w0),
conversional kinetic models. The plot of TG curve shows the rela-
final mass (wf) and instantaneous mass (w) of the feed sample
tionship of the weight loss of feedstock versus the temperature
accordingly to Eq. (4).
whereas the plot of DTG curve displays the relationship of the
derivative weight loss vs the temperature where the maximum da
reaction rate can be observed [38]. ¼ kðTÞ,f ðaÞ (3)
dt

w0  w
a¼ (4)
w0  wf
2.4.1. Non-isothermal method
Under non-isothermal conditions where the temperature is not Taking b as the heating rate (dT , K/min), Eq. (5) was constructed.
dt
constant, the kinetic equations of solid state reaction are solved
The integration of Eq. (5) from the initial temperature (T0) to the
through a non-linear optimization to calculate the kinetic param-
instantaneous temperature (T) resulted in Eq. (6) below.
eters. The single reaction solid degradation and Arrhenius reaction
can be seen in Eq. (1) and Eq. (2) respectively with the unknowns k

da A Ea
as the temperature dependant constant, R as the universal gas ¼ , exp  ,f ðaÞ (5)
dT b RT
constant (8.314  103 kJ/mol K) and T as the absolute temperature
(K) [39].
8 J.T. Bong et al. / Energy 207 (2020) 118289

Fig. 5. (continued).

used to calculate the Ea;A and n of each pyrolysis and co-pyrolysis

ða ðT
 process. FR was known as the differential method whereas both
da A Ea
gðaÞ ¼ ¼ , exp  ,dT (6) KAS and FWO were the integral methods. Both sets of experimental
f ðaÞ b RT
0 T0 and ANN prediction data were substituted into the iso-conversional
models to perform necessary calculations. Then, linear graphs will
be plotted to obtain the relevant kinetic parameters and compared
accordingly.
2.4.2. Iso-conversional methods
The iso-conversional methods, also known as the model-free 2.4.2.1. Friedman (FR). FR equation as shown in Eq. (7) was more
kinetic analysis methods were categorised into differential and sensitive to noise and thus, it was more likely to have errors during
integral methods. In this study, FR, KAS and FWO were chosen to be the estimation of Ea values as a function of a, the extent of reaction
 J.T. Bong et al. / Energy 207 (2020) 118289 9

Table 5 characteristics as KAS in terms of its noise sensitivity and the error
Stage 2 thermal decomposition data for pure microalgae (Pure M), pure microalgae [42]. It covers a large range of a and is applicable for cases where
ash (Pure MA), pure peanut shell wastes (Pure PS), microalgae and microalgae ash
mixtures (M/MA), and microalgae, microalgae ash and peanut shell mixtures (M/
the n value was not assumed however, its accuracy was lower as
MA/PS). compared to KAS.
Pure M Ti Tf Tmax dW/dt Residue


max Ea Ea
lnb ¼ ln A  5:331  1:052 (9)
HR10 414.43 815.54 520.15 2.20 46.28 RgðaÞ RTa
HR20 411.09 838.00 520.30 4.34 41.95
HR30 418.21 824.35 520.02 6.39 43.03 By considering the gradient of the linear plot  1:052 ERa , Ea was
HR50 436.96 869.97 537.42 10.23 43.77
HR100 457.19 913.20 522.05 21.11 43.89
calculated, and by taking the y-intercept, the A was obtained and
compared with the kinetic values acquired from the other iso-
Pure MA conversional methods, which are FR and KAS so that the most
suitable kinetic model can be determined.
HR10 406.45 874.15 505.39 2.59 35.50
HR20 411.43 894.80 523.87 5.19 41.51
HR30 415.91 892.70 521.96 7.65 41.75 2.4.3. Thermodynamic analysis
HR50 412.07 904.36 534.56 12.77 39.34
The thermodynamic parameters of the selected kinetic model
HR100 410.27 834.79 548.63 24.71 46.70
(FWO) which include the Enthalpy (DH, kJ/mol), Gibbs free energy
Pure PS (DG, kJ/mol) and Entropy (DS, kJ/mol K) values of each input under
HR10 438.01 899.32 731.28 12.56 19.98 different heating rates were then calculated through Eqs (10)e(12),
HR20 430.72 966.83 743.97 16.37 19.26 which were derived from Eyring equation [43]. The kinetic pa-
HR30 436.57 882.51 594.65 18.09 25.23
HR50 441.36 1008.04 603.83 28.14 22.24
rameters obtained through kinetic models above were substituted
HR100 448.64 1054.43 612.55 60.79 19.68 into the respective equations to obtain the thermodynamic
parameters.
M/MA
HR10 421.76 731.25 520.52 2.77 50.61 DH ¼ Ea  RT (10)
HR20 427.80 781.76 603.16 6.34 46.36
HR30 447.47 787.71 535.67 7.90 48.67

HR50 441.84 801.61 543.76 12.98 49.10 KB Tm
HR100 424.32 825.37 590.36 25.27 48.22
DG ¼ Ea þ R,Tm ln (11)
hA
M/MA/PS
DH  DG
HR10 416.09 914.01 575.32 3.60 30.12 DS ¼ (12)
HR20 441.43 931.45 589.84 7.30 31.66
Tm
HR30 436.40 962.08 598.90 12.56 28.52
HR50 430.20 943.15 606.17 16.69 36.42
HR100 451.56 997.74 611.45 38.32 34.02
3. Experimental results and discussion

[40]. 3.1. TGA results on thermal degradation behaviour of pure samples



da da Ea Five sets of samples (Pure M, Pure MA, Pure PS, M/MA and M/
ln b ¼ ln ¼ ln½A , gðaÞ  (7) MA/PS) at five different heating rates (HR10, HR20, HR30, HR50 and
dT dT RTa

 HR100) were conducted to observe the trend of the sample’s
A graph of ln b ddTa vs 1
T was plotted so that the Ea can be ob- thermal degradation behaviour. The derivative thermogravimetric
(DTG) analysis measures the change of weight with respect to the
Ea
tained from the gradient,  R,
and the A was obtained from the y- change of temperature during heating where the transformation
intercept, ln½A ,gðaÞ, assuming n ¼ 1. trend of the sample’s degradation can be observed. On the other
hand, the peaks on DTG curves show the maximum rate of weight
2.4.2.2. Kissinger-Akahira-Sunose (KAS). As an integral iso- loss at the respective times. Fig. 2 shows the DTG plot of pyrolysis
conversional method, KAS method are less sensitive to noise and samples obtained from TGA.
have a lower possibility of errors. The equation that was used to It can be observed that there were three obvious phases of Pure
!
 M thermal decomposition through pyrolysis process. In the first
b
plot the ln T 2 vs T1a graph was stated in Eq. (8) below, where stage, the removal of moisture occurred within the range of
a
300e440 K where the peak temperatures during dehydration
the maximum reaction rate temperature was denoted as Ta [41]. increased with the increase of heating rates from HR10 to HR100.
! The second stage ranging from 440 to 880 K indicated the main
b AR Ea decomposition of microalgae structures which includes the pro-
ln ¼ ln ¼ (8)
Ta2 Ea gðaÞ RTa teins, carbohydrates and lipids, resulting in a maximum weight loss


 and the production of main pyrolysis products. The first section in
From the gradient ERa and y-intercept ln EaAR the second stage indicated the decomposition of proteins and car-
gðaÞ , the kinetic
bohydrates. Carbohydrates decomposed later at 560e730 K as
parameters, Ea and A were calculated respectively. compared to proteins (440e560 K) due to its higher crystalline
structure stability. Another small division that covered the last
2.5. Flynn-Wall-Ozawa (FWO) range in stage two is attributed to the lignin decomposition, within
730e880 K, due to its lower volatilization rate as compared to
FWO method expressed in Eq. (9) was also under the integral proteins and carbohydrates [44]. Finally, the decomposition of tars,
category of iso-conversional approaches which had similar char gases and ash matters happened in the last stage of pyrolysis at
10 J.T. Bong et al. / Energy 207 (2020) 118289

Table 6
Comparison between tansig-tansig (TT) and losgis-tansig (LT) predicted R2 values obtained from different kinetic models: Friedman (FR), Kissinger-Akahira-Sunose (KAS), and
Flynn-Wall-Ozawa (FWO).

