Journal of CO₂ Utilization 37 (2020) 97–105

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Journal of CO2 Utilization

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CO2-cofeeding catalytic pyrolysis of macadamia nutshell T

a,1 a,1 b c a,
Sungyup Jung , Dohee Kwon , Yiu Fai Tsang , Young-Kwon Park , Eilhann E. Kwon *
a
Department of Environment and Energy, Sejong University, Seoul, 05006, Republic of Korea
b
Department of Science and Environmental Studies, The Education University of Hong Kong, Tai Po, New Territories, Hong Kong
c
School of Environmental Engineering, University of Seoul, Seoul, 02504, Republic of Korea

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

Keywords: Here in this study, we laid great stress on a development of sustainable waste-to-energy (WtE) platform via CO2-
Waste-to-energy cofeeding catalytic pyrolysis of macadamia nutshell (MNS) at mild temperature region. To this end, one-stage
Catalytic pyrolysis and two-stage (non-catalytic/catalytic) pyrolysis of MNS was performed to establish the fundamental relation-
Macadamia nutshell ship of temperature effect on syngas formation. The formation of gaseous pyrolysates was substantially enhanced
Syngas
when two-stage pyrolysis of MNS was applied, and second heating zone isothermally ran at 700 °C. Such the
Carbon dioxide
enhanced generation of gaseous pyrolysates from two-stage MNS pyrolysis of MNS was likely due to tempera-
ture-driven cracking of volatile organic compounds (VOCs). Also, catalytic two-stage pyrolysis of MNS was
performed at lower isothermal running temperature (500 °C) over Ni/SiO2 and Co/SiO2. The enhanced for-
mation of syngas (H2 and CO) was observed from catalytic pyrolysis of MNS. Therefore, pyrolysis of MNS over
Ni/SiO2 or Co/SiO2 could be a reliable platform for enhancing syngas formation at mild temperature (≤ 500 °C)
under CO2 environment. In addition, all experimental findings suggested that the use of CO2 is beneficial in the
WtE platform, and the use of CO2 could be a practical climate change mitigation measure.

1. Introduction explained by our socio-economic carbon metabolisms [10].

Rapid urbanization in line with industrialization requires the en-
ormous quantity of carbon [1]. To fulfill such the demand, the massive
fossil resources (especially coal and petroleum) has been consumed
world widely [2], which subsequently leads to anthropogenic CO2
emissions [3]. Hence, the surplus carbon inputs (CO2) from the use of
the fossil resources are beyond the Earth’s capacity to sequester them
via the spontaneous carbon cycle [4]. As such, the excess CO2 inputs
into the atmosphere have been perceived as one of the main driving
forces causing the catastrophic global environmental/socio-economic
problems, namely global warming [5]. Thus, considerable efforts have
been devoted to lower the atmospheric concentration of CO2 [6]. For
example, carbon-free energies (wind power, solar (thermal) energy,
geothermal energy, and tidal energy) have drawn considerable atten-
tion in both the academia and industrial sectors [7]. Indeed, harnessing
the renewable resources into energy offers a principle strategy for
lowering the obsessive reliance on fossil fuels [8]. Nevertheless, it is
unable to replace carbon-based chemicals from the renewable resources
(except biomass) because most of them are only transformed into
electricity and heat energy [9]. Indeed, carbon is an essential element
to modern society, of which the high reliance on carbon is likely
In these contexts, employing biomass in production of chemicals
(biorefinery) [11] and energy (biofuels) [12,13] offers a principle
strategy for sating our massive carbon demand due to its intrinsic
carbon neutrality [14]. Despite numerous socio-economic benefits from
the use of chemicals and energy from biomass [15], insecure supply
chain of it due to the regional/seasonal variations [16] has been rea-
lized as one of the main constraints restricting its practical implantation
[17]. Also, ethical dilemma from converting edible crops into biofuels
[18] has evoked the public resistance to use them (1st generation of
biofuel) [19]. To circumvent the noted technical/ethical demerits, a
great deal of researches on the production of energy has dealt with the
valorization of inedible parts of biomass [20]. The use of 2nd and 3rd
generation of biomasses (i.e., lignocellulosic biomass, municipal solid
wastes, and algal biomass) have been considered viable options to
produce biofuels [21]. However, most commercialized biofuels (i.e.,
bioethanol and biodiesel) are synthesized from the specific constituents
in biomass [22]. In fact, the sugar-based compounds (cellulose and
hemicellulose) and lipid in biomass as converted into bioethanol and
biodiesel, respectively [23]. In these contexts, the use of the specific
compounds in biomass implies that the significant amount of waste is
inevitably generated after the biofuel conversion process [24]. To cope

⁎
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.jcou.2019.12.001
Received 14 November 2019; Received in revised form 2 December 2019; Accepted 3 December 2019
2212-9820/ © 2019 Elsevier Ltd. All rights reserved.
