Process Safety and Environmental Protection 160 (2022) 341–353

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Process Safety and Environmental Protection

journal homepage: www.elsevier.com/locate/psep

Investigation on the co-pyrolysis of agricultural waste and high-density

polyethylene using TG-FTIR and artificial neural network modelling ]]
]]]]]]
]]

⁎ ⁎
Jishuo Li a,b, Xiwen Yao a,b, Shoukun Chen a,b, , Kaili Xu a,b, , Bingjie Fan a,b, Dexin Yang a,b,
Liyan Geng a,b, Haiming Qiao c
a
School of Resources and Civil Engineering, Northeastern University, Shenyang 110819, PR China
b
Key Laboratory of Ministry of Education on Safe Mining of Deep Metal Mines, Shenyang 110819, PR China
c
Liaoning Institute of Geology and Mineral Resources, Shenyang 110819, PR China

a r t i cl e i nfo a bstr ac t

Article history: To realize utilization of agricultural and plastic waste to alleviate environmental pollution, the individual
Received 10 January 2022 pyrolysis and co-pyrolysis characteristics of kidney beans stalk (KS) and high-density polyethylene (HDPE)
Received in revised form 2 February 2022 were investigated. Thermogravimetry coupled with Fourier transform infrared spectroscopy (TG-FTIR) was
Accepted 14 February 2022
used to investigate the pyrolysis behaviour, synergistic effect, kinetics and gaseous product evolution of
Available online 16 February 2022
different samples. In addition, an artificial neural network (ANN) model was established to predict the mass
change with temperature during sample pyrolysis or co-pyrolysis. The results showed that the decom­
Keywords:
Agricultural waste position of HDPE was easier than that of KS, and synergistic and inhibitive effects occurred during co-
HDPE pyrolysis. The synergistic or inhibitive effect was most significant from 470 to 510 ℃. The FTIR analysis
TG-FTIR results showed that gaseous products of KS pyrolysis were mainly oxygen-containing compounds including
Synergistic effect CO2, CO, ketones, aldehydes, esters, etc., while those of HDPE pyrolysis were mainly hydrocarbons including
ANN alkanes, alkenes, aromatic rings, etc. The co-pyrolysis of samples with different proportions promoted or
inhibited the production of some gaseous products to different degrees. Moreover, the activation energy of
the two stages during co-pyrolysis was lower than that of the pure sample. The established ANN model can
effectively predict the mass loss of a sample with temperature.
© 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.

1. Introduction
The exhaustion of primary energy and its pollution to the en­
vironment lead many studies to focus on the utilization of biomass
resource (Glushkov et al., 2021; Yan and Xu, 2018). Agricultural
waste is one type of available biomass, and increasing research has
focused on the conversion of this waste into available energy. As a
kind of agricultural waste, a large part of straw is burned in open
fields in northeastern China. The particulate matter, CO, SO2 and
volatile organic compounds (VOCs) produced by straw burning pose
a serious threat to the environment. In addition to agricultural
waste, as one of the main components of municipal solid waste,
polymer waste such as plastics has issues such as large annual
production, low utilization rate and long degradation time in nature,
posing a serious threat to the environment (Chen et al., 2021; Farooq
⁎
Corresponding authors at: School of Resources and Civil Engineering,
Northeastern University, Shenyang 110819, PR China.
E-mail addresses: 1910386@stu.neu.edu.cn (S. Chen),
xukaili@mail.neu.edu.cn (K. Xu).
et al., 2021; Michael Rahul et al., 2021). The problem of waste re­
source utilization has prompted much research to explore an ef­
fective way to convert waste into usable resources.
As a biomass thermal conversion technology, pyrolysis can
transform waste into high-quality alternative liquid fuel (bio-oil)
with a continuous process and factory production mode; this fuel is
easy to store and transport, has high energy density and is con­
venient to use (Safᡠand Mikulˇ, 2021). Bio-oil contains many che­
mical raw materials and products, and hundreds of substances have
been identified in the liquid products of pyrolysis (Dimitriadis et al.,
2021; Ge et al., 2022; Yan et al., 2021). Therefore, pyrolysis of agri­
cultural and plastic waste is an effective resource utilization method
that can help reduce the use of primary energy and alleviate en­
vironmental pollution. Most studies have focused on the co-pyr­
olysis of biomass and high-density polyethylene (HDPE) to
investigate the effects of pyrolysis conditions on liquid products (or
bio-oil). For example, Hassan et al. (2020) found that the co-pyr­
olysis of sugarcane bagasse and HDPE promoted the yield of liquid
products, and the synergistic effect was strongest when the mixing
ratio was 60:40 at 600 ℃. The authors attributed this synergistic