Kinetic Model FR KAS FWO

Source a TT LT TT LT TT LT

Pure M 0.1 0.9973 0.9967 0.9977 0.9969 0.9981 0.9973

0.2 0.9915 0.9955 0.9910 0.9952 0.9919 0.9957
0.3 0.9830 0.9910 0.9820 0.9905 0.9840 0.9915
0.4 0.9629 0.9799 0.9603 0.9786 0.9652 0.9811
0.5 0.9543 0.9507 0.9511 0.9470 0.9572 0.9540
0.6 0.9536 0.9122 0.9503 0.9055 0.9565 0.9182
0.7 0.9336 0.9202 0.9288 0.9142 0.9380 0.9257
0.8 0.9590 0.9529 0.9564 0.9497 0.9613 0.9557
0.9 0.9406 0.9544 0.9373 0.9519 0.9436 0.9567
Average 0.9640 0.9615 0.9617 0.9588 0.9662 0.9640
Pure MA 0.1 0.8157 0.8125 0.8104 0.8070 0.8279 0.8249
0.2 0.2933 0.9637 0.2822 0.9618 0.3045 0.9656
0.3 0.4907 0.9041 0.4819 0.8985 0.4994 0.9093
0.4 0.2635 0.8850 0.2542 0.8774 0.2728 0.8920
0.5 0.2877 0.8551 0.2780 0.8467 0.2973 0.8628
0.6 0.2784 0.3241 0.2686 0.3004 0.2882 0.3473
0.7 0.4966 0.9475 0.5075 0.9425 0.4854 0.9519
0.8 0.7800 0.9675 0.7889 0.9642 0.7705 0.9703
0.9 0.4109 0.9765 0.4481 0.9747 0.3716 0.9781
Average 0.4574 0.8485 0.4578 0.8415 0.4575 0.8558
Pure PS 0.1 0.9921 0.9748 0.9930 0.9748 0.9938 0.9780
0.2 0.9945 0.9898 0.9940 0.9890 0.9949 0.9904
0.3 0.9954 0.9903 0.9951 0.9895 0.9957 0.9909
0.4 0.9925 0.9903 0.9921 0.9897 0.9930 0.9909
0.5 0.9872 0.9811 0.9865 0.9801 0.9879 0.9821
0.6 0.6086 0.5908 0.5851 0.5667 0.6305 0.6134
0.7 0.9013 0.9461 0.8962 0.9434 0.9060 0.9487
0.8 0.9963 0.9924 0.9959 0.9916 0.9966 0.9930
0.9 0.9771 0.9764 0.9732 0.9723 0.9803 0.9796
Average 0.9383 0.9369 0.9346 0.9330 0.9421 0.9408
M/MA 0.1 0.9950 0.9930 0.9960 0.9940 0.9965 0.9947
0.2 0.9903 0.9888 0.9896 0.9880 0.9909 0.9895
0.3 0.9838 0.9859 0.9826 0.9849 0.9848 0.9868
0.4 0.9897 0.9867 0.9890 0.9857 0.9904 0.9875
0.5 0.9896 0.9953 0.9889 0.9950 0.9902 0.9955
0.6 0.9935 0.9974 0.9930 0.9972 0.9939 0.9975
0.7 0.9837 0.9871 0.9824 0.9861 0.9848 0.9879
0.8 0.9399 0.9490 0.9346 0.9453 0.9445 0.9523
0.9 0.9469 0.9596 0.9425 0.9568 0.9508 0.9622
Average 0.9791 0.9825 0.9776 0.9814 0.9808 0.9838
M/MA/PS 0.1 0.8270 0.8633 0.8209 0.8582 0.8433 0.8767
0.2 0.8604 0.8787 0.8512 0.8703 0.8689 0.8863
0.3 0.8869 0.8971 0.8800 0.8907 0.8932 0.9030
0.4 0.9309 0.9399 0.9268 0.9362 0.9347 0.9433
0.5 0.9000 0.9271 0.8949 0.9233 0.9047 0.9307
0.6 0.4409 0.5557 0.4257 0.5419 0.4558 0.5691
0.7 0.0565 0.0954 0.0451 0.0815 0.0689 0.1101
0.8 0.6467 0.7148 0.6346 0.7048 0.6583 0.7243
0.9 0.6836 0.7456 0.6655 0.7306 0.7004 0.7596
Average 0.6925 0.7353 0.6827 0.7264 0.7031 0.7448
Overall Average 0.8063 0.8929 0.8029 0.8882 0.8099 0.8978

