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Co-pyrolysis of sugarcane bagasse and waste high-density polyethylene: Synergistic

effect and product distributions

H. Hassan, B.H. Hameed, J.K. Lim

PII: S0360-5442(19)32240-6
DOI: https://doi.org/10.1016/j.energy.2019.116545
Reference: EGY 116545

To appear in: Energy

Received Date: 23 August 2018

Revised Date: 27 September 2019
Accepted Date: 12 November 2019

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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 Co-pyrolysis of sugarcane bagasse and waste high-density polyethylene: Synergistic

effect and product distributions

H. Hassana,b, B.H. Hameedc,*, J.K. Lima

a
School of Chemical Engineering, Engineering Campus,

Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia

b
Faculty of Chemical Engineering, Universiti Teknologi MARA (UiTM) Malaysia,

Permatang Pauh 13500 Penang, Malaysia

c
Department of Chemical Engineering, College of Engineering,
Qatar University, P.O. Box: 2713, Doha, Qatar

*
Corresponding author. Tel.: +974 4043 4142

E-mail address: b.hammadi@qu.edu.qa (B.H. Hameed)

Abstract

Co-pyrolysis of sugarcane bagasse (SCB) with waste high-density polyethylene

(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-

value organic compounds (alcohol, hydrocarbons, and aromatics) and inhibition of

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

commercial diesel fuels.

Keywords: sugarcane bagasse, high-density polyethylene, co-pyrolysis, synergistic effect.

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

waste, is produced annually. Approximately more than 1200 MW of sustainable renewable

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

SCB an abundant waste in Malaysia. Moreover, this material is commonly used as an

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].

Biomass pyrolysis has emerged as a cutting-edge thermochemical conversion method

in waste treatment due to its capacity to convert biomass into valuable bio-oil, and this

approach is superior to other competing technologies (such as gasification and high-pressure

liquefaction) in terms of convenient process parameter manipulation and economic

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].

Meanwhile, high-density polyethylene (HDPE) can be used as a cheap and abundant

hydrogen donor due to its high hydrogen-to-carbon effective ratio (H/Ceff). HDPE can be

characterized as a high-strength plastic and is extensively used for manufacturing detergent

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

production of oxygenated compounds, such as ketone, aldehyde, furan, and carbohydrate.

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

suitability as an energy source and chemical feedstock.

4
2. Materials and methods

2.1 Feedstock preparation

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

particles with different sizes (300 µm–1 mm).

2.2 Feedstock and product characterizations

Proximate analysis of the SCB and HDPE samples was conducted using the standard

procedures described in ASTM D 7582-10. The ultimate percentages of carbon, hydrogen,

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

characterized by gas chromatography–mass spectrometry (GC–MS) (Perkin Elmer Clarus

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

normalization of the spectrum curve area.

2.3 Synergistic effect

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

individual pyrolysis of SCB and HDPE, as seen in Eq. (1) [12].

, 
= (  .  +  .  ), (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

and HDPE alone.

  =

. 
−
. 
. (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

the inhibiting effect induced by co-pyrolysis [22].

2.4 Experimental setup

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.

2.5 Pyrolysis and co-pyrolysis experiments

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

pyrolysis oil yield and organic compound composition detected by GC–MS.

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

further recovered downstream and quenched in a condenser that was maintained at −5 °C in

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.

3. Results and discussion

3.1 Feedstock characterization

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

oxygenated compounds from biomass pyrolysis, thereby enhancing the transformation of

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

composition of SCB and HDPE is consistent with those previously reported by

Ghorbannezhad et al. [8] and Chin et al. [28].

3.2 Co-pyrolysis product yield at different reaction temperatures

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

of light hydrocarbon gases (C1–C3) [30].

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

production at 400 °C.

3.3 Chemical composition of pyrolysis oil at different reaction temperatures

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-

containing compounds. Among these functional groups, alcohol, hydrocarbons, and

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

instability of bio-oil during transport and storage, whereas the nitrogen-containing

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

conversion to noncondensable hydrocarbons (C1–C3) [17].

Fig. 2(b) shows the difference between experimental and theoretical values at

different reaction temperatures. Alcohol is mainly produced from the secondary reaction of

sugar (levoglucosan) through decarbonylation and repolymerization reactions [21]. All

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,

suggesting that co-pyrolysis inhibited acid production by promoting the conversion of

11
carboxylic acid into aliphatic hydrocarbon via decarboxylation for which oxygen was

rejected in the form of CO2.

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

SCB and HDPE co-pyrolysis.

12
3.4 Co-pyrolysis product yield at different blending ratios

Blending ratio is an important parameter that influences product yield distribution.

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

the char yield was unclear.