https://doi.org/10.1016/j.psep.2022.02.033
0957-5820/© 2022 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.
J. Li, X. Yao, S. Chen et al.
effect to the fact that hydroxyl intermediates from sugarcane ba­
gasse promote continuous pyrolysis of the major volatiles in HDPE,
leading to the formation of aliphatic compounds with lower carbon
numbers. In addition, Chen et al. (2016) found that the effect of
hydrogen replenishment and deoxidation by HDPE could partially
explain the synergistic effect. The authors observed that the oil
phase yield was increased by 31.6% within the temperature range of
400–500 ℃ compared to the theoretical calculated results. More­
over, studies have shown that introduction of HDPE to the pyrolysis
of red oak, almond shell and potato can increase the yield of liquid
products (Önal et al., 2014; Xiong et al., 2015; Xue et al., 2015). The
above literature indicated that the co-pyrolysis of biomass and HDPE
had a synergistic effect on liquid product yield (Wang et al., 2021).
However, there are few studies on the effects of co-pyrolysis of
agricultural waste and HDPE on the composition and evolution of
volatiles. It is worth noting that there is no consensus on whether
co-pyrolysis has synergistic or inhibitory effects on the composition
and evolution of volatiles. For example, Kai et al. (2017) found that
when the mixing ratios of rice straw (RS) and HDPE were different,
co-pyrolysis could both promote and inhibit the release of propane
(m/z = 43), and such promotion or inhibition depended on the pyr­
olysis temperature. However, when the authors investigated the co-
pyrolysis of corn stalk (CS) and HDPE, they found that the generation
of propane was always inhibited under different mixing ratios and
pyrolysis temperatures (Kai et al., 2019). It was concluded that
changes in the sample, mixing ratio, and temperature lead to dif­
ferent effects between agricultural waste and HDPE (He et al., 2021).
Therefore, the evolution of volatiles during the co-pyrolysis of other
agricultural waste and HDPE is worth studying.
Thermogravimetric analysis (TGA) combined with Fourier
transform infrared spectroscopy (FTIR) is one thermal analysis
method that can monitor changes in sample mass and the release of
different gaseous products online. The advantage of this technique
lies in its ability to describe the pyrolysis characteristics, kinetics and
evolution of gaseous products (Sun et al., 2022). Keliona et al. (2020)
used TG-FTIR to study the evolution of hydrocarbons and oxyge­
nated compounds in gaseous products during the co-pyrolysis of
torrefied biomass and different plastics. The authors concluded that
the introduction of HDPE inhibited the production of H2O, acid,
ketone, and aldehydes. Chen et al. (2017) also observed that the co-
pyrolysis of HDPE and enzymatic hydrolysis of lignin promoted the
cracking reaction of oxygenated compounds in the pyrolysis tem­
perature range of 390–542 ℃ and 563–790 ℃, respectively. Hu et al.
(2020) found through TG-FTIR analysis that the co-pyrolysis of tires
and different plastics promoted the production of C–H-containing
compounds. These results are attributed to the fact that plastics have
a high hydrogen content and low oxygen content. Overall, the in­
troduction of HDPE can increase the yield of hydrocarbons and re­
duce that of oxygenated compounds, but whether it can promote or
inhibit a certain compound remains to be studied (Singh et al., 2020;
Xin et al., 2021; Zhong et al., 2021). Therefore, TG-FTIR was used to
investigate the pyrolysis and co-pyrolysis characteristics of kidney
bean stalk (KS) and HDPE in the present paper. In addition to TG-
FTIR, the application of artificial neural networks (ANNs) in biomass
thermal conversion has been widely applied and verified (Ni et al.,
2022b, 2021; Zhao et al., 2022). The characteristics and advantages
of ANNs are mainly shown in three aspects. First, they have a self-
learning function. The self-learning function is particularly im­
portant for prediction. Second, they have an associative storage
function. This kind of association can be realized by the feedback
network of an artificial neural network. Third, they have the ability
to find optimal solutions at high speed. Finding the optimal solution
of a complex problem often requires considerable computation.
Using a feedback artificial neural network designed for a certain
problem and giving full play to the high-speed computing ability of
the computer, it is possible to find the optimal solution quickly
342
Process Safety and Environmental Protection 160 (2022) 341–353
(Almomani, 2020a; Shawaqfah and Almomani, 2021). Le et al. (2021)
used ANNs to perform a systematic review and meta-analysis to
assess the production of H2 by various catalysts in the dry reforming
process. Li et al. (2021) established an ANN model by taking the
composition of biomass elements as input variables and the exergy
efficiency of H2 and cold gas efficiency (CGE) of combustible syngas
as output variables. The results showed that the ANN model could
provide a basis for selecting feedstock with a high exergy efficiency
of H2 and CGE of combustible syngas. Gupta et al. (2022) applied the
ANN method to predict the pyrolysis process of pine, investigating
the effect of the temperature, heating rate and inert gas flow rate.
Sajjad et al. (2020) took the heating rate and temperature as input
variables and the mass loss results obtained by TGA as output
variables for training, testing and verification. With the ANN model,
the R2 determined for both the predicted and experimental results
reached 0.9777, showing good prediction performance. Bi et al.
(2021) used an ANN to predict the change in mass loss with tem­
perature during the pyrolysis and co-pyrolysis of sewage sludge (SS)
and peanut shell (PS), and the established ANN model also showed
good predictive ability. Moreover, many studies have also proved
that it is effective and feasible to use ANN model to predict biomass
pyrolysis behaviour (Almomani, 2020b; Li et al., 2021). Previous
literature has fully demonstrated that ANNs have the ability to
predict mass loss during the pyrolysis and co-pyrolysis of KS
and HDPE.
The purpose of this paper is to study the thermodynamic beha­
viour, kinetics and evolution of gaseous products during pyrolysis
and co-pyrolysis of KS and HDPE. TG-FTIR was used to monitor the
change in mass loss and functional groups of gaseous products with
temperature during these pyrolysis and co-pyrolysis processes. The
pyrolysis characteristic parameters, gaseous product evolution and
synergistic effect were determined according to the experimental
data. The kinetic parameters of KS, HDPE and their mixtures were
calculated by the Coats-Redfern and Doyle methods. In addition, an
ANN model was established to predict the change in mass loss with
temperature under specific pyrolysis conditions, and the predicted
and experimental results were compared. The results can provide a
reference for further understanding the co-pyrolysis mechanism of
agricultural waste and plastics.
2. Materials and methods
2.1. Feedstock
KS, as a representative type of agricultural waste, was produced
in northeastern China. HDPE (particle size: 200 mesh) was pur­
chased from Shanghai Macklin Biochemical Co., Ltd., China. KS was
collected in a rural area in Northeast China in October, dried natu­
rally for two weeks, and then crushed into approximately 80 mesh
particle size. Before the experiment, the feedstock was placed in a
vacuum drying oven and maintained at 105 °C for 24 h. Proximate
analysis was conducted using a TRGF-8000 system provided by
Tianrun Electronic Technology Company Limited. Ultimate analysis
was conducted using a Vario MACRO cube provided by Xinhe Yilong
Instrument Company Limited. The proximate and ultimate analysis
results of the feedstock are shown in Table 1.
2.2. TG-FTIR analysis
Feedstock pyrolysis was performed in a thermogravimetric ap­
paratus (NETZSCH STA449F3) with a 10 mg sample size to study the
degradation of the feedstock in an inert atmosphere. The feedstock
was heated from room temperature to 1000 ℃ at a rate of 20 ℃/min
in a N2 atmosphere with a flow rate of 50 ml/min. The gaseous
products produced during pyrolysis were transferred to an online
FTIR instrument (TenSor 27), which measured the wavenumber
J. Li, X. Yao, S. Chen et al. Process Safety and Environmental Protection 160 (2022) 341–353

Table 1
Properties of feedstock.

