Applied Energy 276 (2020) 115508

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

CO2-assisted gasification of polyethylene terephthalate with focus on syngas T

evolution and solid yield
Zhiwei Wanga,b,c, Kiran G. Burraa, Xueqin Lib,c, Mengju Zhangb,c, Xiaofeng Heb,c, Tingzhou Leic,
Ashwani K. Guptaa,
⁎

a
The Combustion Laboratory, Department of Mechanical Engineering, University of Maryland, College Park, MD 20742, USA
b
Energy Research Institute Co. Ltd., Henan Academy of Sciences, Zhengzhou 450008, China
c
Henan Key Lab of Biomass Energy, Zhengzhou 450008, China

HIGHLIGHTS

• CO -gasification of PET waste for syngas recovery was investigated at 800–950 °C.
• CO
2
yields of 0.5–0.9 g were obtained per gram of PET waste gasified.
• CO utilization of 0.1–0.7 g were achieved per gram of PET waste gasified.
• Char yields with BET surface area ~936 m /g were achieved via gasification.
2
2

ARTICLE INFO ABSTRACT

Keywords: Polyethylene terephthalate (PET) contributes to majority of the global plastics wastes generated and its lack of
CO2-assisted gasification sustainable recycling calls for the development of pathways for this waste transformation to energy and che­
Polyethylene terephthalate (PET) micals extraction that will help avoid landfilling of this waste. In this paper, CO2 assisted gasification of PET was
Syngas evolution investigated at 800 °C to 950 °C using a fixed bed reactor to understand the feasibility of this pathway for PET
CO2 utilization
waste management. Evolutionary behavior of the yields of H2, CO, CH4, total C2-C3 gases and total syngas from
Solid residues
fixed bed reactor were investigated to understand the influence of temperature on isothermal conversion.
Gasification composition and total accumulative syngas rate were also calculated and compared. Solid residues
from gasification were analyzed for morphological characteristics and CO2 consumption. Evolution rate and
yield of H2, CO, CH4 and total syngas from fixed bed reactor changed with increase in reaction time and tem­
perature. CO yields increased from 0.5 to 0.9 g/g (gas mass yield per unit mass of PET), which accounted for 89.9
to 95.2 wt% of the total syngas yield with increase in temperature from 800 °C to 950 °C. The CO mole fraction
accounted for about 73.3 to 79.4 vol% of their total syngas at the different temperatures examined. Brunauer-
Emmett-Teller (BET) surface area of solid resides from CO2 gasification increased from 434 to 936 m2/g with
increase in temperature. These results showed thermal decomposition behavior under CO2 gasification influ­
enced the char structure and the effect became more pronounced with increase in temperature. CO2 gasification
of each mass unit of PET provided with the capability to convert about 0.1 to 0.7 mass unit of CO2 into valuable
syngas (a precursor for various value-added products) which reveals the synergistic possibility of PET waste
management along with CO2 utilization in this process of energy and value-added product recovery.

1. Introduction However, low degradability of the plastics causes serious environ­

Plastics have become an essential part of our modern lifestyle that is
supported by the development and mass production that embarked in
the latter half of the 20th century. The rapid accelerated production of
plastics has now reached more than 350 million tons per annum [1].
mental problems and a big challenge in waste management [2]. Ac­
cording to the United States Environmental Protection Agency (EPA),
35.4 million tons of plastic wastes were generated and 75.8% of this
amount were landfilled in 2017 in the USA. In 2015, 34.5 million tons
were generated and 75.4% of this amount were landfilled [3,4]. If

⁎
Corresponding author.
E-mail address: akgupta@umd.edu (A.K. Gupta).