S. Jung, et al.
with the noted demerits, volatile fatty acids, C5-6 furanic and phenolic
compounds extracted from wastes further processed through the con-
secutive unit operations [25], but its technical completeness has not
been fully matured [13,26]. Thus, it is desirable to develop a new
technical platform to directly convert raw biomass wastes into energy
with a suppression of byproducts concurrently. Among the various fuel
processing techniques, the thermo-chemical processes such as gasifi-
cation and pyrolysis, can be viable options to redistribute biomass
wastes into pyrogenic products such as syngas, biochar, and biocrude
[27–31]. Since the gasification and pyrolysis at high temperature can be
energy intensive processes, recent efforts have been made to convert
biomass wastes into pyrogenic products with more energy efficient
technologies such as microwave-assisted pyrolysis [28,29], pyrolysis
under the vacuum environment [30,31], and catalytic pyrolysis
[26,32,33].
Based on the above, pyrolysis of macadamia nutshell (MNS) was
particularly investigated in this study. MNS is a hard-woody shell,
considered a byproduct from macadamia nut processing, of which the
annual production reaches up to 42,150 metric tons [34]. Nevertheless,
a large portion of it is discarded. Accordingly, the production of acti-
vated carbons from MNS biochar has been proposed as an aspect of
waste valorization [35]. However, energy recovery from MNS wastes
via the thermo-chemical conversion process has been rarely in-
vestigated. To our best knowledge, CO2-cofeeding pyrolysis of MNS and
product analysis at mild temperature region (200–720 °C) was not re-
ported. To establish sustainable and environmentally benign energy
conversion platform via thermo-chemical conversion of MNS, CO2 was
employed as a reactive gas medium for MNS pyrolysis in reference to N2
condition. To enhance energy recovery from MNS pyrolysis, earth
abundant/cheap metals (Ni and Co) catalysts were adopted because
both the Ni-based [36] and Co-based [37–39] have been considered
effective metals for bond scissions of complex organic materials. Ac-
cordingly, the present study laid great stress on shifting the carbon
distributions of three phases of pyrolysates (syngas, biocrude, and
biochar) in accordance with the use of metallic catalysts in the presence
of CO2. Prior to MNS pyrolysis, the thermo-gravimetric analysis (TGA)
test of MNS was performed to fundamentally understand thermolytic
behavior of MNS in N2 and CO2 conditions.
2. Materials and methods
2.1. Sample preparation and chemical reagents
Macadamia nutshell (MNS) was purchased from a macadamia pro-
cessing company in Korea. Prior to all the experiments, MNS was wa-
shed with deionized (DI) water to remove nut residue and dust, and
then dried in a convection oven at 80 °C for 72 h. The dried MNS was
ground to adjust particle size below than 355 μ m using a ball mill
(PULVERISETTE 6 Mono Mill, Fritsch, Germany). To determine the
elemental composition of MNS, the ultimate analysis (Table 1) was
performed with an elemental analyzer. Metal precursors, Ni
(NO3)2∙6H2O (97 %) and Co(NO3)2∙6H2O (97 %), were purchased from
Daejung Chemical (Korea). Silica (Lot # MKCG0862) and di-
chloromethane (≥ 99.9 % purity) were purchased from Sigma-Aldrich
(USA). Ultra-high purity grade N2 and CO2 were purchased from Green
Gas (Gwangju, Korea). A calibration gas mixture (Lot # 160-
401257255-1) for micro-GC was purchased from INFICON (Germany).
Table 1
Ultimate analysis of MNS.
Elemental Component
N (wt.%) C (wt.%) S (wt.%) H (wt.%) O (wt.%)
0.541 50.48 0.377 6.375 42.227
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Journal of CO₂ Utilization 37 (2020) 97–105
H2 gas (20 %, N2 balance) for catalyst reduction was obtained from
RIGAS (Daejeon, Korea).
2.2. Catalyst preparation and characterization
Ni(NO3)2∙6H2O and Co(NO3)2∙6H2O metal precursors were used to
fabricate 5 wt.% metals on a silica support (Ni/SiO2 and Co/SiO2) by
the wetness incipient impregnation methods [40]. Each metal precursor
was dissolved in DI water, and droplets of mixed solution were wetted
on SiO2 until impregnated. The prepared samples were dried at 105 °C
for 1 d, and then the samples were calcined at 500 °C for 4 h. The
samples were further reduced at 450 °C for 4 h (a ramp rate of 2 °C
min−1 from room temperature) under 20 % H2 (N2 balanced). X-ray
diffraction (XRD) was performed using a Rigaku D/MAX-III dif-
fractometer to determine crystal structures of catalysts with a scanning
rate of 8˚/min (Ni and Co) from 10 to 80˚. To confirm the Ni and Co
metal loading on the SiO2, inductively coupled plasma optical emission
spectrometry (Perkin-Elmer, Optima 5300 DV) was utilized. Each Ni or
Co metal loading on the support was 5.1 ± 0.1 wt.%.