Proximate analysis (wt%) Ultimate analysis (wt%)

Moisture Ash Volatile Fixed carbon C H O N S

KS 4.25 1.84 82.4 11.51 38.19 6.10 54.01 1.67 0.03

HDPE – – 100 – 85.72 14.28 – – –

range from 4000 to 500 cm−1. The gaseous products produced from Eq. (5) is the fundamental expression of pyrolysis kinetics. Dif­
pyrolysis in the thermogravimetric apparatus were transferred ferent models can be obtained by processing with different methods.
through connection tubes maintained at 250 °C, and the cell tem­ The Coats-Redfern approximation and Doyle approximation were
perature was maintained at 250 °C to avoid condensation of the introduced to calculate the kinetic parameters of different samples.
condensable gaseous products. The experimental samples were di­ Suppose the pyrolysis reaction follows the first order reaction ki­
vided into five groups, namely, KS, 7KS:3HDPE, 5KS:5HDPE, netics with n = 1 and integrate both sides of Eq. (5) using these two
3KS:7HDPE and HDPE, to investigate the pyrolysis behaviour of the methods, Eq. (5) can be expressed as follows (Hu et al., 2020):
feedstock.
To characterize the thermal decomposition reaction character­ ln(1 ) AR 2RT E
Coats Re dfernmethod: ln = ln 1
istics of different samples, the volatile release characteristic index D T2 E E RT
was introduced in this study. The index D is calculated as follows (6)
according to the characteristic parameters obtained from the TG and
derivative thermogravimetry (DTG) curves of the sample (Yao AE E
Doyle method: ln( ln(1 )) = ln 5.33 1.052
et al., 2016): R RT (7)
DTGmax × DTGmean For the pyrolysis reaction, 2RT/E < < 1, so Eq. (6) can be simpli­
D=
Ts × Tmax × T1/2 (1) fied further as follows:

where DTGmax is the maximum mass loss rate and DTGmean is the
mean mass loss rate. Ts is the temperature corresponding to the
initial decomposition, which refers to the temperature at which the
mass loss rate reaches 1%/min in this paper (Wang et al., 2012). Tmax
is the temperature corresponding to the maximum mass loss rate,
and ΔT1/2 is the half-peak width of the DTG curves. The higher the
index D value is, the easier the thermal decomposition reaction is.
2.3. Kinetic analysis
The Coats-Redfern method and Doyle method are introduced to
determine the kinetic parameters based on the results of pyrolysis
and co-pyrolysis with a heating rate of 20 ℃/min. According to the
Arrhenius equation, the fundamental equation of pyrolysis kinetics
can be expressed as follows (Bockhorn et al., 1999):
d adjusting and changing the weight of neuron connections (Gupta
= k (T ) f ( )
dt (2)
where dα/dt is the decomposition rate and α represents the con­
version degree for the pyrolysis process, which can be calculated as
follows:
m0 mt
=
m0 m (3)
where m0, m∞, and mt represent the initial mass, final mass and mass
at time t, respectively.
According to the Arrhenius relation criterion, the temperature
function k(T) of the thermal decomposition sample can be calculated
based on the first-order reaction as follows:
E expected output value of the network (Sajjad et al., 2020). In this
k (T ) = A exp
RT (4)
where A is the pre-exponential factor (min−1), E is the activation
energy (kJ/mol), R is the universal gas constant (8.314 J/mol/K), and T
is the absolute temperature (K). Substituting Eq. (4) into Eq. (2) and
introducing the heating rate β = dT/dt convert Eq. (2) into the fol­
lowing:
d A E and can be calculated by Eq. (9). R2 indicates the correlation between
= exp (1 ) the prediction and experimental results and can be expressed by Eq.
dT RT (5)
ln(1 ) AR E
ln = ln
T2 E RT (8)
Regarding Eq. (7), for a given heating rate, ln[-ln(1-α)] has a linear
relationship with 1/T, with its slope equal to −1.052E/R and intercept
equal to ln(AE/R)-5.33. Regarding Eq. (8), for a given heating rate, ln
[-ln(1-α)/T2] also has a linear relationship with 1/T, with its slope
equal to -E/R and intercept equal to ln(AE/R).
2.4. ANN
ANNs can be divided into multi-layer and single-layer models.
Each layer contains several neurons connected by directed arcs with
variable weights. Through repeated learning and training of known
information, the network can successfully process information and
simulate the relationship between input and output by gradually
et al., 2022). The model does not need to know the exact relationship
between input and output and does not need many parameters but
only needs to know the non-constant factors causing output
changes, that is, the non-constant parameters. Therefore, compared
with traditional data processing methods, ANN technology has ob­
vious advantages in processing fuzzy data, random data, and non­
linear data and is especially suitable for large-scale, complex
structures and unclear information systems.
The ANN model established in this paper is a multi-layer feed­
forward network trained by error backpropagation (BP), also called a
BP neural network. Its basic principle is the gradient descent
method, which uses gradient search technology to minimize the
mean squared error (MSE) between the actual output value and the
paper, the ANN model was established by taking the mass change of
feedstock as the target variable and temperature (or time) as the
input variable. The dataset of more than 10,000 data points was
divided into three parts: training (70%), validation (15%) and testing
(15%). The mean squared error and R2 were introduced to evaluate
the performance of the model. The MSE indicates the average
squared difference between the prediction and experimental results
(10) (Ashraf et al., 2021).

