Chemical Engineering Journal 392 (2020) 123774

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Chemical Engineering Journal

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CO2 to fuel via pyrolysis of banana peel T

a,1 b,1 a c d
Dohee Kwon , Sang Soo Lee , Sungyup Jung , Young-Kwon Park , Yiu Fai Tsang ,
⁎
Eilhann E. Kwona,
a
Department of Environment and Energy, Sejong University, Seoul 05006, Republic of Korea
b
Department of Environmental Engineering, Yonsei University, Wonju 26493, Republic of Korea
c
School of Environmental Engineering, University of Seoul, Seoul 02504, Republic of Korea
d
Department of Science and Environmental Studies, The Education University of Hong Kong, Tai Po, New Territories, Hong Kong, China

H I GH L IG H T S

• Valorization of banana peel to energy as a form of syngas was achieved by pyrolysis.

• Banana peel pyrolysis in CO produced more than 20 times of CO comparing to N .
2 2

• CO 2-cofeed pyrolysis manipulated biocrude composition and biochar morphology.

• CO was changed into fuel via a sustainable thermolytic platform of food waste.
2

A R T I C LE I N FO A B S T R A C T

Keywords: Considering the global production of banana, a large amount of banana peel (BP) waste is being generated world
CO2 widely. Thus, pyrolysis of BP was investigated to develop a technically reliable platform for the simultaneous
CO2-to-fuel waste management and energy recovery. To synergistically increase the sustainability of BP pyrolysis, this study
Banana peel adopted carbon dioxide (CO2) as a raw material and examined the production of syngas as a function of tem-
Waste valorization
perature in reference to the N2 environment. CO2-cofeed pyrolysis expedited the thermal cracking of volatile
Waste-to-energy
Pyrolysis
pyrolysates from BP, resulting in the gas phase homogeneous reaction between CO2 and the pyrolysates at
≥420 °C. This promoted CO formation in the temperature region, and more than 20 times of CO formation was
shown in comparison with pyrolysis in the N2 environment. These genuine mechanistic roles of CO2 offer a new
mean for converting CO2 into CO. Also, CO2-cofeed pyrolysis of BP increased the aromaticity of biocrude
(pyrolytic oil), expediting dehydrogenation of liquid pyrolysates without using any catalysts. Moreover, mod-
ification of biochar surface morphology under the CO2 condition was observed. Conclusively, this study in-
formed a key clue for maximizing the carbon exploitation in the carbonaceous waste, which directly leads to the
environmental benefits due to the use of CO2 as a reactant. CO2-cofeed pyrolysis can be an innovative and
strategic thermo-chemical process to valorize food wastes.

1. Introduction global environmental burden, such as climate change [5,6]. To seek an

Unilateral use of the fossil resources to exploit them as energies and
chemicals has rapidly increased since the Industrial Revolution [1,2]. In
spite of numerous socio-economic benefits, CO2 emissions from the
exploitation of the fossil resources have subsequently resulted in eco-
logical perturbation [3,4]. In fact, the International Energy Agency
(IEA) reported that global CO2 emissions in 2018 reached up to 33.1 Gt.
CO2 emissions from combustion of fossil fuels are beyond the planet’s
capacity to regulate carbons, of which carbon imbalance triggers the
effective means to abate the global environmental issues in line with
CO2, a great deal of researches on sustainable energies [7–10] and
carbon capture and sequestration (CCS) [11–13] has gained un-
precedented attention over the several decades. Regardless a low eco-
nomic viability [14,15], the public consensus in accordance with
awareness of the detrimental consequences from global warming plays
a crucial role for mandating the use of renewable energies [16]. Thus,
renewable fuel standard (RFS) and renewable portfolio standard (RPS)
have been legislatively mandated in most developed countries [17]. In

⁎
Corresponding author.
E-mail address: ekwon74@sejong.ac.kr (E.E. Kwon).
1
Two authors equally contributed to this study.