2.3. Thermo-gravimetric analysis test
To characterize the thermal decomposition behavior of MNS as a
function of temperature, thermo-gravimetric analysis (TGA, STA 499 F1
Jupiter, Netzsch, Germany) tests were carried out in CO2, N2 and air
environments. The gas flow rates were controlled using an embedded
mass flow controller in the TGA unit (70 mL min−1). Temperature
range was from 35 to 900 °C at a heating rate of 10 °C min−1 with a
10.0 ± 0.1 mg of sample loading. To compensate buoyancy effect
arising from the density change of flow gases, blank tests were per-
formed before each TGA running. Proximate analysis of MNS was
conducted by comparing the mass decay in both the N2 and air con-
ditions: moisture (1.1 wt.%), volatile matters (74.5 wt.%), fixed carbon
(17.3 wt.%), and ash (7.1 wt.%).
2.4. MNS pyrolysis in a lab-scale reactor
For a lab-scale pyrolysis of MNS, a batch-type tubular reactor (TR)
was installed. A 90 cm long quartz tube was used as a reactor body
placed within an external furnace, and inner and outer diameters of the
quartz tube were 2.5 and 2.2 cm, respectively. To install gas inlet and
outlet ports, Ultra-Torr vacuum fittings were connected to both ends of
quartz tube. Then, step-down unions (from 2.54 cm to 0.635 cm) were
directly connected to the vacuum fitting. The assembled TR was placed
into a tubular furnace (RD 30/200/11, Nabertherm, Germany), which
was used as an external heating source. The furnace consisted of two
heating zones, and temperature of each heating zone was operated in-
dependently. Mass flow controller (5850E series, Brooks Instrument,
USA) was used to set the flow rate of CO2 and N2 gases (300 mL min−1)
during all the pyrolysis experiments. For one-stage MNS pyrolysis, MNS
(1.00 ± 0.01 g) on the first heating stage center was pyrolyzed until
720 °C with a constant heating rate (10 °C min−1) under each N2 or CO2
gas flow. In two-stage non-catalytic pyrolysis of MNS, setup for the first
stage was identical with the one-stage pyrolysis, while the second stage
was placed next to the first heating zone, isothermally running at 500 or
700 °C under CO2 condition. The ex-situ catalytic pyrolysis of MNS was
carried out with two-stage pyrolysis setup. Ni/SiO2 or Co/SiO2 catalyst
(1.00 ± 0.01 g) was loaded into the center of second heating zone,
packing within quartz wools, and the second heating stage ran at 500 °C
isothermally.
The gaseous effluents from MNS pyrolysis were monitored using an
on-line micro-GC unit equipped with two GC modules having a thermal
conductivity detector. Two Micro-GC units had molecular sieve column
and plot U column, respectively. A standard calibration gas was used for
quantification of gaseous pyrolysates. Liquid pyrolysates from the TR
was further flowed to a condenser filled with a dichloromethane, which
S. Jung, et al.
Scheme 1. Schematic diagram of experimental setup for MNS pyrolysis using the TR.
was immersed in a cold water. Then, the diluted solutions in a di-
chloromethane were injected into a GC/MS-TOF (ALMSCO, UK),
equipped with a DB-WAX column (Agilent). Experimental setup using
the TR is depicted in Scheme 1.
3. Results and discussion
3.1. The thermolytic behaviors of MNS
To understand thermal profiles of MNS in an oxygen-free condition,
MNS pyrolysis was performed with a TGA unit under two gas (N2 and
CO2) conditions from 40 to 900 °C. Mass decay and thermal degradation
rate (differential thermogram: DTG) of MNS are depicted as a function
of temperature in Fig. 1. Thermolytic behaviors of MNS in both con-
ditions are identical at ≤745 °C. Small mass decay below 200 °C is
Fig. 1. Mass decay and differential thermogram (DTG) curves of MNS as a
function of temperature in the N2 (black) and CO2 (red) atmospheres.