343
J. Li, X. Yao, S. Chen et al. Process Safety and Environmental Protection 160 (2022) 341–353

Fig. 1. TG and DTG curves of KS, HDPE and their mixtures.

n
1 2
MSE = ( ei pi)
n (9)
i=1
n 2
i = 1 ( ei pi )
R2 = 1 n 2
i = 1 ( ei e)
where λei is the experimental value, λpi is the prediction value, and
is the mean experimental result.
3. Results and discussion
3.1. TG analysis
The TG and DTG curves for KS, HDPE and their mixtures de­
termined at a heating rate of 20 ℃/min in a N2 environment are
shown in Fig. 1. The corresponding pyrolysis reaction characteristic
parameters are shown in Table 2. It is obvious that the difference in
mass loss between KS and HDPE is very large due to the different
structures and chemical compositions (Won et al., 2020). With in­
creasing temperature, the pyrolysis behaviour of KS can be divided
into three stages. In the first stage, there is a slight mass loss when
the temperature increases from room temperature to approximately
220 ℃. The mass loss in this stage is mainly due to the release of light
volatiles and evaporation of some water absorbed in the feedstock
(Ashraf et al., 2021). The second stage (220–420 ℃) is the main stage
of pyrolysis, during which KS rapidly decomposes and releases a
large amount of volatiles. Most of the mass loss is attributed to the
decomposition of hemicellulose, cellulose, and partial lignin. In this
stage, intermolecular and intramolecular hydrogen bonds are frag­
mented, and volatile matter including organic carbon products, H2O
and noncondensable gases is released (Yazdani et al., 2019). In the
third stage (420–1000 ℃), there is a slight mass loss due to the
thermal decomposition of lignin and devolatilization of biochar (Ma
et al., 2018). Compared with that of HDPE, the mass loss rate of KS is
slower and the residual mass is larger (Mf = 25.43%).
The decomposition process of HDPE is quite different from that of
KS, the decomposition of HDPE starts rapidly and reaches towards
the end of the process. It is obvious that the initial decomposition
(10) temperature of HDPE (438 ℃) is significantly higher than that of KS
(192 ℃). The temperature at which HDPE reaches its maximum mass
e
loss rate (Tmax = 527 ℃) is also higher than that of KS (Tmax = 330 ℃).
The decomposition of HDPE involves an irregular chain-breaking
reaction in which macromolecular chains generate low molecular
weight polymers and volatilize at higher temperatures. The reason
for the higher initial decomposition temperature is that the dis­
sociation of C–C, C–H and C]C bonds takes place at higher tem­
peratures (Lewandowski and Ryms, 2020). There is a small
temperature range (438–517 ℃) for the release of volatiles and al­
most no residual mass at the end of this stage. This finding indicates
that HDPE has a simple structure and relatively high volatile content.
The ΔT1/2 and index D of HDPE were compared with those of KS,
indicating that HDPE has better volatile release characteristics and
that the pyrolysis reaction is easier to carry out.
Fig. 1(a) shows that the TG curves of the mixtures of KS and HDPE
are located between those of KS and HDPE. As the proportion of
HDPE increases, the temperature at which volatiles begin to release
gradually increases, and the residual mass is gradually decreased.
The main reason is that the volatile content in HDPE is high and
starts to degrade at higher temperatures. In addition, a synergistic
reaction between KS and HDPE may contribute to this result. In the
DTG curves of Fig. 1(b), the mixtures both have two conspicuous
peaks at temperature ranges of 200–400 ℃ and 400–600 ℃. The first
peak represents the decomposition of lignocellulosic compounds
(cellulose, hemicellulose and partial lignin) in the mixtures. The
presence of the second peak is due to the degradation of HDPE. As
the proportion of HDPE increases, the absolute value of the first peak
decreases, and that of the second peak increases. The reason for the

Table 2
Pyrolysis reaction characteristic parameters.

Feedstock Ts (℃) Tmax (℃) ΔT1/2 (℃) DTGmax (%/min) DTGmean (%/min) Mf (%) D (%2/min2/℃3)

KS 192 330 51 −15.62 −1.53 25.43 7.40E-06

3KS:7HDPE 225 499 27 −40.89 −1.76 12.48 2.37E-05
5KS:5HDPE 216 499 33 −28.47 −1.73 15.49 1.38E-05
7KS:3HDPE 202 500 32 −17.12 −1.67 16.72 8.85E-06
HDPE 438 527 26 −72.41 −1.99 1.05 2.40E-05

