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PII: S0360-5442(19)32240-6
DOI: https://doi.org/10.1016/j.energy.2019.116545
Reference: EGY 116545
Please cite this article as: Hassan H, Hameed BH, Lim JK, Co-pyrolysis of sugarcane bagasse and
waste high-density polyethylene: Synergistic effect and product distributions, Energy (2019), doi: https://
doi.org/10.1016/j.energy.2019.116545.
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Abstract
(HDPE) was performed in a fixed-bed reactor under different temperatures (400–700 °C) and
blending ratios (0–100%). Product yields and chemical compositions were compared with
those from the pyrolysis of individual components to ascertain the synergistic effect between
SCB and HDPE. The synergistic effect of SCB and HDPE produced higher liquid yield than
the theoretical value. The effect was strongest at 600 °C and 60:40 HDPE:SCB ratio, with the
maximum difference of 6.02 wt%. The positive synergistic effects on the production of high-
oxygenated compounds were most prominent at 600 °C and 40:60 HDPE:SCB ratio. SCB-
derived hydroxyl radicals favored the secondary cracking of HDPE primary volatiles, thereby
1
promoting the formation of aliphatic compounds with lower carbon numbers. Co-pyrolysis of
SCB and HDPE also produced oil with higher carbon (34% higher) and hydrogen (47%
higher) contents, and with lower oxygen content (70% lower) than those of SCB pyrolysis
oil. It also achieved a high calorific value of 42.41 MJ/kg, which is comparable to those of
1. Introduction
Given the annual increase of global energy demand for nonrenewable fossil fuels,
shortage of supply is expected in the near future, thereby resulting in a global energy crisis.
The United States Energy Information Agency announced that the diminishing coal and crude
oil reserves are expected to be depleted by 2112 and 2042, respectively, while the world’s
energy demand will increase by 56% in 2040 [1]. As a source of renewable energy, biomass
has attracted considerable attention over the last three decades because of its availability, low
cost, and environmental benefits. Given that biomass is abundant and cheap, its exploitation
for energy production can help mitigate the issue of global warming because CO2 emission
resulting from biomass combustion can be used to grow back biomass through photosynthesis
[2,3].
In Malaysia, approximately 168 million tons of biomass, which includes oil palm
waste, sugarcane bagasse (SCB), rice husks, coconut trunk fibers, and timber and municipal
energy sources is predicted to be obtained from biomass by 2030 [4]. Sugarcane cultivation is
a major sector that contributes waste for biomass energy. In fact, more than 700,000 tons of
SCB is produced yearly in the vast sugarcane plantation areas in Northern Malaysia [5]. This
2
amount accounts for 30% to 40% of the by-products from sugar production, thereby making
additive in the construction industries and as a main source of biofuel [6,7]. SCB is a fibrous
solid residue extracted from sucrose-rich juice of stalks and is a potential feedstock for
biofuel production due to its high volatile matter content of nearly 80% (w/w) [8].
in waste treatment due to its capacity to convert biomass into valuable bio-oil, and this
advantages [9,10]. Biomass-derived bio-oil is high in acidity, reactivity, and viscosity but low
in calorific value and combustion efficiency compared with conventional oils; unfortunately,
these properties hinder the application of biomass-derived bio-oil as a direct fuel [11]. To
overcome this challenge, researchers consider the co-pyrolysis of biomass with plastic as an
alternative technique to upgrade the quality of bio-oil. Plastics generally contain numerous
hydrogen atoms and nearly zero oxygen atoms. During co-pyrolysis, plastic can act as a
hydrogen donor to the biomass to balance the oxygen, carbon, and hydrogen percentages in
the feedstock, leading to a positive synergistic effect on the improvement of the bio-oil
quality [12–14].
hydrogen donor due to its high hydrogen-to-carbon effective ratio (H/Ceff). HDPE can be
bottles, oil containers, milk bottles, and toys, making it the third largest plastic type found in
municipal solid waste (MSW) worldwide [15]. In Malaysia, approximately 26,000 tons of
solid wastes are generated daily. Plastic is a common solid waste found in MSW, contributing
approximately 7% to 12% by weight and 18% to 30% by volume to the total waste generated
3
by Malaysian residents [16]. Utilization of plastic wastes as feedstock for the production of
bio-oil can be an effective solution not only for reducing the volume of waste produced and
the dependence on fossil fuels, but also for recovering energy and chemicals.
The quality and quantity of pyrolysis oil were enhanced due to the synergistic effect
between plastics and biomass [17,18]. Such effect was influenced by the type of feedstock
and reaction conditions, including temperature, heating rate, and contact time [19]. Onal et al.