high temperatures beyond 880 K. On the other hand, the DTG
curves for Pure MA resulted in a similar trend to Pure M pyrolysis.
The stage 1 decomposition occurred from 300 to 420 K, stage 2
from 420 to 870 K and stage 3 from 870 to 1200 K. However, there
was a peak in the lipid decomposition section that was lower in
Pure MA as compared to Pure M around 650e700 K, indicating the
decomposition of the leftover lipids that were not completely
extracted during the extraction of Pure M to produce MA.
Three stages were also observed in the DTG curve of Pure PS at
different heating rates. Stage 1 occurred at 300e450 K, represent-
ing the dehydration process. The second stage of Pure PS thermal
degradation (450e1020 K) revolved around its main chemical
components which are hemicellulose, cellulose and lignin. Gener-
ally, the peaks for derivative weight loss of Pure PS at all heating
rates are higher than Pure M and Pure MA, indicating a higher
devolatilization rate during the pyrolytic cracking of Pure PS. The
first two obvious peaks from 450 to 900 K showed the degradation
of hemicellulose and cellulose [45], whereas the lignin degraded at
900e1020 K with a small derivative weight loss percentage as it
was harder to degrade due to its heterogeneity [46]. Lastly, the
small peak from 1100 to 1200 K indicated the volatiles’ decompo-
sition such as tars, char and ashes. According to Soon et al. [47]; the
breakdown of the individual components of biomass which con-
sists of hemicellulose, cellulose, and lignin occurred at different
temperature. This is attributed to the different structures and ar-
rangements exist in these individual components found in biomass
[48]. It is observed that lignin degrades at a higher temperature
compared to hemicellulose and cellulose. This further justified that
 J.T. Bong et al. / Energy 207 (2020) 118289
Fig. 6. Arrhenius plots for pure microalgae (Pure M) with experimental, tansig-tansig (TT) and logsig-tansig (LT) predicted data at different kinetic models (a) Friedman (FR), (b)
Kissinger-Akahira-Sunose (KAS), and (c) Flynn-Wall-Ozawa (FWO.
lignin possess a higher stability compared to the other two indi-
vidual components in biomass [49]. [50] also emphasized that the
degree of difficulty for thermal degradation to occur increases from
hemicellulose, cellulose, to lignin. This has been evidently shown in
our present findings in PS.
3.2. Artificial Neural Network (ANN) model development and
optimization
In the present work, the number of neurons and transfer func-
tions were used to observe the ANN performance. Firstly, ANN was
designed with one hidden layer to ensure the simplicity of the
network, but the MSE could not converge to a minimal value. This
was due to the complex decomposition stages of the M, MA and PS
biomasses used. Literature suggested that the best architecture for
biomass pyrolysis or co-pyrolysis usually involves more than one
hidden layer [32,51,52]. Thus, the network designed was modified
to contain two hidden layers to observe the MSE values. Then
neuron numbers were varied from 2 to 12 to discover its effect on
11
the MSE, where the value was started from 2 due to the complexity
that led to non-convergence, and the network was trained for 20
times to obtain the average MSE. The increase in neuron numbers
stopped at 12 as a long network training time was observed due to
the computational complexity. Fig. 3 shows the average MSE trend
with the increase of neuron numbers for the Pure M outputs with
two different transfer functions which are TT and LT. Four different
combinations of transfer functions such as tansig-tansig (TT), tan-
sig-logsig (TL), logsig-logsig (LL) and logsig-tansig (LT) were tested
out to obtain the average MSE. However, TL and LL combinations
were omitted as the average MSE values obtained were more than
300 and did not show signs of convergence after 20 trainings. It was
observed in Fig. 3 that for TT, the lowest average MSE (2.36  103)
was achieved at 9 neuron numbers whereas for LT, a value of 4.98 
103 was achieved at 11 neuron numbers. The average MSEs then
increased and were ignored after reaching the minimum value. This
was due to overfitting and overtraining issues where the pattern
memorizing and generalization ability of ANN deteriorated at
higher neuron numbers [53]. The minimum average MSE values
12 J.T. Bong et al. / Energy 207 (2020) 118289

Table 7
Comparison between experimental and logsig-tansig (LT) predicted activation energies, Ea from different kinetic models: Friedman (FR), Kissinger-Akahira-Sunose (KAS), and
Flynn-Wall-Ozawa (FWO).

Kinetic Model FR KAS FWO

Parameters a Ea (kJ/mol) % Error Ea (kJ/mol) % Error Ea (kJ/mol) % Error of Ea

Source EXP LT EXP LT EXP LT

Pure M 0.1 140.82 124.45 11.628 135.15 118.72 12.158 136.24 120.59 11.486
0.2 146.46 150.25 2.519 142.16 145.94 2.590 143.31 146.91 2.452
0.3 138.76 151.57 8.452 134.26 147.05 8.702 136.18 148.37 8.218
0.4 130.31 136.19 4.320 125.58 131.45 4.468 128.36 133.96 4.182
0.5 136.78 125.81 8.023 131.80 120.84 8.312 134.76 124.31 7.754
0.6 139.86 126.18 9.781 134.64 120.98 10.144 137.92 124.89 9.445
0.7 140.89 134.25 4.716 135.41 128.77 4.901 139.15 132.82 4.545
0.8 181.54 166.47 8.302 175.70 160.65 8.562 178.11 163.76 8.057
0.9 230.32 232.61 0.984 224.05 226.34 1.012 224.89 227.07 0.958
Average 153.97 149.75 2.740 148.75 144.53 2.837 150.99 146.97 2.666

Pure PS 0.1 146.88 144.71 1.481 141.14 138.95 1.553 142.90 140.81 1.462
0.2 150.46 146.77 2.456 145.67 141.98 2.533 147.58 144.06 2.383
0.3 145.33 143.23 1.442 140.40 138.31 1.492 142.82 140.83 1.395
0.4 159.41 159.01 0.250 154.37 153.98 0.257 156.31 155.93 0.243
0.5 196.79 184.73 6.129 191.63 179.56 6.298 191.97 180.51 5.969
0.6 130.28 115.20 11.579 124.72 109.65 12.088 129.13 114.78 11.112
0.7 229.13 229.13 0.000 223.04 223.04 0.000 223.58 223.58 0.000
0.8 158.45 144.19 9.000 152.07 137.82 9.369 156.68 143.11 8.659
0.9 92.72 96.37 3.789 86.14 89.76 4.037 94.38 97.88 3.573
Average 156.60 151.48 3.272 151.02 145.89 3.395 153.93 149.06 3.166

M/MA 0.1 155.65 146.79 5.690 149.65 141.25 5.608 150.18 142.25 5.282
0.2 139.47 138.92 0.391 135.09 134.53 0.417 136.73 136.23 0.367
0.3 139.03 140.21 0.839 134.50 135.65 0.851 136.47 137.61 0.827
0.4 139.80 142.59 1.953 135.09 137.85 2.001 137.37 140.04 1.909
0.5 137.51 149.95 8.296 132.62 145.02 8.552 135.37 147.23 8.055
0.6 131.57 148.15 11.192 126.48 143.03 11.572 129.90 145.69 10.836
0.7 127.29 145.79 12.694 122.01 140.48 13.147 126.01 143.64 12.273
0.8 111.30 150.87 26.227 105.75 145.24 27.191 111.08 148.77 25.332
0.9 120.97 169.63 28.685 114.99 163.56 29.693 120.67 167.01 27.747
Average 133.62 148.10 9.777 128.46 142.96 10.138 131.53 145.39 9.529

were tabulated in Table 4 and it can be seen that TT transfer
function achieved a minimum value at lower neuron numbers as
compared to LT. Further comparison studies on the values of kinetic
and thermodynamic parameters obtained from experimental, TT
and LT were conducted later to conclude the most suitable transfer
function for the neural network applied in this study.
Fig. 4 shows the plots such as performance validation, error
histogram and regressions obtained from neural network training
for Pure M at HR10. Fig. 4a displays the validation of network
performance plot during the training, validation and testing stage.
The plot reflected that a total of 243 iterations were carried out and
the minimum MSE (2.36  103) was achieved at the 237th
iteration. Despite the fact that the MSE acquired was small, the
error distribution and regressions during the optimization of
network were included in Fig. 4b and c to further analyse the
network’s accuracy. A normal distribution with errors close to zero
was achieved in the error histogram with the value ranging
from 0.1296 to 0.1193, which was within the acceptable range of
±1 [51]. Besides, the R2 values achieved during the training, vali-
dation and testing stages were close to 1. These observations
proved that the ANN data forecasted were close to the experi-
mental TGA results. Thus, it can be applied in the prediction studies
of complex biomass pyrolysis processes such as pyrolysis of
microalgae or food wastes.

Table 8
Experimental and logsig-tansig (LT) predicted kinetics and thermodynamic parameters for microalgae, microalgae ash and peanut shell mixtures (M/MA/PS) using Flynn-Wall-
Ozawa (FWO) model.