3.5 Chemical composition of pyrolysis oil at different blending ratios

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

14
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

increase in hydrocarbon content up to 40% HDPE ratio was accompanied by a decrease in

acid contents, thereby suggesting that the synergistic effect promoted deoxygenation

reactions, such as decarboxylation of carboxylic acid, leading to the large production of

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 promoted the denitrogenation of oxygenated compounds. Conversely, the

synergistic effect on the production of aromatic compounds became noticeable only at the

HDPE:SCB ratio of 40:60, with the maximum difference of 4.22%.

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-

scission reaction favored the decomposition of sugar (levoglucosenone) to other oxygenated

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

cracking of cellulose was favored by the excess HDPE addition.

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

formation of linear long-chain alcohols, such as 1-hexadecanol (C16H34O) and 1-eicosanol

(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

enhanced the stability of the pyrolysis oil [9].

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

internal combustion engines.

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%),

alcohol (4.22%), nitrogen-containing compound (4.65%), and aromatic compounds (2.22%)

(Table S1). Pyrolysis oil from SCB degradation contained high concentrations of oxygenated

compounds, such as sugar and acids, due to cellulose and hemicellulose degradation.

Hemicellulose is a complex structure comprising different heteropolysaccharides, including

mannose, galactose, and glucose, and it yields various products. Sugar derivatives [for

example, D-turanose, heptakis(trimethylsilyl); à-D-Glucopyranoside, 1,3,4,6-tetrakis-O-

(trimethylsilyl)- á-D-fructofuranosyl 2,3,4,6-tetrakis-O-(trimethylsilyl); and Thymol-á-d-

glucopyranoside tetrakis(O-trimethylsilyl)] are generated from hemicellulose degradation.

Meanwhile, carboxylic acids, such as hexadecanoic, formic, and propanoic acids, are

produced from hemicellulose devolatilization. In contrast, HDPE pyrolysis oil is rich in

hydrocarbon compounds. Pyrolysis of polyethylene plastic-like HDPE results in a

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

generation of C3–C22 straight-chain hydrocarbons.

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,

such as 1-hexadecanol (C16H34O) and 1-eicosanol (C20H42O), were detected in co-pyrolysis

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

hydrocarbon products include tetradecane (C14), heptadecane (C17), octadecane (C18),

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

combustion efficiency. In addition to minimizing the effects of aging, high-alcohol

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

led to the formation of levoglucosan through the rupture of glycosidic linkages

(transglycosylation) between the monomer units of cellulose. The secondary reactions of

levoglucosan, such as decarbonylation and depolymerization, led to the formation of

secondary products, such as alcohol [42].

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

degradation of acid and sugar via decarboxylation and decarbonylation reactions,

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

(Project No: 1001/PJKIMIA/8070005) that resulted in this article.

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26
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

and theoretical product yields at different reaction temperatures. (Reaction conditions:

reaction time of 45 min; HDPE:SCB ratio of 40:60).

Fig. 2: (a) Effect of reaction temperature on the experimental and theoretical chemical

composition from the SCB and HDPE co-pyrolysis. (b) Difference between

experimental and theoretical chemical compositions at different reaction

temperatures. (Reaction conditions: reaction time of 45 min; HDPE:SCB ratio of

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

theoretical product yields at different blending ratios. (Reaction conditions: reaction

time of 45 min; reaction temperature of 600 °C).

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

theoretical chemical compositions at different blending ratios. (Reaction conditions:

reaction time of 45 min; reaction temperature of 600 °C).

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 1: Proximate and ultimate analyses of raw materials.

Table 2: Elemental composition and heating values of pyrolysis oil obtained from individual

SCB, HDPE:SCB blending, and commercial diesel.

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 (%)

Exp. Theo. Exp. Theo. Exp. Theo. Exp. Theo.

100 6.42 6.70
18.42
80 24.20 26.20 21.20 32.52 37.40
18.87 37.89 52.33
60 20.86
23.42 19.34 7.42
21.01 6.13
6.72
40 45.23 7.21 15.64 10.27 7.74
10.62
12.62 8.09 44.78
20 45.55 15.89
30.28 25.39
13.62 20.95 26.01 18.09
3.83
0
400 500 600 700
Temperature (°C)

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

Exp. Exp. Theo. Exp. Theo. Exp. Theo. Exp.

Area percentage (%)

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 of sugarcane bagasse and high-density polyethylene was investigated.

• Synergistic effect during co-pyrolysis were quantified.

• Co-pyrolysis enhanced the liquid yield and production of alcohol and hydrocarbon.

• The oxygenated compounds in the pyrolysis oil were decreased.

• Decarbonylation, decarboxylation and H transfer promoted the deoxygenation.