[20] examined the synergistic effect on the composition and product yield of the co-pyrolysis
of almond shell and HDPE. They highlighted that the liquid product yield was greatly
enhanced by 13.22% compared with the theoretical values. This co-pyrolysis oil also
presented higher hydrogen (78% higher) and carbon content (26% higher), lower oxygen
content (86% lower), and higher calorific value (38% higher) than oil from the pyrolysis of
almond shells only. Yuan et al. [21] studied the synergistic effects in the co-pyrolysis of
HDPE and cellulose at various blending ratios. They reported that the synergistic effects
significantly enhanced the generation of small volatile molecules, such as CO2, CO/C2H4, and
H2O, when the cellulose-to-HDPE ratio was 1:3. In addition, these effects inhibited the
Inspired by waste-to-energy concepts, this study aims to utilize SCB and waste HDPE
for co-pyrolysis oil production. SCB and HDPE co-pyrolysis was conducted in this research
in a fixed-bed reactor, and the effects of reaction temperature and blending ratio on the
product distributions (product yield and chemical compositions) and the magnitude of
synergistic effects were evaluated. Moreover, the physical and chemical properties of co-
pyrolysis oil obtained under optimum conditions were characterized to determine its
4
2. Materials and methods
SCB and recycled HDPE waste were selected as feedstock. SCB was obtained from
the local market. Prior to use, it was dried (80 °C for 24 h), smashed, ground, and sieved to
produce particles of sizes from 500 µm to 1 mm. Detergent bottles that are plastic wastes
produced from HDPE were obtained from the household trash collection in Penang. The
collected plastics were cut into small pieces, ground, and sieved with a mesh screen to obtain
Proximate analysis of the SCB and HDPE samples was conducted using the standard
nitrogen, and sulfur were determined using the CHNS Elemental Analyzer (Perkin Elmer
Series, Model 2400). The weight loss and thermal behavior of individual SCB and HDPE
samples were examined using the PerkinElmer TGA 7 apparatus. The high heating values
(HHVs) of the liquid products were measured using the IKA C200 bomb calorimeter
according to ASTM D240-02. Various compounds in the co-pyrolysis oil were separated and
600/600T) equipped with a HP-5MS capillary column (30 mm × 0.25 mm × 0.25 µm) and a
mass selectivity detector. The injection temperature was 250 °C. A split ratio of 2:1 was
applied. The oven temperature was first maintained at 50 °C for 2 min holding time, then
increased to a final temperature of 280 °C at a ramping rate of 3 °C/min that was maintained
for 20 min. The MS was operated at 70 eV ionization energy with mass-to-charge ratio (m/z)
in the range of 50–400. The components were examined using the mass spectral library
5
(NIST08), and the relative concentration of components was calculated after the
The synergistic effect during the co-pyrolysis of SCB and HDPE can be measured by
comparing the experimental and the theoretical values (YTheo, mix) calculated from the
,
= (
. +
. ), (1)
where and represent the mass fractions of SCB and HDPE in the mixture samples,
respectively. and are the respective yields of the product (oil, char, and gas) for SCB
=
.
− .
. (2)
where YExp, mix and YTheo, mix represent the experimental and theoretical values of co-pyrolysis.
YDifference > 0 indicates the enhancing effect of co-pyrolysis, whereas YDifference < 0 indicates
Pyrolysis and co-pyrolysis were both performed in a stainless steel fixed-bed reactor
with diameter and height of 25 and 700 mm, respectively, and under atmospheric pressure.
The reactor was heated with an electric furnace with a heating element surrounding the
reactor. The temperature was measured using a K-type thermocouple inside the reactor. The
PID controllers of the reactor and the furnace were synchronized to ensure that the set
temperature for the reactor and furnace was maintained throughout the experiment.