https://doi.org/10.1016/j.cej.2019.123774
Received 4 October 2019; Received in revised form 4 December 2019; Accepted 9 December 2019
Available online 10 December 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.
D. Kwon, et al.
particular, the practical implementation of biofuels in reference to
other renewable energies has readily been achieved owing to their
compatibilities with fossil fuels [18].
As compared with other renewable energies, biofuels are only
carbon-based because they are derived from the carbon-neutral re-
sources, such as lignocellulosic and algal biomass [19]. Thus, they can
share the distribution networks with fossil fuels by means of simple
blending with gasoline and diesel [20]. They are also affordable to be
used in the internal combustion (IC) engines without any mechanical
modification [21]. Nonetheless, the insecure supply chain of biomass
has been pointed out as one of the biggest constraints for the further
expansion of biofuels [22]. Indeed, the annual production of biomass is
highly depending on the regional and seasonal variations [23,24]. Ac-
cordingly, it is desirable to exploit various waste materials as raw
materials for biofuels [25] and to develop its reliable conversion plat-
form consistently for the better efficiency [26]. The most biofuels are
being transformed from the single nutrient in biomass [27]. For in-
stance, bioethanol and biodiesel are converted from fermentation of
sugar and chemicals reaction (transesterification) of lipid, respectively
[28]. Indeed, biogas via the fermentation process offers the whole
conversion of organic waste into fuel [29]. Nonetheless, the anaerobic
digestion (AD) process are sensitive to the physico-chemical properties
of carbon substrates, which greatly affects the production yield of
biogas (i.e., methane) [30], and the control of carbon deposit onto
microbes and loss (CO2) by the microbial metabolisms is also challen-
ging [31].
In these respects, the thermo-chemical process (pyrolysis and gasi-
fication) of biomass offers an ideal solution to resolve most technical
demerits in the AD process. In short, the thermo-chemical process is
indeed invulnerable to the physico-chemical variations of carbon sub-
strates and can offer a paramount means for mass production in a re-
latively short processing time [32]. Gasification is a process that fully
converts solid carbonaceous materials into syngas (H2 and CO) with
oxygen and/or steam condition at high temperature (≥700 °C) via
oxidation reaction [33,34]. This energy intensive process at high tem-
perature also accompanies mass production of greenhouse gas, CO2.
Pyrolysis is one of the proven thermo-chemical processes to convert
biomass into the three pyrolysates (flammable gas, biocrude, and bio-
char) in an oxygen-free environment at relatively lower temperature
than gasification. Pyrolysis of biomass has been mainly adapted to
produce biochar and biocrude for the further upgrading and various
applications [11,35]. However, energy recovery (syngas formation)
from pyrolysis of biomass was less significantly highlighted, in com-
parison with a gasification, because thermolysis of biomass generally
does not gasify as much as coal [36]. Thus, enhancement of energy
recovery from pyrolysis of biomass wastes, consuming greenhouse gas,
CO2, will be of great importance.
In these rationales, CO2-cofeed pyrolysis of a biomass waste was
mainly investigated to implement a sustainable thermolytic platform
for energy recovery from biomass in reference to pyrolysis in N2 en-
vironment. In addition, low temperature pyrolysis was conducted at
≤700 °C for the syngas formation for more energy efficient syngas and
biochar production. Banana peel (BP) was used as a case study, because
banana (Musa paradisiaca L.) is one of tropical fruits consumed globally.
The global production of banana was estimated to be 125 million tons
in 2017 [37]. Considering 42 wt% of a cluster of bananas, a large
amount of banana peel (BP) waste is being generated world widely. To