https://doi.org/10.1016/j.apenergy.2020.115508
Received 24 April 2020; Received in revised form 29 June 2020; Accepted 12 July 2020
Available online 18 July 2020
0306-2619/ © 2020 Elsevier Ltd. All rights reserved.
Z. Wang, et al.
current production and waste disposal trends continue without their
large scale utilization, huge amount of plastic waste will end up in
landfills or discharged into the environment [5]. In these plastics,
polyethylene terephthalate (PET) is one of the most widely used
polymer amongst the plastics that accounts for about 7% of the global
plastics consumption. It is extensively used in packaging, and many
food products (e.g., beverage bottles and containers). Because of its
intrinsic properties it is suitable for lightweight, and offers large ca­
pacity, and pressure-resistant containers [6,7]. The global consumption
of PET is estimated to reach more than 20 million tons by 2020 while its
recycling rates are not increasing at the same rate [8]. There is urgent
needs to develop other methods for improved utilization of PET waste
and avoid landfilling. Novel chemical pathways, such as aminolysis of
waste PET, can utilizes PET waste for valuable products [9]. However,
it requires too small particle size to obtain high conversion rate that will
hamper its economic feasibility [10]. Bioremediation of PET is feasible
if the ester bonds that form part of the PET polymer chain could be
broken by several mechanisms. But the polymer is essentially non-de­
gradable under room temperature conditions and has low reaction rates
that makes this pathway undesirable. Incineration of PET can overcome
some of the limitations of landfill via waste volumetric reduction.
However, numerous harmful compounds are produced from incinera­
tion, including polycyclic aromatic hydrocarbons, polychlorinated bi­
phenyls, heavy metals, toxic carbon- and oxygen-based free radicals
[11]. This requires extensive flue gas cleaning to avoid impact on the
adjacent communities with unpleasant odors and toxic compounds,
which causes damage to both health and property [12]. The extensive
gas-cleaning required here renders this process economically and en­
ergetically unsustainable.
While landfilling and incineration are still the low cost pathways in
many countries [9], their issues with sustainable and eco-friendly op­
eration makes the development of thermochemical conversion techni­
ques such as gasification and pyrolysis more suitable pathways as they
can efficiently produce fuel and value-added products from the plastic
wastes. These processes involve thermal decomposition of solid carbo­
naceous materials into gas, char and liquid yields having medium to
high heating value. Depending on the operating temperature, the gas­
eous products (also referred to as syngas) that includes H2, CO, CO2,
CH4, C2H6 and trace amounts of other higher series of hydrocarbons
[13]. At high temperatures during gasification, while polymer cracking
reactions and the reforming of cracked hydrocarbons lead to gas yields,
re-polymerization and incomplete cracking leads to the formation of
mixture of heavy aromatic hydrocarbon residues, referred to as tar.
Syngas yield from gasification of versatile feedstock can be used for
energy and power generation, liquid fuel production via Fischer
Tropsch synthesis, and synthesis to other value added chemicals [14].
While gasification of PET blend with other feedstock such as wood and
PE have been investigated in fluidized bed and other reactors, under­
standing of the influence of gasifying agent such as CO2 on pure PET
waste still lacks in the literature [14–17].
CO2-assisted gasification can help assist provide sustainable
pathway for enhanced energy recovery from PET wastes using CO2.
Solid char obtained from PET thermal conversion (pyrolyzed and then
activated under CO2 atmosphere) have activated textural properties of
high surface area and large micropore volume that are favorable for
hydrogen uptake [18]. The absence of mineral matter and other
Table 1
Proximate and ultimate analysis, low heating value of PET.
Proximate analysis (wt.%)a Elemental analysis (wt.%)b
V FC A M C H
94.4 ± 0.1 5.6 ± 0.1 0 0 62.57 ± 0.05
a
Dry basis after heating at 105 °C for 8 h.
b
Dry ash free basis.
c
Calculated by mass balance.
2
Applied Energy 276 (2020) 115508
impurities in the composition of PET waste along with its high carbon
content turns this material into a promising precursor of carbon ma­
terials [19]. Activated carbon from PET was also investigated for ap­
plications in CO2 capture [20]. Solid carbon residue from PET pyrolysis
can be used as adsorbent after chemically activating with KOH for high
surface area and micropore volume [21]. Although these studies show