Kinetic Model FWO

Source EXP LT % Error of Ea

Parameters a Ea (kJ/mol) A (1/s) DH (kJ/mol) DG (kJ/mol) DS (kJ/mol K) Ea (kJ/mol) A (1/s) DH (kJ/mol) DG (kJ/mol) DS (kJ/mol K)
M/MA/PS 0.1 111.30 3.56  1010 106.79 140.34 56.26 105.65 8.65  109 101.13 141.69 68.01 5.08
0.2 120.91 1.46  1011 116.14 142.94 44.95 120.33 1.14  1011 115.56 143.60 47.01 0.48
0.3 144.19 8.59  1012 139.21 146.02 11.42 141.35 4.44  1012 136.37 146.45 16.90 1.97
0.4 151.98 1.76  1013 146.83 150.27 5.78 156.94 5.10  1013 151.78 149.95 3.08 3.16
0.5 111.51 2.92  1011 106.22 130.10 40.05 105.85 7.11  1010 100.56 131.45 51.80 5.07
0.6 131.30 7.07  1011 125.78 145.51 33.10 130.72 5.51  1011 125.20 146.17 35.17 0.44
0.7 163.71 1.67  1012 157.61 173.67 26.92 73.82 3.94  105 67.72 159.44 153.80 54.91
0.8 166.08 1.24  1011 159.43 188.94 49.48 171.04 3.60  1011 164.39 188.60 40.60 2.90
0.9 182.09 1.04  1012 174.96 194.41 32.61 176.66 4.95  1011 169.52 192.65 38.77 2.98
Average 142.56 3.35  1012 137.00 - - 131.37 6.33  1012 125.81 - - 7.85
 J.T. Bong et al. / Energy 207 (2020) 118289 13

Table 9
Comparative studies on the experimental predicted activation energy in the present study with literature.

Source Kinetic analysis

Kinetic method Average Ea (kJ/mol) References

Pure microalgae chlorella vulgaris (Pure M) FR 153.97 Present study

KAS 148.75
FWO 150.99
FWO 158.10 [56]
KAS 156.10
Starink’s 156.44
Vyazovkin 156.44
Pure peanut shell wastes (Pure PS) FR 156.60 Present study
KAS 151.02
FWO 153.93
FWO 32.01 [57]
DAEM 46.15
Microalgae chlorella vulgaris þ microalgae chlorella vulgaris ash mixtures (M/MA) FR 133.62 Present study
KAS 128.46
FWO 131.53
Microalgae chlorella vulgaris þ zeolite catalyst mixtures FWO 147.84 [56]
KAS 145.26
Starink’s 145.55
Vyazovkin 145.59
Microalgae chlorella vulgaris þ limestone catalyst mixtures KAS 138.81 [56]
FWO 142.06
Starink’s 139.12
Vyazovkin 139.33

Table 10
Gaseous composition yield for pure microalgae (Pure M), pure peanut shell wastes (Pure PS), microalgae and microalgae ash mixtures (M/MA), and microalgae, microalgae ash
and peanut shell mixtures (M/MA/PS).

Source Gaseous composition (wt%)

H2 CO CO2 CH4

Pure microalgae chlorella vulgaris (Pure M) 21.3 12.7 27.4 38.6

Pure peanut shell wastes (Pure PS) 17.1 24.5 21.4 37.0
Microalgae chlorella vulgaris and microalgae chlorella vulgaris ash mixtures (M/MA) 22.8 22.4 27.2 27.6
Microalgae chlorella vulgaris þ Microalgae chlorella vulgaris ash þ Peanut shell mixtures (M/MA/PS) 19.9 28.5 24.3 27.3