date, only the limited number of publications reported the recovery of
energy from BP via the pyrolysis process, qualitatively [38]. Also, most
of current researches for BP pyrolysis focused on the production of
biochar and carbonaceous solid materials [38–40]. In this study, fun-
damental understanding of the mechanistic role of CO2 on pyrolysis of
BP was also focused. To this end, the three pyrogenic products (solid
biochar, liquid biocrude, and syngas) from lab-scale CO2-cofeed pyr-
olysis of BP were compared with those from the N2 environment. Also,
the thermo-gravimetric analysis (TGA) tests were done to gain an
2
Chemical Engineering Journal 392 (2020) 123774
insight on the mechanistic role of CO2.
2. Materials and methods
2.1. Chemical reagents and sample preparation
BP was collected from a local restaurant in Korea. To avoid biode-
gradation, the collected BP sample was dried at 80 °C for 3 d. The
sample was processed using a ball mill (Fritsch, PULVERISETTE 6 Mono
Mill, Germany), with an average particle size of 45 mesh (345 µm). The
milled BP sample was stored in a desiccator to avoid moisture ab-
sorption. The ultimate analysis of BP was done using the FlashSmart™
Elemental Analyzer (Thermo-Fisher Scientific, USA). The ultimate
analysis of BP showed the empirical formula of C1H1.6O0.9N0.02S0.006.
The GC calibration gas (Lot # 160-401257255-1) and dichloromethane
(99.8% purity of CH2Cl2) (Lot # MKBS5448V) were purchased from
INFICON (Germany) and Sigma-Aldrich (St. Louis, USA), respectively.
Ultra-high purity N2 and CO2 gases were also purchased from TechAir
(Korea).
2.2. TGA of BP
The mass change of BP in accordance with the thermolytic tem-
peratures was determined using a TGA unit (NETZSCH STA 449 F5
Jupiter, Germany). The TGA test of BP (10.00 ± 0.01 mg, 345-µm
particle size), loaded in a crucible, was done at a temperature ramp of
10 °C/min from 40 to 900 °C. To cancel out the buoyancy effect, the
blank TGA run was done. Note that the buoyancy effect was induced by
density change due to the thermal expansion of N2 and CO2.
2.3. Pyrolysis of BP
A tubular reactor (TR) was assembled with the quartz tubing (1.2-m
length, 23-mm inner dia., and 25.4-mm outer dia.) to exclude the cat-
alytic influences. Except dimension of the TR, all parts to construct the
TR are reported in our previous work [41]. 1.000 ± 0.001 g of BP was
loaded for each pyrolysis run. The flow rate of gas medium was set as
300 mL/min, of which the flow rate was controlled using a mass flow
controller (Brooks, USA). A tubular furnace (RD 30/200/11, Na-
bertherm, Germany) was used. The tubular furnace had two heating
zones. Accordingly, for one-stage pyrolysis of BP, two heating zones
were controlled simultaneously. On the contrary, two heating zones
were separately operated in two-stage pyrolysis of BP. In detail, the first
and second heating zones were dynamic (a temperature ramp: 10 °C/
min, the operation temperature: 40–700 °C) and isothermal (600 °C)
runs, respectively. The gaseous effluents from the TR were transferred
to an on-line micro GC (3000A, INFICON, Switzerland). Note that
condensable pyrolysates (biocrude) were trapped using liquid N2. Mass
balance of all pyrolysates was determined by weighting mass of biochar
and biocrude. Experimental setups for both one-stage and two-stage
pyrolysis were described in the Scheme 1. Note that the mass fraction of
the gaseous pyrolysates were estimated based on mass of biochar and
biocrude. All the experiments were performed at least three times, and
the errors were ≤1%.
Scheme 1. Flow diagram of pyrolysis experiments.
D. Kwon, et al.
2.4. Qualitative and quantitative determination of pyrolysates derived from
pyrolysis of BP
The concentrations of the gaseous pyrolysates (i.e., H2, CH4, CO,
C2H6, C2H4, and C2H2) was determined using a micro-GC unit. The
micro-GC unit was comprised of two GC modules (molecular sieve
column and Plot U column). The GC calibration gas from INFICON and
RIGAS were used to calibrate the micro-GC unit. To determine the