344
J. Li, X. Yao, S. Chen et al.
Fig. 2. Comparison of the calculated and experimental TG curves (a) and their deviation (b).
opposite phenomenon of the two peaks may be due to the HDPE
softening to a plastic state when the temperature exceeds 300 ℃,
which results in the formation of a coating layer on the surface of the
mixture and inhibits the release of volatiles (Zhou et al., 2006).
When the temperature continues to rise to 400 ℃, the coating layer
on the surface of the mixture starts to decompose, and the release of
volatiles is no longer inhibited. When the DTG curves of the mixtures
reach their peak value, the temperatures corresponding to the first
peak are 331 ℃, 328 ℃ and 327 ℃, and the temperatures corre­
sponding to the second peak are 500 ℃, 499 ℃ and 499 ℃. Through
analysis of the pyrolysis reaction characteristic parameters in
Table 2, the Ts value of KS increased from 192 ℃ to 225 ℃ with in­
creasing HDPE content, suggesting that introduction of HDPE de­
layed the thermal decomposition process. With increasing
proportion of HDPE in KS, the absolute value of DTGmean in the
feedstock increased from 1.53%/min to 1.76%/min, indicating that the
introduction of HDPE can improve the pyrolysis rate of feedstock.
Moreover, index D of the feedstock is ranked in the order HDPE >
3KS:7HDPE > 5KS:5HDPE > 7KS:3HDPE > KS, which shows that the
introduction of HDPE helps facilitate KS thermal decomposition.
3.2. Synergistic effect analysis
To analyse whether there is a synergistic effect during pyrolysis
of the KS and HDPE mixture, the parameter ΔW is introduced to
quantify the deviation between the experimental and calculated
values of TG. ΔW can be determined as follows:
W = TGExperiment (xKS TGKS + xHDPE TGHDPE)
Process Safety and Environmental Protection 160 (2022) 341–353
where xKS and xHDPE represent the percentage of KS and HDPE in the
mixture, respectively. ΔW > 0, indicating inhibitory effects; ΔW < 0,
indicating synergistic effects.
Fig. 2(a)–(c) show the TG and DTG curves of different mixtures,
which were determined by calculations and experiments, respec­
tively. By comparison of the DTG curves, it can be seen that the
DTGmax determined experimentally is significantly lower than the
calculated value. As the proportion of HDPE increases, this difference
continues to decrease. When the mixing ratio of KS and HDPE is 5:5,
the experimental TG value is higher than the calculated value. This
result indicates that there are inhibitive effects between KS and
HDPE at this mixing ratio. For the other two mixtures, the calculated
TG value is higher than the experimental value before approximately
500 ℃. This finding indicates that there are synergistic effects be­
tween KS and HDPE at these two mixing ratios. However, when the
temperature exceeds approximately 500 ℃, the two mixtures show
different phenomena. The calculated TG value is always lower than
the experimental value above approximately 500 ℃ at a mixing ratio
of 3:7, which indicates that the inhibitory effects between KS and
HDPE are maintained. For the mixing ratio of 7:3, the inhibitive ef­
fects change to synergistic effects above approximately 513 ℃.
Fig. 2(c) shows the deviation between the calculated and ex­
perimental TG curves. Moisture is removed from the mixture before
220 ℃, and the ΔW value of this stage remains between −1 and 1.
Therefore, this stage is not considered, as it is not the subject of this
study. The ΔW of the two mixtures (3KS:7HDPE and 7KS:3HDPE) is
negative within the temperature range of 220–513 ℃, indicating a
synergistic effect between KS and HDPE. It is worth noting that the
temperature range of this phenomenon is almost identical to that of
(11) the second stage of KS, namely, 220–420 ℃, suggesting that
345
J. Li, X. Yao, S. Chen et al.
Fig. 3. 3D FTIR diagrams of (a) KS and (c) HDPE and 2D FTIR diagrams of (b) KS and (d) HDPE.
decomposition and devolatilization of KS play an important role in
this synergistic effect. The corresponding temperatures for the
minimum ΔW of 3KS:7HDPE and 7KS:3HDPE are approximately
472 ℃ and 479 ℃, respectively. Then, with increasing temperature,
ΔW gradually increases, indicating that this synergistic effect gra­
dually weakens. It can be seen from Fig. 1 that KS is close to the end
state of pyrolysis at approximately 480 ℃, which also indicates that
KS decomposition plays a leading role during this period. After the
temperature reaches approximately 460 ℃, the ΔW values of the
mixtures (3KS:7HDPE and 5KS:5HDPE) are positive and increase
until the temperature reaches approximately 500 ℃ and then start to
drop slightly. This temperature range is within the range of the re­
lease of HDPE volatiles, indicating that HDPE plays a dominant role
in the inhibitory effect between mixtures in this range. The main
reason why HDPE inhibits the pyrolysis process is that HDPE softens
and becomes plastic after the temperature rises and forms a coating
layer on the KS surface to inhibit the release of volatiles (Zhang et al.,
2014). This is also the main reason why the inhibitory effect of the
three mixtures becomes stronger at approximately 480 ℃. As the
temperature continues to rise, the coating covering the KS surface is
decomposed. Thermal degradation of polyolefin, including initiation,
propagation and termination steps, occurs through random chain-
breaking reactions (Bockhorn et al., 1999), and free radicals gener­
ated during KS pyrolysis can react with HDPE to accelerate KS de­
composition and destroy the coating layer on the surface of KS,
resulting in a decrease in ΔW. This is also the main reason why the
ΔW values of the three mixtures begin to decrease above
346
Process Safety and Environmental Protection 160 (2022) 341–353
approximately 500 ℃, and correspondingly, the inhibitory effect of
HDPE is weakened.
3.3. FTIR analysis
3.3.1. FTIR analysis for KS and HDPE pyrolysis
The 3D FTIR spectrum in Fig. 3(a)–(d) shows the evolution of
gaseous products in the 4000–500 cm−1 wavenumber range in re­
sponse to the pyrolysis of KS and HDPE. Moreover, to more accu­
rately describe the main pyrolysis products of different samples, the
temperature corresponding to the peak value of DTG curves was
selected to draw the 2D FTIR spectrum diagram. The IR bands of the
functional groups and their corresponding possible gaseous products
investigated in this paper are shown in Table 3.
Fig. 3(a) shows that gaseous products are not detected until
10 min after the start of pyrolysis. A low absorbance of the gaseous
products is observed at the beginning of KS pyrolysis. With in­
creasing pyrolysis time (or temperature), the absorbance increases
and then decreases. According to the Lambert–Beer law, the absor­
bance of a gas is proportional to its concentration under the same
experimental conditions (Ni et al., 2022a). Fig. 3(a) shows the sig­
nificant characteristic peaks in the wavenumber range of
2400–2260 cm−1. These peaks are attributed to carboxylic stretching
vibrations (Singh et al., 2020). In addition, the second higher char­
acteristic peak (669 cm−1) in the range of 730–630 cm−1 is attributed
to CO2 release. The characteristic peaks (2358 cm−1 and 669 cm−1)
associated with CO2 remain significant above 330 ℃ (the
J. Li, X. Yao, S. Chen et al. Process Safety and Environmental Protection 160 (2022) 341–353

Table 3
Assignments of the IR bands to the functional groups and possible gaseous products (Qiao et al., 2019; Singh et al., 2020; Wang et al., 2020).