3.3. Comparison between the experimental and ANN predicted
weight loss
TG curve measures the weight loss of feedstock as a function of
temperature. The TG curves that compare the experimental data
with TT and LT transfer functions at each heating rate for all sam-
ples can be seen in Fig. 5. Generally, the predicted weight loss (wt %)
by both TT and LT transfer functions from ANN model agreed
closely to the experimental data generated from the TGA. The three
stages of decomposition mentioned in Section 3.1 were observed in
the TG curves generated where each steep line represented a
decomposition phase. Fig. 5a of the experimental, TT and LT for Pure
M TG curves showed that at 300e410 K, dehydration occurred at a
higher rate and the reaction rate slowed down from 410 to 440 K.
Then, the rate of degradation accelerated from 440 to 800 K during
the second stage where the organic structures such as hemicellu-
lose and cellulose degraded, followed by a slower degradation rate
of lignin at the temperature range of 800e880 K. The decomposi-
tion of other matters such as tar, char and ash then occurred at a
lower rate from 880 K up to 1200 K. The breakdown of curves
worked the same for the other samples with a different tempera-
ture range for each decomposition stage. The graphs were labelled
with different thermal degradation stages in Fig. 5 according to the
observation in the DTG curves. The closely overlapped data be-
tween experimental and ANN predicted results had strongly vali-
dated the accuracy of ANN prediction in conjunction with the low
MSE values achieved during the network optimization.
3.3.1. Effect of different heating rates
The TG curves for all set of samples (experimental, TT and LT) at
HR10, HR20, HR30, HR50 and HR100 displayed in Fig. 5 showed
that the increase in heating rates have resulted in an upward shift of
TG curves, causing an increase in the peak derivative weight losses
from 2.20 wt %/min to 21.11 wt %/min in the main degradation stage
of Pure M samples (Stage 2) as tabulated in Table 5. This is because
the increase in thermal energy had resulted in a higher energy
transfer rate from the samples to the atmosphere and thus, causing
an increase in the overall and stage 2 wt losses [4]. The increase in
heating rates also ensured the supply of adequate heat of reaction
to enhance the rate of decomposition of biomass samples to ach-
ieve the desired yield. On the other hand, a rightward shift of the
temperatures at maximum derivative weight loss was observed on
the DTG curves in Fig. 2 along with the increased initial and final
temperature of stage 2 from HR10 to HR100. This showed that the
higher the heating rate, the longer the reaction time required to
achieve the minimum cracking heat of biomass components.
3.3.2. Effect of MA as a catalyst
The pyrolysis of mixtures (M/MA and M/MA/PS) were con-
ducted in the TGA to observe the change in thermal degradation
14 J.T. Bong et al. / Energy 207 (2020) 118289
properties upon the addition of MA as a catalyst. Research proved
that the use of catalyst in the pyrolysis process can affect the con-
tent of products based on the amount of contact between the
catalyst surface and pyrolysis products [54]. In this study, there is
not much dissimilarity between the decomposition temperature
ranges at the three stages for pyrolysis of M/MA as shown in Fig. 2d,
where the range of temperatures for stage 1, stage 2 and stage 3 are
300e430 K, 430e805 K and 805e1200 K respectively. On the other
hand, the addition of MA to M and PS mixtures (Fig. 2e) lowered
down the overall derivative weight losses and the degradation
peaks, with the stage 1 ranging from 300 to 450 K, stage 2 from 450
to 950 K and stage 3 beyond 950 K.
The values for maximum derivative weight loss also increased
for both M/MA and M/MA/PS with the addition of MA as a catalyst
as seen in Table 6. Taking HR10 as an example, the maximum peak
of derivative weight loss for Pure M and Pure PS were initially
2.20 wt %/min and 12.56 wt %/min respectively. With MA as the
catalyst, the maximum peak of derivative weight loss for M/MA/PS
had decreased from 12.56 wt %/min to 3.60 wt %/min. Furthermore,
the residues of Pure M and M/MA at HR10 changed from 46.28% to
50.61% whereas for Pure PS and M/MA/PS, the values changed from
19.98% to 30.12%. The percentage of leftover residue for pure
samples increased when MA was mixed as a catalyst, demon-
strating decreasing weight losses in catalytic pyrolysis. A similar
trend was obtained in our previous study [45], where the addition
of catalysts such as HZSM-5 zeolite, limestone and bifunctional
HZSM-5/LS decreased the maximum derivative weight losses and
decreased the mass losses of microalgae pyrolysis. This showed that
MA is suitable to be used as a catalyst for the pyrolysis of biomass to
produce syngas with a lower maximum degradation rate.
3.4. Kinetic and thermodynamic analysis
Iso-conversional kinetic models such as FR, KAS and FWO were
used to study the kinetic properties of non-catalytic and catalytic
pyrolysis of M, MA and PS combinations, assuming that the
degradation of biomass components occurred as first order reac-
tion, where n ¼ 1. The Arrhenius plots of the three models were
plotted for experimental, TT and LT values at conversions (a) from
0.1 to 0.9 with an interval of 0.1 as shown in Fig. 6 to observe the
values obtained from the line of best fit at each conversion. The
Arrhenius plots displayed similar patterns where negative gradi-
ents were obtained. The slope and y-intercept acquired from the
fitting line were then used for the calculation of kinetic parameters
and the R2 values were used to determine the accuracy of the ki-
netic data calculated. Table 7 records the R2 values generated by the
Arrhenius plots of each set of TT and LT samples. The overall average
R2 values for FR-TT, FR-LT, KAS-TT, KAS-LT, FWO-TT and FWO-LT are
0.8063, 0.8929, 0.8029, 0.8882, 0.8099 and 0.8978 respectively.
These values from all three models have concluded that the R2
values from LT are higher than the ones from TT, indicating that the
LT prediction from ANN is more accurate and closer to the fitted
regression line. Therefore, from this point onwards, LT data were
used for the kinetic and thermodynamic parameters’ calculation to
be compared with the experimental results.
The Ea values can be calculated by substituting the gradient from
the Arrhenius plot at each conversion into the relevant formula for
the specific kinetic model which include FR, KAS and FWO. The Ea
values determined from experimental and LT predicted data were
tabulated in Table 8 along with the percentage error (%) as a
comparison to discover the kinetic model with the best results in
this study. The Ea obtained from the three kinetic models for Pure
M, Pure PS and M/MA mixture ranged from 144.53 to 153.97 kJ/mol,
145.89e156.60 kJ/mol and 128.46e148.10 kJ/mol respectively. The
values for Pure M can be supported by relevant literature findings
where the range Ea values obtained from kinetic models such as FR,
FWO and Starink are 106.14 kJ/mol e 263.87 kJ/mol,
143.88e214.13 kJ/mol and 140.93e214.13 kJ/mol respectively [55].
A report produced by Cai and Ji, (2007) also stated that the Ea for
Pure PS is in the range of 150.00 kJ/mol to 183.30 kJ/mol, indicating
that the results obtained from this study are in a similar range.
Besides, a decrease in Ea was achieved when MA was added as a
catalyst to Pure M, verifying the catalytic activity in the reaction.
Finally, FWO was identified as the most suitable kinetic model for
the current study as it had the lowest % error for experimental and
LT Ea calculations as compared to FR and KAS. Thus, it was used to
further conduct the kinetic and thermodynamic analysis for the M/
MA/PS mixtures.
Table 8 contains the kinetic and thermodynamic parameters
calculated with FWO model using M/MA/PS’s experimental and LT
data. The average experimental activation energy, Ea obtained was
142.56 kJ/mol whereas the LT predicted Ea was 131.31 kJ/mol, with a
percentage error of 7.85%. The average A values for the experi-
mental and LT prediction were 3.35  1012 s1 and 6.33  1012 s1
respectively. On the other hand, thermodynamic parameters were
obtained by using the kinetic parameters for further calculations.