the value of CO2 utilization and PET conversion, they lack insights into
their feasibility and quantification for sustainable development of PET
waste management pathways.
Despite the various studies including pyrolysis, CO2, and steam
gasification of different plastic wastes mixtures, to the best of our
knowledge, there have been no detailed studies on CO2 assisted gasi­
fication of PET for syngas production and product characterization that
provides insights into the feasibility of this pathway. To bridge this
knowledge gap, we investigated the evolutionary behavior of H2, CO,
CH4 and total syngas from PET using CO2 as the gasifying agent.
Thermogravimetric analysis and a fixed bed reactor operated at 800,
850, 900 and 950 °C were used as the test bed facilities. The results are
reported on the evolutionary behavior of syngas, its composition and
distribution, CO2 consumption, solid residue characteristics during ga­
sification of PET with CO2. These novel results about the utility of PET
waste showed the evolution of syngas from PET as well as CO2 con­
sumption, along with attractive solid residues. The BET surface area
and pore volume size revealed their capability in direct utilization of
this greenhouse gas along with the landfill destined PET in gasification
to support energy utilization and waste management. Insights into the
feasibility of CO2 assisted gasification for PET utilization to obtain en­
ergy and value-added products recovery is reported in this paper. This
study reveals the extent of CO2 amounts that can be offset during CO2
assisted gasification of PET wastes, which can help assist in the devel­
opment of sustainable pathway for waste plastics management. The
results reported in this paper are of importance to novel waste-to-en­
ergy research to establish the feasibility of PET waste conversion be­
yond incineration and landfilling. The results show that CO2-assisted
gasification can be utilized for synergistic utilization of PET and CO2 for
value-added syngas production, which has applications in energy and
petro-chemical precursors production.
2. Material and methods
2.1. Materials
PET (Post consumer of bottle grade) was purchased from Illinois,
USA in the form of chunks of about 6 mm × 5 mm × 4 mm size. The
sample of PET was dried at 105 °C for 8 h prior to the fixed-bed ex­
periments. For proximate, elementary, and heating value analysis, the
samples were milled to 100–120 mesh particle size. PET was placed into
grinding vial set (SPEX6801) and pulverized in a grinder (Freezer/Mill,
6875D, the USA) under −196 °C liquid nitrogen atmosphere. Proximate
analysis was carried out using an automatic proximate analyzer (UV-
02053-00, USA) on the basis of China’s National Standard GB/T 212
[22]. Carbon, hydrogen, nitrogen, sulfur content was determined by a
CHNS elemental analyzer (Vario EL cube, Germany) on the basis of
China’s National Standard GB/T 31391 [23]. Low heating value (LHV)
was obtained using a rapid screening device (5E-KCIII, China) on the
basis of China’s National Standard GB/T 213 [24]. Table 1 provides
LHV (MJ·kg−1)
O N S
4.40 ± 0.03 33.03c – – 22.04 ± 0.50
Z. Wang, et al.
Fig. 1. A schematic diagram of the experimental facility and process pathway.
proximate and ultimate analysis, and low heating value of PET.
2.2. Experimental methods
2.2.1. Thermogravimetric analysis
Thermogravimetric analysis (TGA) was carried using TA instru­
ments, STA-Q600 analyzer. During this analysis, PET samples
(10 ± 1 mg) were heated from 100 °C to 1000 °C at a heating rate of
10, 20 and 30 °C/min. Alumina pans were used as the sample holders.
Chemically pure argon (99.998%) was used as purge gas at a flow rate
of 100 ml/min. This analysis provided us with the rate and temperature
range of thermal decomposition of PET.
2.2.2. Fixed-bed reactor analysis
The samples were gasified in an electrically heated furnace, see the
experimental setup shown in Fig. 1. CO2 (99.998%) and N2 (99.998%)
flow rates were maintained at 1.58 slpm and 0.52 slpm (75% CO2 and
25% N2 by volume), respectively (at standard conditions of 21 °C and
1 atm) for the CO2 gasification of PET in the fixed bed. Details on the
fixed bed reactor can be found in our previous study on CO2-gasifica­
tion and pyrolysis of waste tire [25], forestry residues [26], mixture of
forestry residues and waste tire [27,28]. The fixed bed reactor was
operated in the temperature range of 800–950 °C in 50 °C steps. In­
itially, the reactor was heated to the desired temperature with the input
gases flowing. Upon reaching the isothermal conditions, 35 g of PET
sample was introduced into the reactor in a mesh sample holder using
quick-disconnect coupling in the reactor. The evolved gases were dried
and filtered prior to their collection in sampling bottles at 0.5, 1, 2, 3,