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Journal of CO₂ Utilization 37 (2020) 97–105
attributed to moisture within MNS samples in both N2 and CO2 atmo-
spheres. Following rapid thermal degradation is shown at the higher
temperature (206–396 °C), and the mass loss reached to 63 wt.% by 396
°C. This thermal degradation originated from the depletion of the most
volatile organic matters (VOCs) of biomass [41–43]. In this temperature
region, two peaks are overlapped and shown at 294 °C and 362 °C in
DTG curves, respectively. These indicate that there may be more than
one pyrolysis mechanism. Further thermal degradation is shown at
higher temperature, but the degradation rate began to substantially
decrease from 396 °C. Mass decay in the temperature range between
396 and 745 °C was 12 wt.%, and the residual mass at 745 °C was 25 wt.
% in both conditions. The slower thermolysis of MNS between 396 and
745 °C implies the biochar formation, which should be derived from
both dehydrogenation and deoxygenation of the carbon substrate
[41,42]. Note that deoxygenation and dehydrogenation increase C to O
and C to H ratio and accelerates carbonization. Since bonding energies
for CeO (358 kJ mol−1) is lower than and CeH (416 kJ mol−1), re-
spectively [44,45], it is expected that deoxygenation may occur prior to
dehydrogenation. Further studies will be discussed in one-stage and
two-stage pyrolysis studies. At ≥ 745 °C, the only slight mass decay of
MNS is shown in N2 condition, while additional decomposition oc-
curred from CO2 atmosphere. This mass decay at 745 °C is attributed to
the Boudouard reaction (BR: C (s ) + CO2 ⇌ 2CO ). [46], because the BR
is thermodynamically favorable at ≥720 °C [14]. Under CO2 environ-
ment, continuous thermal degradation of MNS from TGA study was
shown beyond 900 °C, describing that the BR is incomplete due to their
slow kinetics. To find an evidence of such the slow kinetics of BR and
possibly other reactions in both environments, TGA test was further
conducted in air condition to estimate remaining carbon at 900 °C. The
final residual mass of MNS was 7.1 wt.% at 600 °C, and there was no
further mass decay up to 900 °C in the air condition, while that in both
CO2 (19.7 wt.%) and N2 (24.4 wt.%) conditions was much higher at 900
°C. These results strongly show that the ash content in MNS is about 7.1
wt.%, and thermolysis of MNS in both conditions is incomplete due to
remaining organic contents there.
Such the series of TGA tests estimated a depletion of moisture and
VOCs, and biochar formation from thermolysis of MNS, but the tests
were not able to prove the reaction mechanism and products distribu-
tion during thermo-chemical conversion of MNS. To understand the
thermolysis of MNS in depth, quantitative analysis of gas and liquid
pyrolysates during the pyrolysis of MNS was necessary in a wide range
of temperature.
S. Jung, et al.
Fig. 2. Gaseous effluents evolution profile (H2 and C1-2 chemical species) from one-stage MNS pyrolysis in N2 (black) and CO2 (red) atmospheres.
3.2. Non-catalytic pyrolysis of MNS
One-stage MNS pyrolysis was conducted in a fixed-bed TR under N2
or CO2 flow (300 mL min−1) to quantify and compare the gaseous and
liquid pyrolysates in both conditions. Pyrolysis temperature was from
90 to 720 °C at a heating rate of 10 °C min−1. The final temperature,
720 °C, was chosen, to elucidate mechanistic roles of CO2 in comparison
with N2 environment when no BR occurs (Fig. 1). Gaseous effluents
from the TR were quantitatively monitored using an on-line micro-GC
system, and the concentration profiles of the gas products are depicted
in Fig. 2. Because MNS pyrolysis in the one-stage reactor has a similar
experimental setting with TGA experiment, the concentration profiles
of gaseous pyrolysates in the one-stage pyrolysis should well reflect the
thermal profiles of MNS from TGA tests (Fig. 1).
From the one-stage pyrolysis, CO generation is initiated at 300 °C
and reached to maximum concentration at 360 °C (Fig. 2), followed by
the continuous decrease of CO evolution until 600 °C in both environ-
ments. Such the CO concentration profiles are well matched with the
thermal profiles of MNS discussed in Fig. 1. The biggest DTG peaks in
TGA tests are shown at 294 and 362 °C, corresponding to a significant
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Journal of CO₂ Utilization 37 (2020) 97–105
depletion of MNS resulting from evolution of gaseous pyrolysates
(Fig. 1) in both conditions. Although thermolytic behavior of MNS in
both conditions from TGA experiments is identical at ≤ 745 °C, CO
evolution profiles in both environments are different in the temperature
range of 600–720 °C (Fig. 2). TGA experiments confirmed that no
heterogeneous reaction between MNS and CO2 occurred at ≤ 745 °C. In
the presence of CO2, however, CO generation continuously increased as
temperature increased at ≥ 600 °C unlike N2 condition. This result is
likely due to the homogeneous reaction between volatiles pyrolysates
from MNS pyrolysis and CO2. Note that there is no BR in this tem-
perature region in the presence of CO2. CH4 evolution is initiated at 330
°C, and continuous evolution of CH4 is shown in both environments
until source depletion (Fig. 2). Corresponding mass decay patterns of
MNS from TGA study indicate that CH4 formation results from cleavage
of polymeric backbone on biomass compounds [14,42].