As the overall average enthalpy, DH computed were positive values
for both experimental and LT (137.00 kJ/mol and 125.81 kJ/mol), the
reaction was proved to be endothermic. Besides, the difference
between Ea and DH for both sets of data were less than 6 kJ/mol,
indicating a low potential barrier between the biomass molecules
that eased the forming of activated complex [56]. The Gibb’s free
energy, DG values obtained at each conversion obtained were all
positive in the range of 140.34e194.41 kJ/mol, and showed an
increasing trend, indicating that the energy of the system increased
with the conversion increment. Lastly, the entropy, DS that mea-
sures the amount of energy unavailable to work were mostly
negative, ranging from 153.80 kJ/mol K to 3.08 kJ/mol K reflected
the low dispersal in the biomass mixtures’ structure. The DS
calculated were found similar to the results obtained by Gouda and
Panda, (2019), where the values are negative, indicating a high
degree of arrangement in the microalgae and Kaner seed struc-
tures. The higher the entropy values, the higher the reaction rate
and the shorter the reaction time to produce the activated complex.
The values obtained from FWO model were found to have the least
error among the three kinetic models. The Ea for experimental and
LT forecasted Pure M and Pure PS were reduced upon the addition
of MA as a catalyst. The Ea values for experimental Pure M and Pure
PS (150.99 kJ/mol and 153.93 kJ/mol) decreased to 142.56 kJ/mol
whereas for LT (146.97 kJ/mol and 149.06), the Ea value were
reduced to 131.37 kJ/mol for catalytic co-pyrolysis. This further
validates the suitability of MA as a catalyst for co-pyrolysis of
biomass mixtures such as microalgae and PS.
Table 9 shows the comparative study on the present findings of
the average Ea with literature. It can be observed that the present
findings for the average Ea Pure M is comparable with the results
obtained from Fong et al. [56] regardless of the kinetic models used.
This could be attributed that the same microalgae chlorella vulgaris
species and similar heating rates are used in both studies. However,
the values of the average Ea for Pure PS are seen to differ when
compared to the findings from Xu et al. [57]. This could be due to
the different physicochemical properties of the PS used and oper-
ating conditions of the TGA when the experiments are conducted.
With the presence of catalyst in the Pure M, it is observed that the
present findings displayed a lower average Ea (128.46e133.62 kJ/
mol) compared to the microalgae chlorella vulgaris and zeolite
catalyst mixtures (145.26e147.84 kJ/mol) and microalgae chlorella
vulgaris and limestone catalyst mixtures (138.81e142.06 kJ/mol)
found in Fong et al. (2019) studies. This indicates that the catalytic
effect of MA in Pure M is much more effective compared to the
 J.T. Bong et al. / Energy 207 (2020) 118289
zeolite catalyst and limestone catalyst. It is said that the best cat-
alytic effect in the reaction can be demonstrated when the mini-
mum energy requirement exists (Xu et al., 2017).
3.5. Gaseous characteristic of co-pyrolysis of MA and PS mixture
Table 10 shows the gaseous composition that obtained from
non-catalytic pyrolysis (e.g. Pure M, Pure PS) and catalytic pyrolysis
(e.g. M/MA, M/MA/PS). From Table 9, it can be clearly seen that the
syngas composition (H2þCO) increased 14.4 wt% and 6.8 wt% as
compared to Pure M and Pure PS respectively after the addition of
MA as catalyst. The increase of syngas composition was potentially
related to chemical reactions and tar mechanisms as shown below
(R1)-(R8):
Pyrolysis: CX Hy OZ / H2 þ CO þ CO2 þ CH4 þ C2 þ Tar þ charR1.
Pyrolysis of hydrocarbon: Cx Hy /2yH2 þ xCharR2.
Tar dry reforming reactions: CX Hy þ xCO2 /2xCO þ Y2 H2 R3
Steam reforming of methane: CH4 þ H2 0 4CO þ 3H2 R4.
Methane decomposition: CH4 /C þ 2H2 R5.
Dehydrogenation: Cn H2nþ2 /Cn H2n þ H2 R6.
Methanation: CH4 þ H2 O 4CO þ 3H2 R7.
Water gas reaction (WG): C þ H2 O 4CO þ H2 R8.
As reported by Liu et al. [58]; the inorganic components in MA
such as SiO2, CaO and Fe2O3 can act as a pyrolytic catalyst in
enhancing the yield and quality of gaseous products [58]. For
instance, the high amorphous SiO2 could increase the active sites
for pyrolysis reaction whereas the char can act as an intermediate
reductant to reduce the metal oxides into metallic states which
enhance the active sites for cracking and heterogeneous reactions
to occur during pyrolysis. In addition, the CH4 composition has
reduced significantly after the addition of MA as a catalyst, sug-
gesting that methanation reaction has taken place which enhances
the syngas production. Similar observation was observed in previ-
ous study in which the addition of catalyst such as Ni, Al2O3, CaO
and Fe2O3 could enhance methane reaction and water gas reaction
[59e61].
4. Conclusion
There were three stages of thermal decomposition for the
biomass samples studied. Even though TT and LT transfer functions
produced similar results to the experimental TG curves, the R2
values showed that LT fitted best to the regression line. The
experimental and LT data were then used to determine the kinetic
and thermodynamics data. The catalytic co-pyrolysis of M/MA/PS
reduced the Ea to 142.56 kJ/mol for experimental results and
131.37 kJ/mol for LT generated data with a DH of 137.00 kJ/mol and
125.81 kJ/mol respectively. The Ea finding is also in good agreement
with the syngas composition of M/MA/PS, where the syngas
composition has increased 14.4 wt% and 6.8 wt% as compared to
Pure M and Pure PS respectively. For future works, studies related to
bench-scale pyrolyzer should be conducted using MA as a catalyst
to provide more insights on the economic feasibility of the pro-
posed system.
CRediT authorship contribution statement
Jang Tyng Bong: Conceptualization, Formal analysis, Investi-
gation, Writing - original draft. Adrian Chun Minh Loy: Writing -
review & editing, Software. Bridgid Lai Fui Chin: Supervision,
Validation. Man Kee Lam: Resources. Daniel Kuok Ho Tang:
Methodology. Huei Yeong Lim: Data curation. Yee Ho Chai: Visu-
alization. Suzana Yusup: Project administration.
15
Declaration of competing interest
None.
Acknowledgments
This work is carried out under the financial support of Funda-
mental Research Grant Scheme (MOHE Ref. No: FRGS/1/2016/TK05/
CURTIN/03/1) under cost center number of 001064. The authors
also would like to thank Curtin University Malaysia and Centre of
Biofuel and Biochemical (CBBR) of Universiti Teknologi PETRONAS
(UTP) for the technical support. Furthermore, support from Min-
istry of High Education Malaysia through HICOE award to CBBR is
duly acknowledged.
References
[1] Ediger VŞ. An integrated review and analysis of multi-energy transition from
fossil fuels to renewables. Energy Procedia 2019;156:2e6. https://doi.org/
10.1016/j.egypro.2018.11.073.
[2] Chin BLF, Gorin A, Chua HB, Twaiq F. Experimental investigation on tar pro-
duced from palm shells derived syngas using zeolite HZSM-5 catalyst. J Energy
Inst 2016;89:713e24. https://doi.org/10.1016/j.joei.2015.04.005.
[3] Vassilev SV, Vassileva CG, Vassilev VS. Advantages and disadvantages of
composition and properties of biomass in comparison with coal: an overview.
Fuel 2015;158:330e50. https://doi.org/10.1016/j.fuel.2015.05.050.
[4] Loy ACM, Yusup S, How BS, Yiin CL, Chin BLF, Muhammad M, Gwee YL. Un-
certainty estimation approach in catalytic fast pyrolysis of rice husk: thermal
degradation, kinetic and thermodynamic parameters study. Bioresour Technol
2019;294:122089. https://doi.org/10.1016/j.biortech.2019.122089.
[5] Khan Z, Yusup S, Ahmad MM, Chin BLF. Performance study of Ni catalyst with
quicklime (CaO) as CO2 adsorbent in palm kernel shell steam gasification for
hydrogen production. Adv Mater Res 2014;917:292e300. https://doi.org/
10.4028/www.scientific.net/AMR.917.292.
[6] Perea-Moreno MA, Manzano-Agugliaro F, Hernandez-Escobedo Q, Perea-
Moreno AJ. Peanut shell for energy: properties and its potential to respect the
environment. Sustain Times 2018;10(9):3254. https://doi.org/10.3390/
su10093254.
[7] AL-Othman ZA, Ali R, Nashad Mu. Hexavalent chromium removal from
aqueous medium by activated carbon prepared from peanut shell: adsorption