6
Approximately 0.1 g of quartz wool was loaded into the reactor to support the bed,
and then 6.0 g of samples (HDPE, SCB or the HDPE–SCB mixture at a mass ratio of 40:60)
was placed inside the reaction chamber. The reactor was sealed tightly at the top of the
reaction chamber fixed with the inert gas flow line. The K-type thermocouple was inserted
into the reactor bed. Then, nitrogen gas (99.99% pure) was introduced into the reactor at 250
mL/min for 15 min to create an inert environment. Such environment is crucial before
pyrolysis occurs. In the co-pyrolysis experiment, the reaction time was set at 45 min on the
basis of previous optimization, while the temperature was varied from 400 °C to 700 °C at a
heating rate of 10 °C/min. The blending ratio was varied from 0% to 100% of the individual
SCB and HDPE. The optimum temperature and blending ratio were selected according to the
The separation and collection of pyrolysis oil consisted of two stages, similar to the
configuration reported by Xue et al. [14] and Gunasee et al. [23]. The first collector (the so-
called wax trap) was attached to the bottom of the pyrolysis tubular reactor chamber, and the
temperature was maintained at 170 °C with a wax trap heater. The pyrolysis vapor was
an ice cube bath. The pyrolysis oil in this study consisted of organic and aqueous phases. The
organic phase was characterized by a waxy texture with high viscosity and dark color, and the
aqueous phase was light yellow in color and was less viscous than the organic phase due to
its high water content (Fig. S1). The gaseous products were collected in gas bags through the
vent valve during experiments. At the end of the reaction, the furnace was shut off, the
reactor was cooled to room temperature, and nitrogen gas flow was maintained to prevent
char oxidation. The liquid in the collectors and the remaining char in the reactor were
recovered and weighed. Between experiments, the reactor, condenser, and piping system
were washed several times with acetone to remove solid residues that may contaminate the
7
samples. The pyrolysis experiments were repeated thrice to ensure reproducibility, and all the
values presented were averaged. Good reproducibility of each data was achieved, with the
standard deviation of less than 5%, as calculated through the STDEV function in Excel.
Table 1 shows the proximate and ultimate compositions of the SCB and HDPE
feedstock. Both SCB and HDPE can be promising sources of energy because of their high
volatile matter contents of 71.79 and 100 wt%, respectively. High volatile matter content is
favorable for the production of high-quality pyrolysis oil due to its high volatility and
reactivity that facilitate their conversion into pyrolysis oil [24,25]. Generally, a feedstock
with higher C and H content and lower O content is useful for obtaining high hydrocarbon
yield with less oxygenated compound content in pyrolysis oil [26]. HDPE as a polyolefinic
polymer has higher C and H contents and no O content compared with SCB, which could be
easily transformed into hydrocarbon fuels (Table 1). Considering its high H/Ceff , HDPE acts
as a hydrogen donor to the biomass-derived free radical pool or reacts directly with
oxygenates to hydrocarbon [27]. The low high heating value (HHV) of SCB (19.01 MJ/kg) is
due to its high O content compared with its H and C contents. The proximate and ultimate
Temperature and heating rate are critical parameters that influence the generation of
volatile matter. Fig. 1 (a) presents the experimental and theoretical product yields derived
8
from SCB and HDPE at different reaction temperatures. The reaction time and SCB-to-
HDPE blending ratio were fixed at 45 min and 60:40. The experimental yield of the liquid
increased from 49.82 wt% to 63.69 wt%, with the increase in temperature from 400 °C to 600
°C, before levelling off to 60.72 wt% at 700 °C. Moreover, at a higher temperature, linear and
branched hydrocarbons had lower thermal stability; thus, C=C bond cracking tended to occur,
consequently increasing the yield of volatile compounds that favor pyrolysis oil production
[24]. The slight decrease in pyrolysis oil at 700 °C can be attributed to the secondary cracking
of primary volatiles that promoted the generation of gases. Conversely, the char yield
decreased with the increase in temperature from 400 °C to 700 °C. This scenario is either due
to (1) the primary decomposition of the SCB lignocellulosic structure or (2) the secondary
decomposition of the primary volatiles on the primary char, promoting the generation of more
condensable and noncondensable vapors [29]. The inhibition of char yield at a high
temperature (500–700 °C) favored the increase in gas yield, thereby reaching a maximum
yield of 21.33 wt% at 700 °C. This result may be attributed to the strong cracking of the
liquid component C–C bond into short-carbon-chain components that promote the production
For discussing the synergistic effect during SCB and HDPE co-pyrolysis in detail,
Fig. 1(b) depicts the differences between the experimental and theoretical yields at different
reaction temperatures. The yields of pyrolysis oil were higher than those of the theoretical
values, except for 700 °C. Furthermore, the maximum difference reached 4.24 wt% at 600
°C, thereby indicating that the influence of the synergistic effect in pyrolysis oil production
was the strongest at this temperature. The positive synergistic effect on liquid yield during
SCB and HDPE co-pyrolysis could be attributed to the interaction between the HDPE-
derived H radical and the SCB-derived radical; such interaction inhibited the generation of
low-molecular-weight gaseous product and enhanced the formation of oil with high-
9
molecular-weight organic compounds, subsequently resulting in a high yield of pyrolysis oil
at 600 °C [12]. In addition, the experimental char yields were higher than the theoretical
values, except for the yields at 700 °C. The highest difference also reached 20.07 wt% at 400
°C and might be due to the suppression of the cross-reaction between the HDPE-derived H
radical and the SCB-derived radical [31]. Such cross-reaction interfered with the stabilization
of the primary products from cellulose thermal degradation, resulting in high char formation
[31]. An opposite trend was observed for the gas yield. The gas yields were lower than the
theoretical values, and the difference reached a maximum of −24.09 wt% at 400 °C.