Group Frequency, wavenumber Assigned wavenumber Assignment Possible products

4000–3500 3735 OeH stretch Water, Phenols, Alcohols

3620–3540 3566 OeH stretch Tertiary alcohol, OH stretch
3095–3075 3085 CeH Terminal (vinyl) C-H stretch; Hydrocarbons
2935–2915 2929 CeH stretch Methylene C-H asymmetric stretch
3100–2600 2821 CeH stretch Hydrocarbon
2400–2260 2358 C]O stretch CO2 (carboxylic stretch)
2309 C]O stretch
2240–2060 2186 CO CO
2250–2000 2116 C]O Oxygen-contenting compounds
1840–1590 1768 C]O stretch Ketones, Aldehydes, Esters, Carboxylic acids, Primary amides
1680–1620 1639 C]C stretch (skeletal vibration) Aromatic ring stretch
1650–1450 1508 Aromatic ring Light aromatics
1485–1445 1461 ]CH2 bend Aromatic ring (aryl)
1300–950 1172 CeO stretch Phenols, alcohols, ethers
1225–950 1092 CeH out of plane bend Aromatics
920–900 913 CeH out of plane bend Mono-substituted alkenes
750–710 715 eCH2 rocking Methylene -(CH2)n- rocking (n > 3) or meta di-substituted aromatics
900–670 859 CeH out of plane bend Aromatics
730–630 669 CO2 CO2

temperature corresponding to the maximum mass loss rate). The
reason for the presence of these absorbance peaks is that the organic
acids, proteins and saccharides in KS do not decompose completely
to form CO2 but rather destroy the thermally unstable bonds and
form small molecules with C]O and C–O functional groups (Wang
et al., 2020). The obvious characteristic peaks (1768 cm−1 and
1172 cm−1) in the ranges of 1840–1590 cm−1 and 1300–950 cm−1
shown in Fig. 3(a),(b) can also explain this phenomenon, which in­
dicates that carboxylic acids, ketones, esters, aldehydes, primary
amides, alcohols, and phenols may be produced at this temperature
(Peng et al., 2015). Unlike that associated with CO2 release, the ab­
sorbance of the characteristic peak (2186 cm−1) associated with CO is
very low. This result is the same as that found in other studies and
may be related to the amount of CO release (Ni et al., 2022a; Qiao
et al., 2019; Zhao et al., 2020). The characteristic peak (1508 cm−1) in
the range of 1650–1450 cm−1 mainly indicates the presence of light
aromatics. The characteristic peaks (3735 cm−1 and 3566 cm−1) in
the ranges of 4000–3500 cm−1 and 3620–3540 cm−1 are due to O–H
stretching vibrations, indicating the possible presence of H2O, phe­
nols, alcohols and tertiary alcohols as products.
Due to the different internal structures and compositions of KS
and HDPE, the gaseous product evolution of HDPE is different from
that of KS. Compared with that in Fig. 3(a),(b), the number of char­
acteristic peaks in Fig. 3(c),(d) is small, indicating that the gas
composition produced by HDPE pyrolysis is relatively lower. The two
most significant characteristic peaks (2929 cm−1 and 2821 cm−1) in
the range of 3200–2800 cm−1 are due to C–H stretching vibrations,
indicating the generation of alkanes and alkenes (Nahid and Hamid,
2009). The absorbance of characteristic peaks in the range of
3200–2800 cm−1 during HDPE pyrolysis is significantly higher than
that for KS, indicating that more hydrocarbons are produced. The
characteristic peaks (1461 cm−1 and 1639 cm−1) within the ranges of
1485–1445 cm−1 and 1680–1620 cm−1 indicate the presence of
compounds containing aromatic rings. It was observed that the
primary products during HDPE pyrolysis are alkanes, alkenes and
aromatics with small amounts of aldehydes, benzene, etc.
3.3.2. FTIR analysis of mixture pyrolysis
Fig. 4(a)–(f) describe the evolution of gaseous products during
mixture pyrolysis within the wavenumber range of 4000–500 cm−1.
It can be seen from Fig. 1(b) that the DTG curves of the mixtures both
have two obvious peaks, so the temperature corresponding to the
two peaks is selected to further study the gaseous product dis­
tribution of the mixture.
The gas evolution during pyrolysis of the mixture can be divided
into two stages. In the first stage (200–400 ℃), the gas produced is
mainly attributed to the decomposition of hemicellulose and cellu­
lose in KS, generating CO2, CO, H2O, aromatic compounds, hydro­
carbons, etc. The gases produced in the second stage (400–600 ℃)
are primarily ascribed to the decomposition of HDPE, which mainly
releases gaseous products of hydrocarbons. By comparing 2D FTIR
diagrams at the two temperatures, it can be found that the kinds of
gaseous products decreased at higher temperatures, which also
verified the above results. In Fig. 4(a)–(f), the most significant
characteristic peaks are both attributed to C–H stretching vibrations.
As the proportion of HDPE increases, the absorbance of the char­
acteristic peak increases. It can be seen from the 2D FTIR diagrams in
Fig. 4 that there are characteristic peaks of C–H at two different
temperatures. The first characteristic peak of C–H at approximately
330 ℃ is much weaker than the second peak at approximately
500 ℃. This finding indicates that the C–H stretching vibrations
observed at higher temperatures during mixture pyrolysis are
mainly caused by HDPE. This result is consistent with the study of
Kai et al. (2019), who found that adding HDPE during corn stalk
pyrolysis promotes the release of hydrocarbons. The CO2 release
regularity of different mixtures was shown to take different forms.
The absorbance of characteristic peaks related to CO2 decreases with
increasing HDPE proportion in the mixture. The characteristic peaks
related to CO2 of KS and the mixtures both reached their maximum
values at approximately 15 min, and the corresponding pyrolysis
temperature at this moment was approximately 330 ℃. Except for
the HDPE amount, the variation trend of this characteristic peak
with increasing time is consistent. However, the maximum absor­
bance values are different and decrease with increasing HDPE pro­
portion. In Fig. 4(e), in addition to characteristic peaks related to CO2
and hydrocarbons, the characteristic peak (1768 cm−1) of C]O
within the range of 1840–1590 cm−1 is obvious. However, by com­
paring the 3D FTIR diagrams, the absorbance of the C]O peak de­
creases with increasing HDPE proportion. This result indicates that
the introduction of HDPE to the process of KS pyrolysis reduces the
yield of carbon oxides including ketones, aldehydes, esters, car­
boxylic acids, primary amides, etc. Similarly, Chen et al. (2016)
concluded that the introduction of HDPE into waste newspaper can
decrease the C-OH and C]O band intensities.
The integrated value of the absorbance of the characteristic peak
is proportional to the concentration of the gas to which it is asso­
ciated through the Lambert–Beer law. Therefore, the integrated ab­
sorbance values and the comparison of experimental and calculated