kinetics, equilibrium and thermodynamic studies. Chem Eng J 2012;184:
238e47. https://doi.org/10.1016/j.cej.2012.01.048.
[8] Ding J, Wang H, Li Z, Cui K, Karpuzov D, Tan X, Kohandehghan A, Mitlin D.
Peanut shell hybrid sodium ion capacitor with extreme energy-power rivals
lithium ion capacitors. Energy Environ Sci 2015;8(3):941e55. https://doi.org/
10.1039/C4EE02986K.
[9] Prabhakar MN, Shah AUR, Rao KC, Song JI. Mechanical and thermal properties
of epoxy composites reinforced with waste peanut shell powder as a bio-filler.
Fibers Polym 2015;16:1119e24. https://doi.org/10.1007/s12221-015-1119-1.
[10] Dubinsky Z, Aaronson S, Berner T. Some economic considerations in the mass
culture of microalgae. Algae Biomass : production and use. Amsterdam:
Elsevier/North-Holland Biomedical Press; 1980. p. 819e32.
[11] Hornung A, Apfelbacher A, Sagi S. Intermediate pyrolysis: a sustainable
biomass-to-energy concept-biothermal valorisation of biomass (BtVB) pro-
cess. J Sci Ind Res (India) 2011;70:664e7.
[12] Thangalazhy-Gopakumar S, Adhikari S, Chattanathan SA, Gupta RB. Catalytic
pyrolysis of green algae for hydrocarbon production using HþZSM-5 catalyst.
Bioresour Technol 2012;118:150e7. https://doi.org/10.1016/
j.biortech.2012.05.080.
[13] Kebelmann K, Hornung A, Karsten U, Griffiths G. Intermediate pyrolysis and
product identification by TGA and Py-GC/MS of green microalgae and their
extracted protein and lipid components. Biomass Bioenergy 2013;49:38e48.
https://doi.org/10.1016/j.biombioe.2012.12.006.
[14] Loy ACM, Gan DKW, Yusup S, Chin BLF, Lam MK, Shahbaz M, Unrean P,
Acda MN, Rianawati E. Thermogravimetric kinetic modelling of in-situ cata-
lytic pyrolytic conversion of rice husk to bioenergy using rice hull ash catalyst.
Bioresour Technol 2018a;261:213e22. https://doi.org/10.1016/
j.biortech.2018.04.020.
[15] Georgin J, Dotto GL, Mazutti MA, Foletto EL. Preparation of activated carbon
from peanut shell by conventional pyrolysis and microwave irradiation-
pyrolysis to remove organic dyes from aqueous solutions. J. Environ. Chem.
Eng. 2016;4(1):266e75. https://doi.org/10.1016/j.jece.2015.11.018.
[16] Gurevich MLI, Bonelli PR, Cukierman AL. In-situ catalytic pyrolysis of peanut
shells using modified natural zeolite. Fuel Process Technol 2017b;159:160e7.
https://doi.org/10.1016/j.fuproc.2017.01.032.
[17] Tripathi M, Sahu JN, Ganesan P. Effects of process parameters on production of
biochar from biomass waste through pyrolysis: a review. Renew Sustain En-
ergy Rev 2016;55:467e81. https://doi.org/10.1016/j.rser.2015.10.122.
[18] Pourkarimi S, Hallajisani A, Alizadehdakhel A, Nouralishahi A. Biofuel pro-
duction through micro- and marcoalgae pyrolysis - a review of pyrolysis
16 J.T. Bong et al. / Energy 207 (2020) 118289
methods and process parameters. J Anal Appl Pyrolysis 2019;142. https://
doi.org/10.1016/j.jaap.2019.04.015.
[19] Jahirul MI, Rasul MG, Chowdhury AA, Ashwath N. Biofuels production through
biomass pyrolysis - a technological review. Energies 2012;5:4952e5001.
https://doi.org/10.3390/en5124952.
[20] Saber M, Nakhshiniev B, Yoshikawa K. A review of production and upgrading
of algal bio-oil. Renew Sustain Energy Rev 2016;58:918e30. https://doi.org/
10.1016/j.rser.2015.12.342.
[21] Ng QH, Chin BLF, Yusup S, Loy ACM, Chong KYY. Modeling of the co-pyrolysis
of rubber residual and HDPE waste using the distributed activation energy
model (DAEM). Appl. Therm. Eng., 2018. Appl. Therm. Eng. 2018;138:336e45.
https://doi.org/10.1016/j.applthermaleng.2018.04.069.
[22] Gurevich Messina LI, Bonelli PR, Cukierman AL. Copyrolysis of peanut shells
and cassava starch mixtures: effect of the components proportion. J Anal Appl
Pyrolysis 2015;113:508e17. https://doi.org/10.1016/j.jaap.2015.03.017.
[23] Hua MY, Li BX. Co-pyrolysis characteristics of the sugarcane bagasse and
Enteromorpha prolifera. Energy Convers Manag 2016;120:238e46. https://
doi.org/10.1016/j.enconman.2016.04.072.
[24] Tang Z, Chen W, Chen Y, Yang H, Chen H. Co-pyrolysis of microalgae and
plastic: characteristics and interaction effects. Bioresour Technol 2019;274:
145e52. https://doi.org/10.1016/j.biortech.2018.11.083.
[25] Bridgwater AV, Meier D, Radlein D. Fast pyrolysis of biomass:: a handbook,
vol. 1; 2008. p. 30e188. https://doi.org/10.1016/S0146-6380(99)00120-5.
[26] Shen L, Min F, Liu L, Zhu J, Xue C, Cai C, Zhou W, Wang C. Application of
gaseous pyrolysis products of the waste cooking oil as coal flotation collector.
Fuel 2019;239:446e51. https://doi.org/10.1016/j.fuel.2018.11.056.
[27] Achkar R, El-Halabi M, Bassil E, Fakhro R, Khalil M. Voice identity finder using
the back propagation algorithm of an artificial neural network. Procedia
Comput. Sci. 2016;95:245e52. https://doi.org/10.1016/j.procs.2016.09.322.
[28] Shahbaz M, Taqvi SA, Minh Loy AC, Inayat A, Uddin F, Bokhari A, Naqvi SR.
Artificial neural network approach for the steam gasification of palm oil waste
using bottom ash and CaO. Renew Energy 2019;132:243e54. https://doi.org/
10.1016/j.renene.2018.07.142.
[29] Karaci A, Caglar A, Aydinli B, Pekol S. The pyrolysis process verification of
hydrogen rich gas (HerG) production by artificial neural network (ANN). Int J
Hydrogen Energy 2016;41:4570e8. https://doi.org/10.1016/
j.ijhydene.2016.01.094.
[30] Naqvi SR, Hameed Z, Tariq R, Taqvi SA, Ali I, Niazi MBK, Noor T, Hussain A,
Iqbal N, Shahbaz M. Synergistic effect on co-pyrolysis of rice husk and sewage
sludge by thermal behavior, kinetics, thermodynamic parameters and artifi-
cial neural network. Waste Manag 2019;85:131e40. https://doi.org/10.1016/
j.wasman.2018.12.031.
[31] Naqvi SR, Tariq R, Hameed Z, Ali I, Taqvi SA, Naqvi M, Niazi MBK, Noor T,
Farooq W. Pyrolysis of high-ash sewage sludge: thermo-kinetic study using
TGA and artificial neural networks. Fuel 2018;233:529e38. https://doi.org/
10.1016/j.fuel.2018.06.089.
[32] Sun Y, Liu L, Wang Q, Yang X, Tu X. Pyrolysis products from industrial waste
biomass based on a neural network model. J Anal Appl Pyrolysis 2016;120:
94e102. https://doi.org/10.1016/j.jaap.2016.04.013.
[33] Du R-L, Wu K, Xu D-A, Chao C-Y, Zhang L, Du X-D. A modified Arrhenius
equation to predict the reaction rate constant of Anyuan pulverized-coal
pyrolysis at different heating rates. Fuel Process Technol 2016;148:
295e301. https://doi.org/10.1016/j.fuproc.2016.03.011.
[34] Opfermann JR, Kaisersberger E, Flammersheim HJ. Model-free analysis of
thermoanalytical data-advantages and limitations. Thermochim Acta
2002;391:119e27. https://doi.org/10.1016/S0040-6031(02)00169-7.
[35] García R, Pizarro C, Lavín AG, Bueno JL. Biomass proximate analysis using
thermogravimetry. Bioresour Technol 2013;139:1e4. https://doi.org/10.1016/
j.biortech.2013.03.197.
[36] Loy ACM, Yusup S, Chin BLF, Gan DKW, Shahbaz M, Acda MN, Unrean P,
Rianawati E. Comparative study of in-situ catalytic pyrolysis of rice husk for
syngas production: kinetics modelling and product gas analysis. J Clean Prod
2018b;197(1):1231e43. https://doi.org/10.1016/j.jclepro.2018.06.245.
[37] Kriesel D. A brief introduction to neural networks. Proc Am Power Conf
1991;53:943e5.
[38] Chin BLF, Yusup S, Al Shoaibi A, Kannan P, Srinivasakannan C, Sulaiman SA.
Kinetic studies of co-pyrolysis of rubber seed shell with high density poly-
ethylene. Energy Conserv. Manag. 2014b;87:746e53. https://doi.org/10.1016/
j.enconman.2014.07.043.
[39] Brown ME, Phillpotts CAR. Non-isothermal kinetics. J Chem Educ 1978;55:
556. https://doi.org/10.1021/ed055p556.
[40] Friedman HL. Kinetics of thermal degradation of char-forming plastics from
thermogravimetry. Application to a phenolic plastic. J Polym Sci Polym Symp
1964;6:183e95.
[41] Akahira T, Sunose T. Joint convention of four electrical institutes. Res. Rep.
Chiba Inst. Technol. (Sci. Technol.) 1971;16:22e31.
[42] Flynn JH, Wall LA. A quick, direct method for the determination of activation
energy from thermogravimetric data. J Polym Sci B Polym Lett 1966;4:323e8.
https://doi.org/10.1002/pol.1966.110040504.
[43] Mallick D, Poddar MK, Mahanta P, Moholkar VS. Discernment of synergism in
pyrolysis of biomass blends using thermogravimetric analysis. Bioresour
Technol 2018;261:294e305. https://doi.org/10.1016/j.biortech.2018.04.011.
[44] Sanchez-Silva L, Lo
pez-Gonza
lez D, Villasen~ or J, Sa