Compared with HDPE, SCB started to decompose at a low temperature (200 °C) whereas
HDPE decomposition started at 430 °C (Fig. S2). At a relatively low temperature (400 °C),
only the cellulose and hemicellulose constituents of SCB with a small fraction of HDPE
underwent thermal decomposition. The HDPE melted into the SCB and prevented the
volatiles produced by SCB pyrolysis from escaping [31], consequently causing low gas
The relative contents of each chemical compound in the pyrolysis oil were evaluated
on the basis of the percentage areas of the chromatographic peaks obtained by GC–MS. The
compositions of the pyrolysis oil were on a water-free basis, and the water content of the
pyrolysis oil was 11.29%. The main compounds present in the pyrolysis oil can be classified
into eight main functional groups as follows: sugar, ester, alcohol, carbonyl (aldehyde and
ketone), acid, aromatics, hydrocarbons (alkane, alkene, and alkyne), and other nitrogen-
aromatics are high-value organic chemicals for biofuel production. Conversely, oxygenated
compounds such as acids, esters, ethers, aldehydes, and ketones can be undesirable products.
Acids mainly contribute to corrosiveness, whereas ether and esters are related to the
10
decreased heating value of pyrolysis oil. Ketones and aldehydes are responsible for the
compounds are harmful to the environment [32]. Fig. 2(a) reveals the effect of reaction
temperature on the theoretical and experimental chemical compounds from the co-pyrolysis
of SCB and HDPE. The sugar compounds increased dramatically from 2.36% to 30.28% as
the temperature increased from 400 °C to 500 °C and vanished at 700 °C. The acid yield
decreased significantly from 45.23% to 2.60%, with increasing reaction temperature from
400 °C to 600 °C and increased to 7.42% at 700 °C due to the secondary cracking reactions
favored at high temperature. The hydrocarbon and alcohol values increased with the
increased temperature from 400 °C to 600 °C before reaching a plateau value at 700 °C. High
hydrocarbon content can be attributed to the fact that the end-chain fission and β-scission
reactions for long-chain hydrocarbons derived from HDPE thermal degradation were favored,
owing to the increased activation energy at high temperature, thereby resulting in its
Fig. 2(b) shows the difference between experimental and theoretical values at
different reaction temperatures. Alcohol is mainly produced from the secondary reaction of
experimental values of alcohol were higher than the theoretical values and indicated that the
synergistic effect during SCB and HDPE co-pyrolysis promoted the secondary reaction of
levoglucosan to form alcohol. The maximum difference of 34.16% could be reached at 600
°C. For the hydrocarbons, the experimental values were higher than the theoretical values at
500 and 600 °C, and the maximum difference could reach 5.37% at 600 °C. Conversely, the
experimental values for the acid groups were initially higher than the theoretical values at a
lower temperature (400 °C). Later, the results were reversed as the temperature increased,
11
carboxylic acid into aliphatic hydrocarbon via decarboxylation for which oxygen was
Regarding the sugar compounds, the experimental values were significantly lower
than the theoretical counterparts when the reaction temperature was 600 °C, with a maximum
difference of −23.76%. However, at 400 and 700 °C, the synergistic effects for the sugar
compounds were not evident because of the small difference between the experimental and
theoretical values. Notably, no sugar was observed at 700 °C due to the secondary
decomposition of the primary sugar, that is, levoglucosan, to alcohol via decarbonylation.