H2 formation is initiated from 510 °C, and its maximum con-
centration was achieved at the highest pyrolysis temperature (720 °C)
in N2 condition (Fig. 2). Continuous mass decrease of MNS at ≥ 510 °C
corresponds to H2 formation according to TGA studies under both
conditions (Fig. 1). In this temperature region, H2 generation is likely
S. Jung, et al.
attributed to dehydrogenation of MNS. Although the identical thermal
decomposition of MNS is shown from TGA experiments in both en-
vironments, H2 evolution under CO2 is lower than N2 condition at ≥
600 °C (Fig. 2). Because this temperature region is where CO formation
began to substantially increase when CO2 applied (Fig. 2), relative H2
concentration in CO2 condition became lower than N2 condition due to
dilution effect, not suppression of H2 formation.
The formation of CO, CH4 and H2 is expected from CeO, CH and
CCee bond cleavages on polymeric back bones of MSN at ≤ 600 °C in
both conditions. As discussed in the TGA studies (Fig. 1), a formation of
biochar should result from deoxygenation and dehydrogenation of
biomass compounds, which mainly consisted of organic C, O, and H
elements. During the thermolysis of MNS, CO evolution could be from
deoxygenation of MNS, while a formation of CH4 and H2 could be at-
tributed to dehydrogenation of it. Evolution patterns of both CO and
H2/CH4 confirmed that CO formation was occurred prior to the gen-
eration of CH4 and H2 (Fig. 2). This means that deoxygenation is pro-
ceeded earlier than dehydrogenation, and the result agrees with the
aforementioned discussion that CeO (358 kJ mol−1) has lower bonding
energy than CeH (416 kJ mol−1) [44,45], leading to deoxygenation
prior to dehydrogenation. In detail, the most dramatical mass decay by
362 °C is mainly attributed to deoxygenation of MNS, and the following
mass decay is possibly contributed to the dehydrogenation.
Interestingly, additional CO evolution occurred in the presence of
CO2, though TGA confirmed the no heterogeneous reaction between
CO2 and MNS at ≥ 600 °C. This tells that CO2 could have homogeneous
reaction with VOCs derived from MNS pyrolysis, resulting in the pro-
duction of CO at the high temperature region. In N2 condition, the
homogeneous reaction did not occur due to an absence of O source.
Two C2 gaseous effluents, C2H6 and C2H4 are also observed from
one-stage MNS pyrolysis at ≥ 360 °C, though their quantities (≤0.03
mol%) produced from one-stage pyrolysis are negligible, comparing to
the amount of CO and H2. The formation of C2 or long-chain hydro-
carbons probably requires additional reaction mechanism beyond CeC,
CO or CHee cleavages.
Two-stage MNS pyrolysis is also conducted to examine the product
distribution in a different reactor setup and thermolysis condition in
CO2 environment. In detail, additional second heating zone is operated
isothermally at 500 or 700 °C, and the effect of second heating zone
temperatures on MNS pyrolysis is investigated (Fig. 3). When the
second heating zone temperature is 500 °C, concentration profiles of
gaseous products are similar with one-stage pyrolysis. However, sub-
stantial improvement of gaseous effluents (CO, H2, CH4, C2H4 and
C2H2) is shown when the second heating zone ran at 700 °C iso-
thermally (Fig. 3). As noted in both the TGA and one-stage pyrolysis
experiments (Figs. 1 and 2), deoxygenation of biomass is responsible for
CO generation at ≤ 600 °C, and the maximum evolution of CO was
shown around 360 °C. In two stage pyrolysis, the maximum peak in
terms of CO evolution is shown at 420 °C, and the concentration in-
crease more than 7 times at the maximum when the second heating
zone ran at 700 °C. However, CO concentration is same with one-stage
pyrolysis at ≥ 600 °C. This indicates that the substantial improvement
of CO generation around 420 °C is not originated from homogeneous
reaction between CO2 and VOCs.