and 4 min intervals from the start of gasification for their subsequent
analysis using a GC. After 4 min the gases were analyzed directly using
the GC at 2.7 min time interval until 47.7 min. Argon was used to flush
the gas sampling lines as well as the reactor to remove the residual
gases from previous tests. N2 was used as the tracer gas to obtain the
mass flow rates from relative mole fractions obtained from gas chro­
matography (Agilent 3000A Micro GC) analysis of the tar and moisture-
free product gases, assuming the inert role of N2 in the gasification
reactions. He and Ar were used as carrier gases for GC with its inlet
temperature maintained at 100 °C. Electrical power consumption for
the furnace was measured by an electricity monitor (EML-2000, Ca­
nada). Morphology of these solid residues was characterized using a
Scanning Electron Microscope (JSM-6510, Japan) with 20 kV beam
3
Applied Energy 276 (2020) 115508
voltage on the solid residues sputtered with Platinum. The BET surface
area and total pore volume were measured by surface area and porosity
analyzer (Micromeritics Tristar II 3020, USA). Each experiment was
repeated twice, and the average value of results were reported.
The N2 flow rate was used here as the tracer gas to evaluate the mass
flow rate of each gaseous compound using Eq. (1) under the assump­
tions of ideal gas behavior, inertness of N2 in the analyzed gases and
compositional invariance between bypass line and sampling line.
Xi
Mi = VN2
XN 2 i
(1)
where, Mi is mass flowrate of i species, Xi is mole fraction of i species as
measured by the GC, XN2 is mole fraction of N2, VN2 the standard vo­
lumetric flow rate of N2 at reactor inlet, and ρi is density of i species at
100 °C.
3. Results and discussion
3.1. Thermogravimetric analysis
Fig. 2(a, b) shows TG (in wt. %) and DTG (in wt. %/min) data for
PET at heating rates of 10, 20 and 30 °C.min−1 in surrounding Argon
atmosphere. Note that the DTG refers to the rate of conversion of
sample (gravimetrically measured) into volatile pyrolysis products
leaving the sample pan. The different heating rate revealed similar
decomposition behavior with delayed heating effects and increased
mass conversion rate. The results showed mass conversion rate started
from approximate 380 °C and finished at 490, 511 and 535 °C for
heating rates of 10, 20 and 30 °C⋅min−1, respectively. Approximate
85 wt% of the PET was decomposed between 380 and 700 °C. There
was one peak for each DTG curve at different heating rate. The max­
imum peak of mass conversion rate was 20.6, 41.2 and 68.1 wt.%/min
at 428, 440 and 443 °C for heating rates of 10, 20 and 30 °C⋅min−1,
respectively. In addition, the beginning of weight loss in DTG curve was
observed at ~380 °C corresponding to thermal decomposition of the bis
(hydroxyethyl) terephthalate monomer fraction [29]. The weight loss
stage observed between ~400 and ~500 °C, was due to the thermal
decomposition of the PET produced through thermal polymerization
and the gasification with CO2. Increase in heating rate shifted the peak
towards higher temperature due to mass transfer effects which delayed
the sample decomposition rate compared to the heating rate, see
Z. Wang, et al.
Fig. 2. (a) TG and (b) DTG curves for PET at a heating rate of 10, 20 and
30 °C⋅min−1.
Fig. 2(b). The peak height showed significant effects of increase in
heating rate. Meng et al. used macro-TGA facility to compare the pyr­
olysis with N2 and gasification with CO2. Their results showed insig­
nificant differences with CO2 assisted gasification and a slight en­
hancement of PET decomposition compared to pyrolysis with N2 under
the TGA operating conditions [30].
3.2. CO2 gasification in fixed bed reactor
3.2.1. Effect of temperature on gases evolution
Fig. 3(a-e) shows the effect of reactor temperature on evolved gases
flow rate of H2, CO, CH4, C2-C3 and total syngas flow per unit mass of
solid sample [g/(g . min)]. As expected at the beginning of the reaction,
there was no gas release. This was due to the thermal–mechanical de­
gradation that began with heating for homolytic scission of a car­
bon–carbon covalent bond in PET [31], generating free radicals that
undergo some chemical reactions to release gases in subsequent stage.
The results show that increase in reactor temperature increased the
flow rate of H2, CO, CH4 and total syngas. Increase in temperature also
shifted the peak position towards shorter times for all gaseous com­
ponents. The CO yield at the beginning of chemical reaction is attrib­
uted to pyrolytic breakdown of PET from de-carbonylation, along with
homogeneous reactions of volatiles with the CO2 present. Slow rate of
pyrolytic breakdown of PET at 800 °C delayed the maximum of gas
release of CO, therefore, parabolic shape like CO flow rate at 800 °C was