This trend was corroborated by the increased alcohol content at 700 °C. In contrast, the
experimental values of nitrogen-containing compounds were higher than the theoretical ones,
except at 600 °C, with the maximum difference of 12% at 400 °C. For the esters, the
experimental values were lower than the theoretical values, thereby indicating that the
synergistic effect during SCB and HDPE co-pyrolysis inhibited the production of ester and
that the maximum difference of −19.92% at 400 °C. For the carbonyls, the synergistic effect
toward the production of carbonyl was initially negative with an increased temperature from
400 °C to 600 °C and was later positive as the temperature reached 700 °C due to the
cleavage of ketone and aldehyde from benzene derivatives with the maximum difference of
2.90 at 700 °C. The increase in carbonyl contents resulted in the decrease of aromatic content
at 700 °C. Aromatic derivatives, namely, phenol and furan, are the products of lignin
degradation that occurred in a wide temperature range of 200–600 °C. According to Fig. 2(a),
the experimental yield of aromatics was higher than its theoretical yield at 600 °C, with the
maximum difference of 4.22%. Thus, 600 °C was optimal for lignin degradation where the
aromatic derivatives were produced at the maximum rate. After considering both pyrolysis oil
yields and chemical composition, 600 °C was selected as the best reaction temperature for
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3.4 Co-pyrolysis product yield at different blending ratios
The HDPE-to-SCB ratios in the feedstock varied at 0:100, 20:80, 40:60, 60:40, and 100:0 at a
fixed reaction temperature of 600 °C and a reaction time of 45 min. Fig. 3 (a) depicts the
experimental and theoretical product distributions obtained from the thermal decomposition
of individual SCB and HDPE samples, as well as their binary mixture. As the HDPE ratio in
the feedstock increased, the pyrolysis oil yields considerably increased, whereas the gas
yields decreased gradually. During co-pyrolysis, polyolefin polymers, such as HDPE, act as
hydrogen donors for biomass to enhance the pyrolysis oil production. Increasing the ratio of
HDPE increased the H/C ratio in the mixture; thus, more hydrogen transferred from HDPE to
react with the SCB-derived radicals. This reaction stabilized the primary product of SCB
decomposition and increased the fraction of condensable gases that can be converted into
pyrolysis oil. The solid yield showed an opposite trend with further decrease in char yield
from 23.12 wt% to 0 wt% with an increase in HDPE ratio. This phenomenon can be
attributed to the cracking effect undergone by SCB-derived char that promoted further
decomposition of SCB, resulting in a decreased char yield. Pyrolysis of HDPE alone yielded
no char, owing to the absence of fixed carbon content present in HDPE [20].
Fig. 3(b) shows the difference between the experimental and theoretical yields at
different blending ratios. The HDPE ratio in the feedstock increased, the experimental oil
yield was greater than the theoretical yield, and the experimental gas yield was lower than the
theoretical yield. Therefore, a synergistic effect occurred on SCB and HDPE co-pyrolysis,
thereby resulting in high pyrolysis-oil yield and low gas yield. The synergistic effect on the
production of pyrolysis oil was significant at the HDPE:SCB ratio of 60:40, with the
maximum difference of 6.02 wt%. These results are in good agreement with those from Chen
et al. [12], who reported that the highest synergistic effect on the oil yield was obtained under
13
the highest plastic ratio. For solids, the difference between the experimental and estimated
data was minimal, suggesting that the effect of the interaction between SCB and HDPE on
Fig. 4(a) shows the effect of the HDPE content on the theoretical and experimental
chemical compounds from SCB and HDPE co-pyrolysis. SCB pyrolysis generated 43.35% of
sugar, 30.60% of acid, 8.37% of aromatic, 6.59% of ester, and small amounts of alcohol and
aromatic compounds. Acid mainly came from the depolymerization and fragmentation of the
cellulose and hemicellulose components of the SCB material. Hydrocarbon and alcohol are
the major products of HDPE degradation, with the area percentage of 68.76% and 20.22%,
respectively. Overall, the composition of co-pyrolysis oil resembled that of HDPE oil.
Fig. 4(b) shows the difference between the experimental and theoretical results of the
chemical compositions at different blending ratios. The experimental values of alcohol were
larger than the theoretical values with increased HDPE fraction, with the maximum
difference of 34.16% at the HDPE:SCB ratio of 40:60. High concentrations of linear long-
chain alcohol compounds (Table S1) could be attributed to the interaction between HDPE-
derived H radical and SCB-derived hydroxyl radical [17]. The hydroxyl radical that favored
the formation of alcohol could be formed by the β-scission of a tertiary carbon radical in any
of the first to the fifth position in the cellulose structure during dehydration reaction. For the
hydrocarbon, the experimental values were higher than the theoretical counterpart when the
HDPE ratio was at 20% and 40%, but they became lower than the theoretical values when the
HDPE ratio exceeded 40%. Thus, the synergistic effect on hydrocarbon production during the
SCB and HDPE co-pyrolysis can be positive or negative depending on the blending ratio
between SCB and HDPE. The maximum difference of hydrocarbon reached 5.37% at the
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HDPE:SCB ratio of 40:60, possibly due to the oxygen-containing compounds and reactive
free radical derived from cellulose decomposition that promoted the secondary cracking of