H2 evolution in one-stage pyrolysis is initiated at ≥510 °C, and the
maximum generation is at the maximum experiment temperature
(Fig. 2). However, two-stage pyrolysis initiated H2 generation much
earlier at ≥ 360 °C, leading to maximum H2 evolution at 420 °C when
the second heating zone isothermally ran at 700 °C (Fig. 3). There is
also remarkable production of CH4 and C2H4 at ≥ 360 °C in two-stage
pyrolysis, while they are negligibly produced in the one-stage pyrolysis
and two-stage pyrolysis ran at 500 °C. The starting temperatures for
CH4 and C2H4 formation in one-stage pyrolysis are identical with two-
stage pyrolysis, the evolution of CH4 and C2H4 in two-stage pyrolysis
(700 °C) jumped more than two orders of magnitude higher, comparing
with one-stage pyrolysis. In addition, a formation of C2H2 is shown
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Journal of CO₂ Utilization 37 (2020) 97–105
(0.22 mol% at 450 °C) in the two-stage pyrolysis, employing 700 °C
second heating zone, whereas C2H2 is not produced from both one-stage
pyrolysis and two-stage pyrolysis, ran at 500 °C. This is likely attributed
to the reaction mechanism only occurred in the two-stage pyrolysis
setup.
Overall evolution patterns commonly showed dramatic enhance-
ment of gaseous effluents between 300 and 600 °C in two-stage pyr-
olysis, isothermally running at 700 °C. Also, C2H4 was only shown in
the two-stage pyrolysis setup, meaning that additional reactions in the
second heating zone promoted evolution of gaseous pyrolysates. It is
expected that VOCs generated from MNS pyrolysis in the first heating
zone is delivered to the second heating zone, and additional thermal
cracking of VOCs in the second heating zone could significantly con-
tribute to the formation of gaseous effluents at 700 °C. Such the great
improvement of gaseous effluents only showed at 700 °C of the second
heating zone, while the gas evolution is not enhanced at 500 °C.
Therefore, it is hypothesized that VOCs seem to be rapidly converted
into gaseous effluents at ≥ 700 °C, but one-stage pyrolysis or two-stage
pyrolysis, isothermally running at 500 °C, are not able to promptly
convert VOCs into permanent gases.
To confirm the conversion of VOCs (i.e., liquid tar) to gaseous
pyrolysates, mass balance of solid char, liquid tar and gas products is
constructed in both one-stage pyrolysis and two-stage pyrolysis (700 °C)
(Fig. 4-a). Mass content of solid char in the two-stage pyrolysis is
consistent with one-stage pyrolysis because solid char formed in the
first heating zone is remained in there. The second heating zone could
not have influence on the gas or liquid formation from the solid char. As
hypothesized, liquid tar content significantly dropped to 2.2 wt.% in
two-stage pyrolysis from 13.3 wt.% in one-stage pyrolysis. This con-
firmed that VOCs is converted into permanent gaseous effluents at 700
°C. It can be further estimated that the remaining liquid compounds
after thermal cracking at 700 °C should lose functional groups having
oxygen and hydrogen due to the formation of CO, H2 and hydrocarbons.
From the analysis of GC/MS chromatograms, composition of the liquid
tar is further analyzed to investigate their functional groups (Table 2
and Fig. 4-b). Since lignocellulosic biomass is composed of cellulose,
hemicellulose and lignin parts, the liquid tar produced from one-stage
MNS pyrolysis mainly consisted of oxygenates and heterocyclic com-
pounds (Table 2). However, significant loss of oxygen-containing
functional groups with increased aromaticity is shown after two-stage
pyrolysis at 700 °C from GC/MS results. This is likely contributed to the
enhancement of CO, H2 and hydrocarbons in the two-stage pyrolysis
(Fig. 3).
3.3. Catalytic pyrolysis of MNS
Non-catalytic MNS pyrolysis showed the syngas formation, origi-
nated from the direct production of gaseous effluents from MNS pyr-
olysis or thermal cracking of VOCs. When two-stage pyrolysis is em-
ployed, isothermally running at 700 °C, substantial improvement of
syngas formation is shown, suppressing liquid tar formation. However,
two stage pyrolysis, running at 500 °C, was not able to enhance the
syngas formation. Elevation of pyrolysis temperature is suggested to
produce more gaseous pyrolysates, but employment of higher tem-
perature to promote syngas formation may consume excessive energy to
generate energy-related products. To make the two-stage pyrolysis
more promising, operating at mild temperature should be necessary.
Catalyst is a substance that can enable to proceed a chemical reaction
with lower activation energy in different conditions (desirable for lower
temperature and pressure). In this regard, earth abundant and in-
expensive metal catalysts are prepared to conduct catalytic pyrolysis in
two-stage reactor at lower pyrolysis temperature (500 °C).