347
J. Li, X. Yao, S. Chen et al.
Fig. 4. (a), (c), and (e) 3D diagrams of mixtures and (b), (d), and (f) 2D FTIR diagrams of mixtures.
values for the gaseous products are shown in Fig. 5 to discuss the
influence of the introduction of HDPE on KS pyrolysis. In addition,
the parameter ΔI is introduced to quantify the deviation between
the experimental and calculated values of the integral value. ΔI can
be determined as follows:
I = IExperiment (xKS IKS + xHDPE IHDPE)
where xKS and xHDPE represent the percentage of KS and HDPE in the
mixture, respectively. Iexperiment represents the experimental integral
value of a certain gas. IKS and IHDPE represent the calculated integral
value of a certain gas.
Process Safety and Environmental Protection 160 (2022) 341–353
As shown in Fig. 5(a), KS pyrolysis produces a large number of
oxygen-containing compounds, while HDPE pyrolysis produces
mostly hydrocarbons. The maximum absolute value of the integral
difference in Fig. 5(b) is the integral value of CO2 absorbance in
7KS:3HDPE, indicating that HDPE promotes KS pyrolysis to produce
CO2 at this ratio. The reason for this result may be that the in­
(12) troduction of HDPE inhibits the generation of light aromatics, re­
sulting in more combinations of C and O to generate CO2 (Kai et al.,
2019). However, HDPE inhibits KS pyrolysis to produce CO2 in
5KS:5HDPE. The inhibition of CO2 generation may be caused by the
combination of C and H in HDPE to form hydrocarbons, which can
also be explained by the positive ΔI values of hydrocarbons in
348
J. Li, X. Yao, S. Chen et al.
Fig. 5. (a) Integral value of absorbance and (b) integral difference between the experimental and calculated values.
Fig. 5(b). In 5KS:5HDPE and 3KS:7HDPE, the introduction of HDPE
inhibited the production of most gases, and the inhibition became
more obvious with increasing HDPE proportion. These results may
be caused by the coating layer formed on the surface of the mixture,
which inhibits the release of volatiles (Zhang et al., 2014). Moreover,
it is observed that different proportions of HDPE can inhibit or
promote the generation of different gaseous products. Therefore, the
desired gaseous products can be obtained by controlling the addition
of the HDPE ratio.
3.4. Kinetic analysis
The pyrolysis data of KS, HDPE and their mixtures were used to
conduct kinetic analysis based on a first-order reaction model.
Through analysing the mixture pyrolysis process in Section 3.1, it can
be found that KS contributes more to pyrolysis at a lower tem­
perature, while HDPE contributes more at a higher temperature.
Therefore, KS and HDPE pyrolysis can be described by a single first-
order reaction process, whereas their mixture pyrolysis should be
better divided into two stages, including a lower temperature stage
and a higher temperature stage. The fitting curves of 1/T~ln(-ln(1-α)/
T2) and 1/T~ln(-ln(1-α)) (Fig. 6) are determined by the Coats-Redfern
method and Doyle method, respectively. The corresponding kinetic
parameter E and correlation coefficient (R2) obtained are shown in
Table 4. The table shows that the kinetic parameter E calculated by
the two methods is very close, and R2 is greater than 0.97. These
results indicate that the kinetic parameters determined by these two
methods are reliable and can describe the pyrolysis process well.
In Table 4, it can be found that the activation energy required for
the pyrolysis of HDPE (approximately 329.93 kJ/mol with the Coats-
Redfern method and 336.11 kJ/mol with the Doyle method) is much
higher than that for the pyrolysis of KS. These results indicated that
the thermal stability of HDPE is much higher than that of KS, as also
verified from the starting temperature of KS (192 ℃) and HDPE
(438 ℃) decomposition. When analysing the activation energy re­
quired for pyrolysis of the mixtures of KS and HDPE, it can be found
that the kinetic parameters of the low-temperature and high-tem­
perature stages are significantly different. The activation energy re­
quired for pyrolysis of the mixtures at the low temperature stage is
closer to that required for pyrolysis of individual KS, whereas the
349
Process Safety and Environmental Protection 160 (2022) 341–353
former value is smaller than that of the latter. This finding indicates
that the decomposition of KS becomes easier with the introduction
of HDPE. For pyrolysis of mixtures at higher temperature stages, the
required activation energy is closer to that required for pyrolysis of
individual HDPE, whereas the former value is also smaller than that
of the latter. The greater the proportion of HDPE in the mixture, the
closer the two values are. These results are ascribed to the interac­
tions of the radicals generated by KS and HDPE, leading to varying
degrees of decreased activation energy compared to that with in­
dividual pyrolysis (Xu et al., 2020).
3.5. Prediction of pyrolysis behaviour by the ANN model
Many studies have proven that it is effective and feasible to use
ANN models to predict biomass pyrolysis behaviour (Ashraf et al.,
2021; Bi et al., 2020; Ni et al., 2022a). In this paper, an ANN model is
conducted to predict the mass change of a mixture (5KS:5HDPE)
with temperature at a heating rate of 20 ℃/min. The ANN model
adopted in this paper is a two-layer feedforward network with sig­
moid hidden neurons and linear output neurons. The number of
neurons in the hidden layer is determined by repeated trial and error
since there is no standard rule to determine the number. After
constantly trying different numbers of neurons during model op­
eration, the best-performing model is selected with 3 neurons in the
hidden layer. The TG data are normalized for training (70%), vali­
dation (15%), and testing (15%) in the ANN model. Correspondingly,
the performance is determined by the MSE and R2 values. After
running this model, the R2 values for training, validation and testing
are 0.9999, which indicates good prediction performance; their MSE
values are 0.2707, 0.2616 and 0.2639, respectively. Fig. 7 shows a
comparison of the predicted and experimental results and the errors
between them. The error histogram in Fig. 7(b) shows that most of
the errors between the predicted and experimental results are be­
tween −0.163 and 0.2733. The largest and smallest values of the
errors are −2.125 and 2.018, respectively, whereas most error values
are approximately 0.05513. These results indicate that the predicted
results are in good agreement with the experimental results ob­
tained by running the ANN model. The good performance of this
ANN model verified that an ANN can be used to predict the pyrolysis
behaviour of biomass.
J. Li, X. Yao, S. Chen et al. Process Safety and Environmental Protection 160 (2022) 341–353