little higher than that at 850 and 900 °C during 10–15 min. The peaks in
the yield of gases enhanced along with their rate of evolution for all the
gases (except for total C2-C3 gases) with increase in temperature. This is
attributed to the endothermicity of CO2-assisted gasification that
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Applied Energy 276 (2020) 115508
promoted increased reaction rates and enhanced product equilibrium
with increase in reactor temperature. Total C2-C3 gases yield peak re­
duced at temperature above 850 °C and this is attributed to accelerated
cracking reaction of higher hydrocarbons at higher temperatures. The
flow rates of H2, CH4 and total C2-C3 gases became negligible after some
31.7 min, as the pyrolytic reactions reach their complete conversion,
which included reactions such as volatiles cracking, and volatile phase
hydrocarbon reforming. This can be justified from the tar/volatile hy­
drocarbons reactions with CO2 (CmHn + mCO2 → 2mCO+(n/2)H2),
which converted higher hydrocarbons into CO and H2 [32].
CO evolution, extended to over 47.7 min, and is due to slow reaction
of char gasification using carbon dioxide as the gasifying agent.
However, CO would begin to decrease from the remaining CO2 into the
gasifier that gradually ceased to participate in its conversion via
Boudouard reaction until the carbon was consumed completely [33].
The flow rate of CO yield at the four temperatures examined reduced to
some 5 to 15% of their peak value at gasification times of 20–25 min
and this value remained almost constant over the entire time duration
of gasification (~48 min). This phenomenon is attributed to the com­
plete conversion of pyrolytic and gas-phase reactions, and the Bou­
douard reaction. The reaction of char and CO2 (C + CO2 ⇌ 2CO) that
dominated the gasification of PET ((C10H8O4)n) after hydrogen and
oxygen elements were used up, is similar to the gasification of other
oxygenated solid wastes [34].
Fig. 4 shows syngas components’ mass yield and distribution. The
yield of CO dominated most of the syngas mass yield that provided 0.46
to 0.90 g/g (gas mass yield per unit mass of material), which accounted
for 89.9 to 95.2% of the total syngas yield as the temperature increased
from 800 to 950 °C. CH4 dominated most of the CmHn yield, which
accounted for 47.8 to 75.4% of the total CmHn at 800 to 950 °C, re­
spectively. A slight decline in CH4 concentration with increase in
temperature to 950 °C is attributed to exothermic behavior of char
gasification reactions (C + 2H2 → CH4), which resulted in its con­
sumption [35]. H2 yield were increased from 0.008 to 0.013 g/g at 800
to 950 °C, respectively.
Fig. 5 shows mole fraction of H2, CO, CH4, and C2-C3 in accumulated
product gas yield as well as H2/CO ratio at different gasification tem­
peratures. The results showed that increase in gasification time in­
creased the mole fraction of H2, CH4 and C2-C3 first and then decreased
to an almost a constant value. Mole fraction of CO sharply increased to
a high value followed by a slow steady increase. H2/CO ratio data
showed the similar trend to H2 mole fraction. With increase of tem­
perature, the peak of H2 mole fraction and the peak of H2/CO ratio
increased. The accumulated mole fractions could be a reference for
determining optimal reaction time to obtain desired mole fraction of
syngas. The CO mole fraction in syngas dominated at all the experi­
mental temperatures examined, which accounted for about 73.3 to
79.4 vol% of their total syngas due to the Boudouard and hydrocarbon
reforming reactions in CO2 gasification atmosphere. H2 also accounted
for significant proportion (16.2–18.2 vol%) at different temperatures
examined. The decreased proportion of H2 with temperature could be
associated with its increased reaction with CO2 to form CO as increase
in temperature thermodynamically favors increased CO compared to H2
in the presence of CO2. However, in terms of total mass yield, higher
yield of H2 was released at higher temperatures as more tar gets de­
composed into H2 and CO with higher selectivity towards CO (due to
the presence of CO2) to relatively lower H2 mole fraction in the syngas
while increase in CO mole fraction. Increase in temperature from 800 to
950 °C showed the expected decrease in CH4 mole fraction from 5.9 to
3.7 vol% and decrease in C2-C3 mole fraction from 3.2 to 0.7 vol%. The
reason for this decrease in CH4 and C2-C3 was due to CO2 reforming of
these hydrocarbons in gas-phase to yield more CO.
3.2.2. Solid yield and CO2 consumption
Fig. 6 (a-d) shows the morphology of solid residues enlarged surface
(5000×) at different temperatures. There were no pores on the surface
Z. Wang, et al. Applied Energy 276 (2020) 115508