constituents of biocrude qualitatively (i.e., condensable pyrolysates),
GC/TOF-MS (Agilent 7850B/Bench Top, ALMSCO, UK) was used,
which was equipped with a capillary column (DB-Wax, Agilent, USA).
3. Results and discussion
3.1. One stage pyrolysis of BP in CO2 and N2 environments
To gain an insight on the CO2-cofeed impact on pyrolysis of BP,
1.000 ± 0.001 g of BP was pyrolyzed in the one-stage reactor in the
CO2 atmosphere. Given that the Boudouard reaction (C + CO2 ⇌ 2CO )
under 1 atm starts to be activated at 720 °C [42], the initiation of it
leads to the enhanced generation of CO via a gasification reaction. Since
the Boudouard reaction is well known and broadly applied gasification
process, this work investigated the thermolysis of BP for syngas for-
mation and mechanistic roles of CO2 at milder temperature region
(between 300 and 700 °C) to exclude any effect from the Boudouard
reaction. The same pyrolysis test of BP in N2 was performed to adopt it
as the reference. To study the mechanistic role of CO2, the gaseous
effluents were quantified as a function of pyrolysis temperature, and
their concentration profiles (i.e., H2 and C1-2 gaseous species) were
plotted (Fig. 1).
The concentration profiles of the gaseous effluents in N2 demon-
strate a typical thermolytic trend of biomass. As depicted, CO is created
earlier than that of H2 in pyrolysis of BP [41]. This is ascribed to low
bonding energy of C-O. For instance, bonding energies of C-O and C-H
are 358 and 416 kJ/mol, respectively. Accordingly, the formation of H2
by dehydrogenation of polymeric carbon structure of biomass is ob-
served at ≥480 °C [43], of which the temperature initiating the for-
mation of H2 in reference to CO is higher. Moreover, the formation of
H2 increased as the thermolytic temperature increased (Fig. 1), which is
consistent with the dehydrogenation mechanism (cleavage of C-H
bond) that its reaction kinetics is proportional to the thermolytic tem-
peratures [44]. As such, the concentration of H2 reached the maximum
level at 630 °C. At ≥630 °C, the concentration of H2 starts to decrease.
This is likely ascribed to the source depletion foe dehydrogenation. The
concentrations of CH4, C2H6, C2H4, and C2H2 from pyrolysis of BP in N2
are negligible as compared with those of H2 and CO. Thus, the lower
concentration levels of CH4, C2H6, C2H4, and C2H2 suggest that the
pyrolysis of BP in N2 mainly follows direct bond scissions from the
biopolymeric backbone of BP and dehydrogenation. CO formation is
nearly negligible at the temperatures initiating H2 formation. Such the
observation implies occurrence of cyclization, which results in the
carbonization of biomass to produce biochar at ≥480 °C [11,45].
However, the evolution trend of the gaseous effluents in CO2 is
different from that in N2. Especially, the evolution of CO from CO2-
cofeed pyrolysis of BP is noticeably different. As depicted in Fig. 1, CO
formation exponentially increases at ≥420 °C, and the highest molar
concentration was 6.2 mol% at 700 °C. On the contrary, other gaseous
effluents (H2, CH4, C2H6, C2H4, and C2H2) show the lower concentra-
tion levels as compared with those in N2. Thus, such the lower levels in
Fig. 1 are likely due to the dilution induced by the CO enhancement in
CO2. Note that the on-line GC measurement offers the molar ratio of
analytes, and the relative molar concentration can be obtained. When
CO level exponentially increased at 420 °C, concentration of others,
specifically H2, could be slightly decreased due to the dilution effect.
Nonetheless, the concentration profiles (C2-hydrocarbon species) from
both N2 and CO2 are different. In detail, the highest concentrations of
3
Chemical Engineering Journal 392 (2020) 123774
C2-hydrocarbon species from CO2 appear earlier than those from N2.
Such the observations provide a key clue in line with the mechanistic
role of CO2. Given that the CO enhancement is only observed from the
CO2 environment, the identified enhancement in Fig. 1 strongly sug-
gests that there is an additional source of C and O. As such, the lower