HDPE primary products, resulting in the formation of more light hydrocarbons [33]. The
acid contents, thereby suggesting that the synergistic effect promoted deoxygenation
aliphatic hydrocarbon. This fact is supported by the maximum inhibition effect of the acid
(−18.41%) at the HDPE:SCB ratio of 40:60. Decreased acid compounds are desirable for
improving the fuel and chemical properties of pyrolysis oil by enhancing stability, calorific
value, and combustion efficiency, as well as lowering the rate of aging and corrosion
problems during storage [34,35]. For the ester and carbonyl compounds, small differences
were observed between the experimental and theoretical values. For the nitrogen-containing
group, negative synergistic effects were observed at all HDPE ratios, with the maximum
difference reaching −1.28% at the HDPE:SCB ratio of 60:40, thereby indicating that the
synergistic effect on the production of aromatic compounds became noticeable only at the
The addition of HDPE to SCB significantly changed the relative distribution of sugar
compounds. The relative yield of experimental values was lower than that of the theoretical
values when the HDPE ratios were at 20% and 40%. Notably, the sugar compound was
nearly eliminated from the pyrolysis oil at the HDPE:SCB ratio of 40:60 and demonstrated a
difference of −23.76%. Thus, the effect of hydrogen supplied by HDPE from the midchain β-
compounds (such as ketones and aldehydes) that can be decomposed further to other
hydrocarbons [12]. However, given that the HDPE content increased to 60%, the sugar
15
compounds increased progressively to 33.61%, implying that the effect of the secondary
The chemical pathways for the co-pyrolysis of SCB and HDPE could be explained by
the mechanism proposed by previous researchers [17,21]. Compared with HDPE, SCB was
decomposed earlier due to its lower decomposition temperature. The thermal decomposition
of SCB produced numerous oxygen-containing compounds, such as sugar and acid, and a few
hydrocarbons and aromatics. At this stage, many reactive free radicals, such as the hydroxyl
radical (·OH), could be produced from thermal decomposition of SCB. The SCB-derived
oxygenated compounds and reactive free radicals initiated the depolymerization of HDPE by
the abstraction of hydrogen to generate the different chain lengths of aliphatic hydrocarbons
(alkane and alkene) with activated H radical. The H radical derived from HDPE
polymerization could interact with the SCB-derived hydroxyl radical, resulting in the
(C20H42O). Furthermore, the SCB-derived hydroxyl radicals favored the secondary cracking
of HDPE primary volatiles, thereby promoting the formation of aliphatics with a lower
carbon number. Hydrogen supplied by the HDPE from the midchain β-scission reaction
promoted the degradation of acid and sugar via decarboxylation and decarbonylation
reactions, where oxygen was removed as CO2 and CO, respectively. High hydrocarbon
content leads to higher H, C, H/C ratios and heating value in the experimental values, relative
to the theoretical values (Table 2). HHV is beneficial for engine performance because of its
increased thermal efficiencies and power outputs [2]. Moreover, low oxygenated compounds
A mixture of 40% HDPE and 60% SCB was selected as the optimum blending ratio
because this combination yielded the highest hydrocarbon and alcohol contents with the
minimum oxygenated compound in the produced liquid oil, along with a reasonable yield.
16
3.6 Properties of pyrolysis oil
Table 2 presents the elemental composition and heating values of pyrolysis oil
obtained from SCB alone, HDPE:SCB mixture, and commercial automotive diesel fuels. The
pyrolysis oil from the SCB and HDPE co-pyrolysis exhibited high percentages of C and H
with low percentages of O and N compared with the SCB pyrolysis oil. The H/C ratio
increased from 1.03 to 1.77 with the addition of HDPE, whereas the oxygen content of co-
pyrolysis oil (11.84 wt%) considerably lowered compared with the individual SCB-derived
oil (39.56 wt%). In addition, the percentages of C, H, and H/C ratios and calorific value
derived from the SCB and HDPE co-pyrolysis were higher than the theoretical values,
whereas the percentages of O, S, and N were lower than the theoretical values. Furthermore,
pyrolysis oil from the SCB and HDPE co-pyrolysis exhibited an elevated calorific value
(42.05 MJ/kg) compared with its counterpart from SCB alone (20.26 MJ/kg). This high
calorific value can be attributed to high hydrocarbon and low acid and sugar contents in the
pyrolysis oil; these features are beneficial for enhancing the quality of the pyrolysis oil and
reducing the costs related to catalytic hydrodeoxygenation to increase the fuel stability for an
enhanced performance during fuel combustion [36]. This heating value is comparable to that
of commercial automotive diesel fuels (42–46 MJ/kg) [12,37]. The high calorific value made
pyrolysis oil a promising fuel for use in modified internal combustion engines because of its
high thermal efficiencies and power outputs [38]. Therefore, blending of HDPE with SCB
can effectively convert pyrolysis oil into a compatible fuel that can be used in modified
Pyrolysis oils from SCB, HDPE, and their HDPE:SCB blend with a ratio of 40:60
were analyzed by GC–MS. Figs. 5 (a) to (c) illustrate the chromatograms. The relative
contents of the main compounds were denoted as the area (%) associated with the total ion
intensity (Table S1). The major compounds from SCB decomposition were sugars (43.35%)
17
and acids (30.60%), and the other compounds included hydrocarbon (8.37%), ester (6.59%),
(Table S1). Pyrolysis oil from SCB degradation contained high concentrations of oxygenated
compounds, such as sugar and acids, due to cellulose and hemicellulose degradation.