Metal catalysts are fabricated on SiO2 support, and crystal orienta-
tion of the Ni and Co catalysts is examined with XRD (Fig. 5). Such the
metal catalysts showed corresponding peaks of each metal and a SiO2
support; those peaks are identified with the JCPDS library (Ni: 65-0380,
S. Jung, et al. Journal of CO₂ Utilization 37 (2020) 97–105

Fig. 3. Gaseous effluents evolution profile (H2 and C1-2 chemical species) from MNS pyrolysis in CO2. Non-catalytic MNS pyrolysis in both two-stage and one-stage
setups are compared.

Fig. 4. (a) Mass balance of pyrolysates from MNS pyrolysis in the CO2 and (b) GC/MS chromatograms of liquid tar in one-stage and two-stage pyrolysis (isothermally
run at 700 °C).

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Table 2
Chemical composition of liquid tar in both one-stage and two-stage pyrolysis
(isothermally run at 700 °C) in the CO2 condition.
No. RT (min) Chemical Composition Formula 1stage Pick 2stage Pick
Areaa Areaa

1 11.5641 benzene C6H6 N.D. 169414947

2 12.4629 ethyl acetate C4H8O2 16601390 N.D.
3 14.0758 propan-1-ol C3H8O 79869941 N.D.
4 15.6216 3-methylbut-3-en-2- C5H8O N.D. 3681890
one
5 16.1592 acetic acid C2H4O2 483150864 N.D.
6 16.7557 toluene C7H8 N.D. 31860325
7 17.0833 2-methylpropan-1-ol C4H10O 94990746 N.D.
8 20.7376 3-hydroxypropanal C3H6O2 44649274 N.D.
9 20.9812 2,4-dimethylpentan-3- C7H14O 14345591 N.D.
one
10 22.1153 succinaldehyde C4H6O2 14415260 N.D.
11 22.3757 methyl 2- C4H6O3 43484755 N.D.
oxopropanoate
12 22.4598 styrene C8H8 N.D. 45050940 Fig. 5. XRD patterns of 5 wt.% Ni and Co catalysts supported on SiO2.
13 23.0058 furan-2-carbaldehyde C5H4O2 173959248 N.D.
14 24.7363 2-oxopropyl acetate C5H8O3 18319891 N.D.
15 24.9967 furan-2-ylmethanol C5H6O2 48007561 N.D. When Ni/SiO2 and Co/SiO2 catalysts are placed on the second
16 25.2235 butan-2-one C4H8O 15607594 N.D. heating zone, running isothermally at 500 °C, CO evolution increased
17 26.4753 benzofuran C8H6O N.D. 3239788 approximately three times more than non-catalytic pyrolysis (Fig. 6) at
18 27.3742 1H-indene C9H8 N.D. 46366231
≤ 600 °C. The initiation temperature for CO generation over metal
19 27.9202 5-methylfuran-2(3 H)- C6H6O2 70670241 N.D.
one catalysts is close to that non-catalytic pyrolysis, but more exponential
20 28.7351 benzonitrile C7H5N N.D. 1845350 increase of CO formation is shown due to catalytic thermal cracking of
21 30.0372 4-hydroxy-5,6-dihydro- C5H6O3 32973378 N.D. VOCs over metal catalysts at 500 °C of the second heating zone. This
2H-pyran-2-one tells that the Ni and Co metal catalysts helped to lower thermal cracking
22 31.1545 phenol C6H6O 69265652 1025162
(N2)
temperature for cleavage of various carbon networks in VOCs.
31.1797 Non-catalytic pyrolysis in both one-stage and two-stage setups
(CO2) (isothermally ran at 500 °C) did not generate H2 gas at ≤ 510 °C, while
23 31.5829 2-methoxyphenol C7H8O2 140753853 N.D. catalytic pyrolysis promoted H2 generation between 300 and 500 °C
24 32.6246 m-cresol C7H8O 16247453 N.D.
(Fig. 6). In catalytic pyrolysis, another H2 evolution at ≥ 510 °C is
25 33.0279 naphthalene C10H8 N.D. 195889582
26 34.0527 p-cresol C7H8O 40083138 N.D. identical with non-catalytic pyrolysis. Although catalytic pyrolysis en-
27 34.4811 4-methoxy-3- C8H10O2 147794362 N.D. hanced H2 and CO generation, both Ni and Co catalysts did not promote
methylphenol the generation of hydrocarbons. From these results, it can be inter-
28 35.0776 cyclopropylmethanol C4H8O 83030560 N.D. preted that both Ni and Co catalysts promote dehydrogenation and
29 35.3044 3,4-dimethylphenol C8H10O 27654167 N.D.
deoxygenation of VOCs at 500 °C. Non-catalytic pyrolysis, employing
30 36.5813 4-ethyl-2- C9H12O2 41329123 N.D.
methoxyphenol 500 °C in the second stage, did not affect to the production of gaseous
31 36.7914 2-methylnaphthalene C11H10 N.D. 3390404 pyrolysates, while H2 and CO generation greatly enhanced by the ad-
32 37.1862 1-methylnaphthalene C11H10 N.D. 1294351 dition of Ni and Co catalysts.