concentration levels of C2-hydrocarbon species imply that carbons in
C2-hydrocarbon species and volatile pyrolysates from BP pyrolysis serve
a role for the source of C. However, the additional source of O cannot be
elucidated. Considering the experimental setup, CO2 is postulated as the
feasible source of both C and O. More precisely, the CO enhancement
can be interpreted as the result of the gas phase reaction between CO2
and volatile pyrolysates including C2-hydrocarbon species. Based on
these rationales, depriving carbons from volatile pyrolysates by CO2
through the reaction to form CO leads to the lower concentration levels
of C2-hydrocarbon species. The highest concentrations of C2-hydro-
carbon species in CO2 appear earlier than those in N2 because C2-hy-
drocarbon species react with CO2 via the gas phase reaction.
The concentration profile of H2 from the CO2 environment is in-
teresting. As depicted, the concentration of H2 from the CO2 environ-
ment is nearly constant at ≥550 °C, where the concentration of CO is
enhanced exponentially. The constant concentration levels for H2 in
Fig. 1 cannot fully be explained by the dilution by the CO enhancement
because exponential decrease of H2 formation is expected when CO2
dramatically increased at ≥600 °C. Accordingly, such the phenomena
offer that the hypothesized gas phase reaction between volatile pyr-
olysates (including C2-hydrocarbon species) from BP pyrolysis and CO2
affects dehydrogenation. Considering the genuine mechanistic features
of CO2 in Fig. 1, we assumed that CO2-cofeed impact on pyrolysis of BP
likely influences the carbon distribution of three pyrolysates (i.e., gas,
biocrude, and biochar) in line with the overall mass balance. CO2 likely
affects the compositional matrix of biocrude (as pyrolytic oil) con-
densed from volatile pyrolysates. To confirm these, mass balance was
established in Fig. 2(a). In addition, the constituents of the condensable
pyrolysate were determined qualitatively. Since the volatile pyrolysates
produced from BP pyrolysis were gas phase products through the tub-
ular furnace, they were condensed using a solvent trap to make liquid
products (biocrude) in dichloromethane. To visualize each constituent
in the biocrude (condensable pyrolysate or pyrolytic oil), the chroma-
togram was shown in Fig. 2(b). The major constituents in biocrude were
labelled and their details were summarized in Table 1.
Since biomass consisted of complex polymeric structure such as
cellulose, hemicellulose, and lignin with impurities, pyrolysis of BP
resulted in the formation of various carbon-based constituents. In
Fig. 2(a), the mass portions of three pyrolysates from N2 and CO2 are
not much different. Nonetheless, the compositional matrix of biocrude
is indeed different. Such the differences are evidenced by the peak area
of the chemical species in Table 2. All experimental findings (Figs. 1
and 2, and Table 1) experimentally support that CO2 plays a crucial role
to modify the compositional matrix of the gaseous effluents and bio-
crude. Interestingly, most chemical species in Table 1 are the oxyge-
nated hydrocarbons. Identification of the oxygenated chemical com-
pounds in biocrude is consistent with the ultimate analysis of BP. Note
that the chemical formula of BP was determined as C1H1.6O
0.9N0.02S0.006. On the assumption that there is no additional source of O,
the high content of the oxygenated compounds in biocrude from pyr-
olysis of BP in CO2 must result in the less formation of CO. On the
contrary, the CO enhancement was observed in CO2 (Fig. 2). Thus, it is
pertinent that the identified CO enhancement in Fig. 2 is a result of the
gas phase reaction between CO2 and volatile pyrolysates. For the fun-
damental investigation, it is desirable to clarify the hypothesized gas
phase reaction.
3.2. Characterization of the thermal degradation of BP in CO2 and N2
environments
To confirm the hypothesized gas phase reaction, a series of the TGA
D. Kwon, et al. Chemical Engineering Journal 392 (2020) 123774