Fig. 3. Evolution of gases flow rate per unit mass of solid sample (a) Hydrogen flow rate, (b) Carbon monoxide flow rate, (c) Methane flow rate, (d) Total C2-C3 flow
rate, and (e) Total syngas flow rate.

Fig. 4. Syngas components’ mass yield and distribution.
of char at 800 °C (see Fig. 6(a). The pores became more apparent from
850 to 950 °C, which revealed increase in hole structures with increase
in temperature (see Fig. 6). These results show the influence of CO2
gasification on the char structure which became more pronounced as
the temperature was increased. Similar result showed that char pro­
duced under CO2 exhibited thick and smoother vascular bundles with
irregular shape and an abundance of finer and more rounded cavity
structures, which is attributed to be from the CO2/char gasification
reactions [36].
The devolatilization in CO2 gasification resulted in more pores in
the surface of char with increase in temperature. Moreover, increase of
pores could increase the inter-activity surface of CO2 and char with the
subsequent result of enhanced Boudouard reaction. Increased granu­
larity from increased CO2 activity led to increased access sites for
Boudouard reaction. Most pore structure models assume that gasifica­
tion occurs on the surface of the micropores, which make up most of the

5
Z. Wang, et al.
Fig. 5. Mole fractions of gas components in accumulated product gas yield.
surface area of char [37]. Similar char particles of biomass and waste
tire were also observed to be generally irregular and became more
porous [38] or of larger surface area [39] with increase in the process
temperature.
Fig. 7 shows the solid residues yield, and solid surface area (BET) of
the solid yield at different temperatures. Increase in temperature de­
creased the solid residues yield from 0.078 g/g at 800 °C to 0.037 g/g at
950 °C as CO2 activity increased leading to more char consumption in
Boudouard reaction to yield in more CO. This also help support the
increase in CO yield with increase in temperature (Fig. 4). The BET
surface areas were 434.4, 583.1, 820.9 and 936.2 m2/g; the total pore
volumes were 203.1, 243.0, 308.4, and 586.1 × 10−3 cm3/g at tem­
perature from 800 to 950 °C, respectively. BET surface area and total
pore volume increased significantly when gasification temperature in­
creased from 800 °C to 950 °C due to increased activation degree of PET
[19]. The BET surface areas of the chars were related to their gasifi­
cation activity. The gasification rate of chars with higher surface area
were faster than that of chars with lower surface area [40]. Moreover,
narrow micropore surface area appears to be a good parameter for
describing the reactivity of PET char, since the ratio between the re­
action rate and the surface area remained constant with conversion,
indicating that the gasification process was governed by micropores
[37]. The rate of gasification of char could be influenced by the mass
transfer in the small size pores; the reacting CO2 would diffuse quickly
through the larger pore volumes. However, it would diffuse more
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Applied Energy 276 (2020) 115508
slowly into the smaller pore volumes which contribute to most of the
surface area [41]. In addition, the presence of CO2 was found to en­
hance pore size, because gasification could remove carbon atoms from
the interior of the particles, resulting in the enlargement of opened
micropores as well as the opening up of closed micropores [42]. The
characteristic of solid residues was similar to the study on activated
carbon from PET, which has a high density, good conductivity and little
ash content. These properties make activated carbon from PET waste
suitable for application in industrial sorption processes [43].
Fig. 8 shows a comparison of CO2 consumption rate and CO yield
rate at different temperatures along with cumulative CO2 consumption
at 47.7 min. From approximately 25 min, CO2 consumption rate and CO
yield flow rate becomes similar and both changed with increase in
temperature. CO2 offers a direct role in these reactions that are relevant
in the gasification. The influence of Boudouard reaction and the con­
sumption of char in CO2 gasification, unlike pyrolysis significantly de­
creases the char by-product and enhance CO yield [26]. CO2 addition
under high temperatures has a positive effect on syngas production