33 38.1186 cyclopentadiene C5H6O2 11797778 N.D.
dioxide
34 38.5808 biphenyl C12H10 N.D. 7031145
35 39.1267 2-methoxy-4- C9H10O2 15668395 N.D. 4. Conclusions
vinylphenol
36 39.3115 (Z)-ethyl but-2-enoate C6H10O2 15999457 N.D. This work investigated CO2-cofeeding catalytic pyrolysis of MNS to
37 39.992 (E)-4-oxobut-2-enyl C6H8O3 15660128 N.D.
examine the formation of syngas fuels under various pyrolysis condi-
acetate
38 40.6473 1H-indole C8H7N N.D. 664467 tions and catalysts. CO2 expedited CO generation at ≥ 610 °C due to
39 41.4033 5-(hydroxymethyl) C6H6O3 28934548 N.D. homogeneous reaction with VOCs. Two-stage pyrolysis greatly en-
furan-2-carbaldehyde hanced the formation of gaseous pyrolysates (H2, CO, CH4, and C2H4) at
40 42.0923 acenaphthylene C12H8 N.D. 16323328
≤ 610 °C when the second heating zone ran at high temperature (700
41 42.2434 (E)-2-methoxy-4-(prop- C10H12O2 29399401 N.D.
1-enyl)phenol
°C). Such the enhanced generation of syngas and fuels in two-stage
42 43.6296 dibenzo[b,d]furan C12H8O N.D. 4169912 pyrolysis stemmed from the thermal cracking of VOCs at the second
43 44.4192 4-hydroxy-3- C8H8O3 13900757 N.D. heating zone, losing oxygen-containing functional groups with increase
methoxybenzaldehyde of aromaticity. Catalytic two-stage pyrolysis was carried out over earth
44 45.0493 9H-Fluorene C13H10 N.D. 12057580
abundant metal catalysts (Ni and Co) to lower second heating zone
45 51.0894 phenanthrene C14H10 N.D. 43878774
46 51.6102 anthracene C14H10 N.D. 2912045 operating temperature (500 °C). Significant enhancement of H2 and CO
47 52.383 butyric acid C4H8O2 32076425 N.D. formation was shown over Ni and Co catalysts because the catalysts
48 54.0464 4H-cyclopenta[def] C15H10 N.D. 2403237 promoted deoxygenation and dehydrogenation of VOCs. These results
phenanthrene
greatly offer a sustainable approach to produce syngas and fuels from
a biomass-derived wastes at mild operating temperature with greenhouse
N.D.: Not detected.
gas, CO2. For the practical application of CO2-cofeeding MNS pyrolysis
for syngas and biochar formation, process optimization should be fol-
Co: 15-0806, and SiO2: 29-0085). On Ni/SiO2, 44.3˚, 51.7˚, 76.2˚ peaks
lowed to find a proper reactor setup and operating condition. This work
corresponding to Ni (111), Ni (200), and Ni (220) were observed with a
would contribute to helping the development of more practical systems
peak of SiO2 support at 22.5˚. SiO2 peaks also appeared on Co/SiO2 at
under the CO2 condition for the future works.
the same position, Co (111) peak was shown at 44.1˚.

103
S. Jung, et al.
Fig. 6. Gaseous effluents evolution profiles from two-stage catalytic pyrolysis of MNS over Ni (red) and Co (blue) catalysts, comparing to non-catalytic pyrolysis
(black). Isothermal running temperature at the second heating zone was 500 °C.
Authors contribution statement
S. Jung: Experiment design and data interpretation, original draft
preparation.
D. Kwon: Leading experiment and data interpretation, partial draft
writing.
Y.F. Tsang: Partial data interpretation, manuscript review and
editing.
Y.-K. Park: Partial data collection and interpretation, manuscript
review and editing.
E.E. Kwon: Supervision, Writing - Review & Editing.
Declaration of Competing Interest
The authors have no conflicts of interest to declare.
Acknowledgements
This work was also supported by the National Research Foundation
of Korea (NRF) grants funded by the Korea government (MSIT) (NRF-
2019R1A4A1027795 and NRF-2019H1D3A1A01070644).
104
Journal of CO₂ Utilization 37 (2020) 97–105
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