Fig. 1. Concentration of the gaseous effluents (H2 and C1-2 chemical species) from one-stage pyrolysis of BP.

Fig. 2. (a) Mass balance of three pyrogenic products from N2 and CO2, and (b) chromatogram of biocrude derived from one-stage pyrolysis of BP in N2 (black color)
and CO2 (red color). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

4
D. Kwon, et al. Chemical Engineering Journal 392 (2020) 123774

Table 1
Identified chemical species in biocrude from BP pyrolysis in N2 and CO2 conditions (Peak area in N2 and CO2 are scale-downed as 106).
No. Retention Time, [min] Compounds Formula Area in N2 Area in CO2 Variation*, [%]

1 11.04 butan-2-one C4H8O 13.79 16.66 20.84

2 11.30 2,3-dimethylbutane C6H14 21.03 26.79 27.42
3 14.74 2-pentanone C5H10O 5.41 6.79 25.62
4 15.65 acetic acid C2H4O2 278.72 326.60 17.18
5 16.21 oxiran-2-ylmethanol C3H6O2 84.30 72.02 −14.58
6 17.87 4-methoxybutane-1,2-diol C5H12O3 9.01 8.27 −8.19
7 18.97 3-methylpentan-2-one C6H12O 6.30 10.97 74.17
8 19.76 propanoic acid C3H6O2 17.69 18.05 2.02
9 21.42 3,4-dimethylfuran-2,5-dione C6H6O3 18.40 26.92 46.35
10 22.19 furan-3-carbaldehyde C5H4O2 34.54 48.30 39.81
11 23.57 D-limonene C10H16 79.57 108.52 36.39
12 24.98 1-(furan-2-yl)ethanone C6H6O2 10.18 14.69 44.28
13 25.43 dihydrofuran-2(3H)-one C4H6O2 37.98 59.47 56.59
14 26.40 guanidine CH5N3 10.79 9.80 −9.19
15 27.16 4-pentenal C6H10 18.17 27.32 50.39
16 28.45 2-methylpenta-1,4-diene C6H10 17.13 17.55 2.42
17 30.14 cyclotene C6H8O2 4.35 4.43 1.87
18 30.35 phenol C6H6O 29.48 47.56 61.32
19 30.68 2-methoxyphenol C7H8O2 6.08 9.52 56.50
20 31.68 m-cresol C7H8O 10.75 18.78 74.68
21 32.30 cis-3-hexenal C6H10O 5.33 6.26 17.40
22 33.20 p-cresol C7H8O 19.03 26.91 41.43
23 33.71 3-Hydroxydihydrofuran-2(3H)-one C4H6O3 6.59 8.83 34.06
24 34.20 cyclobutanol C4H8O 77.00 104.59 35.83
25 35.55 4-ethylphenol C8H10O 8.01 11.65 45.33
26 35.77 2,4-dimethylphenol C8H10O 4.51 5.72 26.76
27 36.29 3,5-dihydroxy-6-methyl-2H-pyran-4(3H)-one C6H8O4 9.58 16.33 70.43
28 38.08 cyclobutane C4H8 6.92 5.30 −23.39
29 38.51 1,4:3,6-dianhydro-A-D-glucopyranose C6H8O4 7.08 7.13 0.75
30 39.35 1H-indole C8H7N 6.75 5.79 −14.27
31 40.96 5-acetyloxolan-2-one C6H8O3 6.52 4.01 −38.49
32 46.47 3-methylcyclopentane-1,2-dione C6H8O2 4.41 5.55 25.87

tests was carried out in various atmospheric environments. To align all
experimental findings (Figs. 1 and 2, and Table 1) with the TGA result,
the TGA tests of BP was done at a temperature ramp of 10 °C/min from
40 to 900 °C. Mass change of BP and its thermal degradation rate were
presented (Fig. 3).
As well reflected in Fig. 3(a), mass changes upon the thermolytic
temperatures in N2 and CO2 are very similar at ≤715 °C, such the si-
milarities are well evidenced by the mass decay and differential ther-
mogram (DTG) curves. On the contrary to the results in Fig. 3(a), Fig. 2
already showed that the evolution trends of the gaseous effluents from
pyrolysis of BP in CO2 were different from those in N2. Thus, such the
discrepancies in Figs. 2 and 3(a) can be a key clue for the gas phase
reaction between volatile pyrolysates and CO2 because any hetero-
geneous interactions between the solid sample (BP) and CO2 results in
the subsequent difference in the TG and DTG curves. Note that the TGA
test only offers mass change in accordance with the thermolytic tem-
perature. However, at ≥715 °C, the more mass conversion was
achieved only from CO2, and the identified mass change is mainly

Table 2
Identified chemical species in biocrude from two-stage BP pyrolysis in N2 and CO2 conditions (Peak area in N2 and CO2 are scale-downed as 106).
No. Retention Time, [min] Compounds Formula Area in N2 Area in CO2 Variation*, [%]

1 11.67 benzene C6H6 100.50 105.84 5.31

2 16.12 toluene C7H8 198.71 204.57 2.95
3 19.26 1H-pyrrole C4H5N 19.47 24.94 28.06
4 19.51 pyridine C5H5N 8.75 N.D. –
5 19.81 benzo[d]oxazol-2(3H)-one C7H5NO2 N.D. 4.92 –
6 20.47 m-xylene C8H10 17.64 26.06 47.73
7 21.93 styrene C8H8 54.99 70.89 28.91
8 25.65 allylbenzene C9H10 3.79 8.52 124.68
9 26.00 benzofuran C8H6O 7.32 7.97 8.84
10 26.91 1-ethyl-4-methylbenzene C9H12 34.37 51.50 49.87
11 28.14 benzonitrile C7H5N 7.55 5.48 −27.42
12 29.01 phenyl acetate C8H8O2 N.D. 7.02 –
13 30.89 phenol C6H6O 21.83 28.94 32.54
14 32.55 naphthalene C10H8 164.82 112.90 −31.50
15 33.80 o-cresol C7H8O N.D. 8.39 –
16 36.09 2-methylnaphthalene C11H10 29.75 21.78 −26.80
17 36.50 1-methylnaphthalene C11H10 15.41 16.87 9.47
18 37.24 1H-indole C11H10 13.27 7.42 −44.04
19 40.24 acenaphthylene C8H7N 14.46 6.40 −55.74
20 41.59 9H-fluorene C12H8 10.17 4.69 −53.85
21 44.56 anthracene C13H10 39.50 14.34 −63.69
22 50.61 phenanthrene C14H10 7.19 2.24 −68.78
23 53.48 6,8-dimethoxyquinoline-5-amine C14H10 6.06 N.D. –