[44]. Due to the high thermal stability of CO2, these reactions are sig­
nificantly endothermic so that temperatures above 700 °C are required
for some reasonable conversion [45,46]. The CO evolution peaks co­
incided with CO2 consumption peaks suggesting direct influence of
CO2. However, CO2 was released with volatiles production at the be­
ginning of thermal decomposition of PET. The breaking of ester func­
tional groups attached to benzyl portion lead to the decomposition of
Z. Wang, et al.
(a) 800 °C-5000×
(c) 900 °C-5000×
Fig. 6. The morphologies of solid residues at different temperatures.
Fig. 7. Solid residues yield and surface area at different temperatures.
polymer core and release of CO2 via decarboxylation. In parallel with
ester rearrangements, the broken linkages form carbonyl groups de­
compose to release CO [13]. Volatiles generated were assumed to
stream out of the feedstock immediately, while the char yield generated
during initial pyrolysis was assumed to consist of a porous carbon
structure [47], so that the Boudouard reaction could dominate reaction
in the next stage of CO2 gasification to further consume the char and
simultaneously increase its porosity.. When the pyrolytic breakdown of
PET reached its maximum gas release of CO, the CO evolution peaks,
and CO2 consumption peaks appeared at the same time. More CO2
consumption was observed during the thermal decomposition process
possibly due to high carboxylic content in PET [48]. Note that CO
production peak during the initial pyrolytic phase (first 3–8 min at
different temperatures) showed higher CO evolution rate from char-
gasification phase that occurs from 8 to 40 min. Kinetics of char gasi­
fication with CO2 as gasifying agent was much slower than kinetics of
the pyrolysis process [49].
The increased yield of CO with increase in temperature is mainly
attributed to Boudouard reaction and the reforming reaction of CO2
with decomposition of hydrocarbon volatiles at high temperatures. The
reaction between volatiles and CO2 also produces H2, which is among
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Applied Energy 276 (2020) 115508
(b) 850 °C-5000×
(d) 950 °C-5000×
the reasons that mole fraction of both H2 and CO increased with in­
crease in temperature. This also reveals the advantages of CO2 gasifi­
cation of wastes in its ability to consume CO2 and convert it into useful
syngas. The CO2 consumption increased continuously with increase of
temperature, which amounted to 4.7, 8.0, 16.4 and 23.9 g during
47.7 min at 800 to 950 °C. Thus, gasification of each mass unit of PET
provided with the capability of consuming approximate 0.13 to 0.68
mass unit of CO2 at corresponding temperatures to yield value-added
syngas.
3.2.3. Possible decomposition pathways
From the evolution of flow rate of gas components, solid residues
yield and CO2 consumption shown in Figs. 3, 7 and 8, the possible
decomposition pathways of CO2-assisted gasification of PET is sum­
marized in Fig. 9. There could be four stages in the whole gasification
process. In the first stage, PET was heated and melted with little CO2
consumption (also see Fig. 8), and there was no gas release (also see
Fig. 3). In the second stage, thermal decomposition and gasification
occurred, however, CO2 also released from PET, and CO2 consumption
showed negative due to higher release rate of CO2 than consumption
rate (also see Fig. 8), the oxygen in CO2 was conjectured to be derived
from high oxygen content of PET. All gas flow rates reached their
maximum values in this stage (also see Fig. 3). In the third stage, CO2
consumption became positive and reached its maximum value. This
indicated that Boudouard reaction and tar/higher hydrocarbons reac­
tions accelerated with CO2, however, gases flow rate started to decrease
(also see Figs. 3 and 8) because the sample weight was reduced along
with gasification process. In fourth stage, both CO2 consumption rate
and CO flow rate showed plateau behavior (also see Fig. 8), and other
gases flow rate became zero (also see Fig. 3). This indicated that all
reactions were finished except Boudouard reaction during this stage.
4. Conclusions
This paper provides thermal characteristics on weight loss, the rate
of mass conversion and evolutionary behavior various gases in syngas
during gasification of PET in CO2 atmosphere using TGA and a fixed
Z. Wang, et al. Applied Energy 276 (2020) 115508