mannose, galactose, and glucose, and it yields various products. Sugar derivatives [for
Meanwhile, carboxylic acids, such as hexadecanoic, formic, and propanoic acids, are
hydrocarbon mixture mainly comprising alkenes (67.32%) and alkanes (1.44%). Variation in
the hydrocarbon constituents of the HDPE-derived oil indicates the presence of a series of
saturated and unsaturated hydrocarbons that resulted from random scissions of the original
polymer chains of the HDPE structure [12]. Yuan et al. [21] claimed that HDPE is
decomposed by radical chain, β-scission, and hydrogen chain reactions that lead to the
Alcohol (44.78%) and hydrocarbon (37.89%) were the major compounds detected in
co-pyrolysis oil (Table S1). High concentrations of linear long-chain alcohol compounds,
oil. Hydrocarbon compounds in co-pyrolysis oils consist of linear hydrocarbons with carbon
numbers ranging from C12 to C27. The co-pyrolysis oil can be a precursor for diesel-like
fraction due to the presence of hydrocarbon products in the range of C13–C25; these
18
heneicosane (C21), tridecene (C13), octadecene (C18), nonadecene (C19), eicosene (C20), and
docosene (C22) [39]. Hydrocarbons are the most desirable components in pyrolysis oil
because of their HHV and octane number [40]. Conversely, alcohols can act as excellent
additives to petroleum fuels for enhancing fuel octane number, contributing to the increase of
compounds in pyrolysis oil improve the viscosity and stability of the pyrolysis oil [41].
Sugar and acid were nearly absent in the co-pyrolysis oil with the HDPE:SCB ratio of
40:60 at 600 °C. Depolymerization of cellulose occurred at a temperature below 300 °C and
4. Conclusion
The co-pyrolysis of SCB and HDPE was carried out in a fixed-bed reactor to
investigate the product distributions and synergistic effects at various reaction temperatures
and blending ratios. The synergistic effect of SCB and HDPE produced a higher liquid yield
than the theoretical value. The effect was strongest at 600 °C and 60:40 HDPE:SCB ratio
with the maximum difference of 6.02 wt%. The strongest synergistic effects on the
production of alcohol, hydrocarbon, and aromatics, as well as the inhibition of acid and sugar,
with the maximum difference of 34.16%, 5.37%, 4.22%, −18.41%, and −23.76%,
respectively, were achieved at a temperature of 600 °C and HDPE:SCB ratio of 40:60. The
interactions of the hydroxyl radical from the initial decomposition of cellulose with the H
radical generated from the random scission of the original polymer chains in the HDPE
structure led to the formation of linear long-chain alcohol compounds. The hydroxyl radical
19
generated from the thermal decomposition of SCB favored the secondary cracking of HDPE
primary volatiles, thereby promoting the formation of aliphatic compounds with shorter chain
lengths. Hydrogen supplied by HDPE from the midchain β-scission reaction promoted the
respectively, where oxygen was removed as CO2 and CO. The calorific value of pyrolysis oil
from SCB and HDPE co-pyrolysis was comparable to that of commercial diesel. Co-pyrolysis
oil can be a precursor for diesel-like fraction, owing to the presence of hydrocarbon products
in the range of C13–C25, which enhances the fuel potential of pyrolysis oil.
Acknowledgements
The first author acknowledges the scholarship support from the Ministry of Higher
Education (MOHE), Malaysia. The authors acknowledge the research grants provided by the
Universiti Sains Malaysia, Malaysia, under Research University (RU) TOP-DOWN grant
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Figure captions:
Fig. 1: (a) Effect of reaction temperature on the experimental and theoretical product yields
derived from the SCB and HDPE co-pyrolysis. (b) Difference between experimental
Fig. 2: (a) Effect of reaction temperature on the experimental and theoretical chemical
composition from the SCB and HDPE co-pyrolysis. (b) Difference between
40:60).