5
D. Kwon, et al.
Fig. 3. (a) Thermogram (TG) and differential thermogram (DTG) curves of BP from N2 and CO2, (b) TG and DTG curves of BP from air.
attributed to the Boudouard reaction. To confirm the completion of
Boudouard reaction, the same TGA test was done in air. Because the
residual component after BP pyrolysis in the air is ash, which does not
have a carbon source for the Boudouard reaction, the residual mass
from BP pyrolysis in CO2 condition should be identical when the Bou-
douard reaction is done. As evidenced, the final residual masses in both
the CO2 (11.2 wt%) and air (11.6 wt%) environments are similar, which
informs that most carbon in BP biochar is converted in CO through the
Boudouard reaction.
3.3. Two-stage pyrolysis of BP in CO2 and N2 environments
As demonstrated in Fig. 3(a), 60 wt% of the original sample mass
was thermally decomposed at ≤420 °C. Nonetheless, the CO en-
hancement by the gas phase reaction only occurred at ≥420 °C. Such
the observation clarifies that the gas phase reaction was not activated at
≤420 °C. Thus, it is desirable to prove the temperature region that CO2
reacts with volatile pyrolysates from pyrolysis of BP below 720 °C,
where no Boudouard reaction occurs for a gasification reaction. To
confirm this, two-stage pyrolysis of BP was done. As noted, the tubular
furnace has two heating zones. The first heating zone was operated
dynamically, and the second heating zone was operated isothermally at
600 °C. The gaseous effluents (H2 and C1-2 chemical species) in ac-
cordance with the thermolytic temperatures were quantified (Fig. 4).
The overall evolution trends of the gaseous effluents are similar
with those in Fig. 1. However, the more CO was formed from 360 to
450 °C from CO2. At ≤360 °C, the expected CO enhancement was not
observed, which is due to the heat transfer delay. Nonetheless, Fig. 4
marginally evidences that the gas phase reaction can universally be
applied by modifying the experimental setup in pyrolysis of BP. Thus,
the CO enhancement suggests that CO2 can be converted into fuel. In
detail, the enhanced production of CO by CO2-cofeed can further pro-
duce H2 via the water-gas-shift (WGS: CO + H2O ⇌ CO2 + H2) reaction
[46]. Interestingly, Fig. 4 demonstrates that the concentrations of H2
(from 300 to 450 °C) and C1-2-hydrocarbon species are enhanced.
Considering the dilution from the CO enhancement, the enhanced for-
mation of H2 and C1-2-hydrocarbons offers another mechanistic feature
associated with CO2. For instance, CO2-cofeed pyrolysis of BP likely
expedite the thermal cracking of volatile pyrolysates evolved from BP
and dehydrogenation while consuming carbons by CO2. These parti-
cular mechanistic roles may greatly affect the compositional matrix of
pyrolysates. For the further study, the overall mass balance from
6
Chemical Engineering Journal 392 (2020) 123774
pyrolysis of BP was established in Fig. 5(a), and the constituents of the
condensable pyrolysates were qualitatively specified. Like Fig. 2(b), the
chromatogram was presented in Fig. 5(b) to visualize each constituent
in biocrude. The constituents in biocrude were labelled, and their de-
tails were summarized in Table 2.
The overall mass balances from the two-stage pyrolysis of BP in both
the atmospheric environments are not much different, which is con-
sistent with the findings in the one-stage pyrolysis (Fig. 2(a)). None-
theless, Fig. 5(b) demonstrates that the compositional matrix of bio-
crude is greatly affected by CO2. In detail, the low molecular benzene
derivatives, such as benzene, toluene, xylene, and styrene, were gen-
erated more in the CO2 environment. On the contrary, the high mole-
cular benzene derivatives, such as polycyclic aromatic carbons (PAHs:
naphthalene, anthracene, and phenanthrene), were generated less in
the CO2 environment. In general, the enhanced cracking of volatile
hydrocarbon species and dehydrogenation expedites the formation of
PAHs [47], which is discrepant with the general knowledge associated
with the PAH formation mechanisms [47]. However, considering
carbon conversion into CO by the gas phase reaction, consuming car-
bons by CO2 likely reduce a chance to form PAHs. Thus, the mechanistic
roles of CO2 identified in this study offers a favorable condition to
control aromaticity of pyrogenic products. Accordingly, the further
endeavors should be given to advance the mechanistic role of CO2 in
the near future.
Pyrolysis of BP is achieved by re-distribution carbons into three
pyrolysates. Thus, it is desirable to seek any differences in biochar.
Accordingly, the surface morphology of two biochar samples generated
from BP in both the N2 and CO2 environments was further examined,
and the SEM snapshots of two biochar samples were presented in Fig. 6.
As depicted, the surface morphology of BP biochar from CO2 is different
from that from N2. Considering the thermolytic temperature (600 °C),
the effect of the Boudouard reaction must not be counted. Thus, the
noted mechanistic roles of CO2 likely result in the different surface
morphology of BP biochar. However, unfortunately, the precise me-
chanistic explanation in line with the morphologic modification of
biochar is not been given at this stage of study.
4. Conclusions
To establish a sustainable platform for the simultaneous waste
management and energy recovery, CO2-cofeed pyrolysis of BP was
mainly investigated as a case study. The gas phase reaction between
D. Kwon, et al. Chemical Engineering Journal 392 (2020) 123774