Fig. 8. A comparison of CO2 consumption and CO evolution during gasification.

Fig. 9. Possible decomposition pathways of CO2-assisted gasification of PET.

bed reactor. The TGA results on PET showed different heating rate re­
vealed similar decomposition behavior with delayed heating effects and
increased rate of mass conversion. The maximum peak of mass con­
version rate of 20.6, 41.2 and 68.1 wt.%/min at 428, 441 and 443 °C for
different heating rates was observed from this analysis revealing the
uniformity of PET sample along with its decomposition behavior. CO2
gasification in fixed bed results showed the peaks in the yield of gases
along with their reaction rate enhanced with increase in temperature
for all the gases, except for C2-C3 gases. CO yields increased from 0.46
to 0.90 g/g, which accounted for 89.9 to 95.2 wt% of the total syngas
yield from 800 °C to 950 °C, respectively. The CO mole fraction was the
maximum, which accounted for over about 73.3 vol% of their total
syngas. The morphologies of PET residues solid investigated results
showed thermal reaction under CO2 gasification influenced the char
surface structure and the effect became more pronounced with increase
in temperature. The BET surface area of solid resides increased from
434 to 936 m2/g along with pore volumes increased from 800 to 950 °C.
Each unit mass of PET in CO2 gasification could consume from 0.1 to
0.7 mass unit of CO2 from 800 to 950 °C. This study suggests that syngas
produced from PET using CO2 as the gasifying agent offers robust so­
lution in converting waste plastic to alternative syngas fuels while si­
multaneously providing solution to manage the issues of greenhouse
gas emission.
CRediT authorship contribution statement
AKG provided conceptualization, project administration, super­
vision, Resources, and Writing and review editing of the paper. ZW,

8
Z. Wang, et al.
KGB, XL did the investigation, data curation, Formal analysis, metho­
dology, visualization and inital writing MZ, XH and TL provided
Resources, supervision, review and editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ­
ence the work reported in this paper.
Acknowledgments
This research was supported by the US Office of Naval
Research (ONR) and is gratefully acknowledged. The support
provided to Zhiwei Wang from Henan Province Talent Project
(194200510028), Henan Academy of Sciences Research Projects
(18ZX06001,18YY06003,18DB06012, 190706001), and China
Scholarship Council (CSC) under the “International Clean Energy Talent
Project” is gratefully acknowledged. Kiran G. Burra received 2020
Hulka Energy fellowship and this support is gratefully acknowledged.
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