Fig. 3: (a) Effect of blending ratio on the experimental and theoretical product yields derived
from the SCB and HDPE co-pyrolysis. (b) Difference between experimental and
Fig. 4: a) Effect of blending ratio on the experimental and theoretical chemical compositions
from the SCB and HDPE co-pyrolysis. (b) Difference between experimental and
Fig. 5: GC–MS chromatograms of the pyrolysis oil (a) SCB; (b) HDPE; (c) HDPE:SCB
(40:60) (Reaction conditions: temperature of 600 °C; reaction time of 45 min). The
labelled number represents the compounds present in pyrolysis oil (Table S1 in SD).
27
List of Tables
Table 2: Elemental composition and heating values of pyrolysis oil obtained from individual
28
Table 1:
SCB HDPE
a
Proximate analysis (wt%)
Moisture 10.91 -
Volatiles 71.79 100
Fixed carbonb 11.33 -
Ash 5.97 -
Ultimate analysis (wt%)c
C 42.07 84.89
H 5.60 14.19
N 0.26 0.38
S 0.06 0.54
O (by difference) 52.01 0.00
H/C molar ratio 1.60 2.01
O/C molar ratio 0.93 0
HHV (MJ/kg) 19.01 51.32
a
As received basis.
b
Calculated by difference.
c
Dry basis and ash-free.
33
Table 2:
HDPE:SCB (40:60)
Component (wt%) SCB HDPE Experimental Theoretical Commercial
Diesel [13]
C 55.06 85.42 76.61 67.20 84-87
H 4.71 14.30 11.29 8.55 11-15
N 0.56 0 0.13 0.34 0.01-0.3
S 0.11 0.28 0.13 0.18 -
O (by difference) 39.56 0 11.84 23.74 0
H/C molar ratio 1.03 2.01 1.77 1.42 -
O/C molar ratio 0.54 0 0.12 0.32 -
HHV (MJ/kg) 20.26 43.2 42.05 29.44 42-46
34
100
(a)
Exp. liquid Exp. char Exp. gas
Theo. liquid Theo. char Theo. gas
75
Yield (wt%)
50
25
0
400 500 600 700
Temperature (°C)
25
20 (b) Liquid Char Gas
Difference in yield (wt%)
15
10
5
0
-5
-10
-15
-20
-25
400 500 600 700
Temperature (°C)
Fig. 1
28
160
T
h (a) Sugar Ester
140
e Alcohol Carbonyl
o Acid Hydrocarbon
.
120 Aromatic Nitrogenated compounds
Area percentage (%)
80
(b) Sugar Ester
Alcohol Carbonyl
60
Acid Hydrocarbon
Aromatic Nitrogenated compounds
40
Difference area (%)
20
-20
-40
-60
400 500 600 700
Temperature (°C)
Fig. 2
29
100
(a) Exp. liquid Theo. liquid
Exp. char Theo. char
80 Exp. gas Theo. gas
Yield (wt%)
60
40
20
0
00:100 20:80 40:60 60:40 100:00
HDPE:SCB ratio
8
(b) Liquid Char Gas
6
Difference in yield (wt%)
4
2
0
-2
-4
-6
-8
-10
20:80 40:60 60:40
HDPE:SCB ratio
Fig. 3
30
160
(a)
140
120
100
5.64
8.37
23.21 20.45 30.92
80 32.52
37.89 44.60
30.60
23.43 25.80 68.76
60
21.01 28.74
6.59 16.22
40 14.61 7.42
5.32 10.62
44.78 13.82 6.63
20 43.35
30.86 34.68 26.01
33.61
17.34 20.22
0
00:100 20:80 40:60 60:40 100:00
HDPE: SCB ratio
40
(b) Sugar Ester
30 Alcohol Carbonyl
Acid Hydrocarbon
20 Aromatic Nitrogenated compounds
Difference area (%)
10
-10
-20
-30
20:80 40:60 60:40
HDPE:SCB ratio
Fig. 4
31
58
100
(a) SCB
80
58
Area peak (%)
60
58
40
59
20
57 57
42
0
3.45 8.45 13.45 18.45 23.45 28.45 33.45 38.45 43.45 48.45 53.45 58.45 63.45
Time (min)
31
100
(b) HDPE
80
Area peak (%)
22 21
60 21
17 22
40
20
20 19 51
16
15
0
3.45 8.45 13.45 18.45 23.45 28.45 33.45 38.45 43.45 48.45 53.45 58.45 63.45
Time (min)
100 22
9 31
(c) HDPE: SCB (40:60) 31
80
10
Area peak (%)
60 8
36
40 32
8
22
11
20 56
0
3.45 8.45 13.45 18.45 23.45 28.45 33.45 38.45 43.45 48.45 53.45 58.45 63.45
Time (min)
Fig. 5
32
Research highlights
• Co-pyrolysis enhanced the liquid yield and production of alcohol and hydrocarbon.