Fig. 4. Concentration of the gaseous effluents (H2 and C1-2 chemical species) from two-stage pyrolysis (isothermal run at 600 °C) of BP in N2 and CO2.

Fig. 5. (a) Overall mass balance of three pyrogenic products from two-stage pyrolysis (isothermal run at 600 °C) of BP, (b) Chromatogram of biocrude from two-stage
pyrolysis of BP in N2 (black color) and CO2 (red color). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of
this article.)

7
D. Kwon, et al.
Fig. 6. FE-SEM images of biochar from pyrolysis of BP in N2 and CO2 at 600 °C.
CO2 and volatile pyrolysates was confirmed in both the one-stage and
two-stage pyrolysis, which led to more than 20 times of CO generation
in CO2-cofeed pyrolysis, comparing to the pyrolysis in N2 between 300
and 700 °C. Conclusively, the CO enhancement implied CO2 could be
converted into fuels (H2, CO and C1-2 hydrocarbons) at significantly
lower temperature region than the gasification temperature without
oxygen and steam. Moreover, CO2 expedited thermal cracking of vo-
latile pyrolysates evolved from BP and dehydrogenation. Nonetheless,
the aromaticity of biocrude from pyrolysis of BP in CO2 was sig-
nificantly reduced because the formation of the high molecular benzene
derivatives, such as PAHs was non-catalytically restricted. The use of
CO2 in pyrolysis of BP offered a new way to modify the surface mor-
phology of biochar. As a case study for CO2-cofeed pyrolysis of heavily
produced biomass waste, BP, it was proven that CO2 enhanced the CO
production, manipulated biocrude, and modified surface morphology of
biochar, which may apply to various biomass feedstocks. Controlling H
to C ratio from biomass to pyrogenic products is a promising strategy
that can be feasible and potentially useful to various applications. For
the practical use of this platform, further elucidated CO2-cofeed BP
pyrolysis studies have to be conducted. Long-term pyrolysis studies at
various isothermal temperature and use of different reactor setups will
be promising future works. Further parametric optimizations also
should be established in the near future.
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.
Acknowledgements
This work was supported by the New & Renewable Energy Core
Technology Program of the Korea Institute of Energy Technology
Evaluation and Planning, using financial resources granted by the
Ministry of Trade, Industry & Energy, Republic of Korea
(20163010092290).
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