nchez P, Valverde JL.
Thermogravimetricemass spectrometric analysis of lignocellulosic and ma-
rine biomass pyrolysis. Bioresour Technol 2012;109:163e72. https://doi.org/
10.1016/j.biortech.2012.01.001.
[45] Teng SY, Loy ACM, Leong WD, How BS, Chin BLF, Ma
sa V. Catalytic thermal
degration of chlorella vulgaris: evolving deep neural networks for optimiza-
tion. Bioresour Technol 2019;292:121971. https://doi.org/10.1016/
j.biortech.2019.122089.
[46] Gupta S, Gupta GK, Mondal MK. Slow pyrolysis of chemically treated walnut
shell for valuable products: effect of process parameters and in-depth product
analysis. Energy 2019;181:665e76. https://doi.org/10.1016/
j.energy.2019.05.214.
[47] Soon VSY, Chin BLF, Lim ACR. Kinetic study on pyrolysis of oil palm frond. IOP
Conf Ser Mater Sci Eng 2016;121:012004. https://doi.org/10.1088/1757-899X/
121/1/012004.
[48] Yeo JY, Chin BLF, Tan JK, Loh YS. Comparative studies on the pyrolysis of
cellulose, hemicellulose, and lignin basd on combined kinetics. J Energy Inst
2019;92:27e37. https://doi.org/10.1016/j.joei.2017.12.003.
[49] Chin BLF, Yusup S, Al Shoabi A, Kannan P, Srinivasakannan C, Sulaiman SA.
Comparative studies on catalytic and non-catalytic co-gasification of rubber
seed shell and high density polyethylene mixtures. J Clean Prod 2014a;70:
303e14. https://doi.org/10.1016/j.jclepro.2014.02.039.
[50] Font R, Marcilla A, Verdú E, Devesa J. Thermogravimetric kinetic study of the
pyrolysis of almond shells and almond shells impregnated with CoCl2. J Anal
Appl Pyrolysis 1991;12:249e64. https://doi.org/10.1016/0165-2370(91)
80001-O.
[51] Çepeliog € Mutlu I,
ullar O, _ Yaman S, Haykiri-Acma H. Activation energy pre-
diction of biomass wastes based on different neural network topologies. Fuel
2018;220:535e45. https://doi.org/10.1016/j.fuel.2018.02.045.
[52] Kasmuri NH, Kamarudin SK, Abdullah SRS, Hasan HA, Som AM. Integrated
advanced nonlinear neural network-simulink control system for production
of bio-methanol from sugar cane bagasse via pyrolysis. Energy 2019;168:
261e72. https://doi.org/10.1016/j.energy.2018.11.056.
[53] Kalogirou SA. Artificial intelligence for the modeling and control of combus-
tion processes: a review, Progress in Energy and Combustion Science. 2003.
https://doi.org/10.1016/S0360-1285(03)00058-3.
[54] Chen Z, Wang M, Jiang E, Wang D, Zhang K, Ren Y, Jiang Y. Pyrolysis of tor-
refied biomass. Trends Biotechnol 2018;36:1287e98. https://doi.org/10.1016/
j.tibtech.2018.07.005.
[55] Fang P, Gong Z, Wang Zhenbo, Wang Zhentong, Meng F. Study on combustion
and emission characteristics of microalgae and its extraction residue with TG-
MS. Renew Energy 2019;140:884e94. https://doi.org/10.1016/
j.renene.2019.03.114.
[56] Fong MJB, Loy ACM, Chin BLF, Lam MK, Yusup S, Jawad ZA. Catalytic pyrolysis
of Chlorella vulgaris: kinetic and thermodynamic analysis. Bioresour Technol
2019;289:121689. https://doi.org/10.1016/j.biortech.2019.121689.
[57] Xu Z, Xiao X, Fang P, Ye L, Huang J, Wu H, Tang Z, Chen D. Comparison of
combustion and pyrolysis behavior of the peanut shells in air and N2: kinetics,
thermodynamics and gas emissions. Sustainability 2020;(2):464. https://
doi.org/10.3390/su12020464.
[58] Liu H, Chen Y, Yang H, Gentili FG, So €derlind U, Wang X, Zhang W, Chen H.
Hydrothemal carbonization of natural microalgae containing a high ash
content. Energy 2019;249:441e8. https://doi.org/10.1016/j.fuel.2019.03.004.
[59] Cao JP, Huang X, Zhao XY, Wang BS, Meesuk S, Sato K, Wei XY, Takarada T.
Low-temperature catalytic gasification of sewage sludge-derived volatiles to
produce clean H2-rich syngas over a nickel loaded on lignite char. Int J
Hydrogen Energy 2014;39(17):9193e9. https://doi.org/10.1016/
j.ijhydene.2014.03.222.
[60] Ren J, Liu YL, Zhao XY, Cao JP. Methanation of syngas from biomass gasifica-
tion: an overview. Int J Hydrogen Energy 2020;45(7):4223e43. https://
doi.org/10.1016/j.ijhydene.2019.12.023.
[61] Wang BS, Cao JP, Zhao XY, Bian Y, Song C, Zhao YP, Fan X, Wei XY, Takarada T.
Preparation of nickel-loaded on lignite char for catalytic gasification of
biomass. Fuel Process Technol 2015;136:17e24. https://doi.org/10.1016/
j.fuproc.2014.07.024.