Fig. 6. Kinetic plots for pyrolysis of KS, HDPE and their mixtures.

350
J. Li, X. Yao, S. Chen et al. Process Safety and Environmental Protection 160 (2022) 341–353

Table 4
Calculation results of the activation energy.

Feedstock Coats-Redfern method Doyle method

2
E R E R2

KS 54.43 0.97965 61.78 0.98645

7KS:3HDPE Lower temperature stage 45.08 0.98507 51.99 0.98919
Higher temperature stage 143.00 0.99597 148.18 0.99659
5KS:5HDPE Lower temperature stage 47.20 0.99489 54.00 0.99614
Higher temperature stage 213.50 0.98281 218.42 0.98201
3KS:7HDPE Lower temperature stage 44.40 0.99449 51.34 0.99592
Higher temperature stage 258.92 0.9873 258.29 0.9884
HDPE 329.93 0.99783 336.11 0.99863

Fig. 7. (a) Comparison of the predicted and experimental results and (b) the corresponding error histogram.

4. Conclusion
In this paper, TG-FTIR was used to study the thermochemical
behaviour characteristics, kinetic parameters and gas evolution of KS
and HDPE pyrolysis and co-pyrolysis. In addition, an ANN model was
established to predict the TG results of KS and HDPE pyrolysis and
co-pyrolysis. The TG results showed that the initial temperature
corresponding to KS volatile release (192 ℃) was lower than that of
HDPE (438 ℃), and the temperature gradually increased with in­
creasing HDPE proportion in KS. Different from the individual pyr­
olysis, the DTG curve of the mixture co-pyrolysis has two obvious
peaks in the ranges of 200–400 ℃ and 400–600 ℃. This result in­
dicates that the mass change at lower temperatures is mainly caused
by KS decomposition, while the mass change at higher temperatures
is caused by HDPE decomposition. Moreover, index D of the feed­
stock is ranked in the order HDPE (2.40E-05) > 3KS:7HDPE (2.37E-
05) > 5KS:5HDPE (1.38E-05) > 7KS:3HDPE (8.85E-06) > KS (7.40E-
06), which shows that the introduction of HDPE decreases the dif­
ficulty of KS thermal decomposition. When studying the co-pyrolysis
behaviour of the mixture, it was found that the ΔW value of the
mixture (5KS:5HDPE) was always greater than 0, indicating that the
mixing ratio had the strongest inhibitory effects between KS and
HDPE. The ΔW values of two mixtures (3KS:7HDPE and 7KS:3HDPE)
showed a synergistic effect between KS and HDPE in the tempera­
ture range of 220–513 ℃. The synergistic effect was maximal at
472 ℃ and 479 ℃. With increasing temperature, the synergistic effect
weakens and becomes an inhibitory effect, reaching a maximum at
approximately 500 ℃.
The activation energies of KS and HDPE are 54.43 kJ/mol (Coats-
Redfern) and 61.78 kJ/mol (Doyle) and 329.93 kJ/mol (Coats-Redfern)
and 336.11 kJ/mol (Doyle), respectively. The activation energy cal­
culation of KS and HDPE co-pyrolysis was divided into two stages: a
lower-temperature stage and a higher-temperature stage. The acti­
vation energies of KS and HDPE co-pyrolysis are lower than those of
individual KS and HDPE pyrolysis at the two stages. The FTIR results
showed that the main gaseous products of KS pyrolysis are CO2
(2400–2260 cm−1 and 730–660 cm−1), CO (2186 cm−1), ketones, al­
dehydes, esters, carboxylic acids and primary amides

351
J. Li, X. Yao, S. Chen et al.
(1300–950 cm−1), light aromatics (1650–1450 cm−1), H2O
(4000–3500 cm−1) and tertiary alcohols (3620–3540 cm−1). The main
gaseous products of HDPE pyrolysis are alkanes and alkenes
(3200–2800 cm−1) and compounds containing aromatic rings
(1485–1445 cm−1 and 1680–1620 cm−1). There is always an inhibitive
effect in the co-pyrolysis of 3KS:7HDPE. With decreasing HDPE
proportion, there is a synergistic effect corresponding to gaseous
products including hydrocarbons, C]O-containing species, phenols,
alcohols and aromatics. More importantly, the established ANN
model showed good performance for predicting the thermochemical
behaviour of the feedstock, with an R2 value of 0.9999.
Declaration of Competing Interest
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This research work was funded by Natural Science Foundation of
China (52004055), Natural Science Foundation of Liaoning Province
(2021-MS-103), and Fundamental Research Funds for the Central
Universities (N2101004).
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