Journal of CO₂ Utilization 39 (2020) 101182

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Journal of CO2 Utilization

journal homepage: www.elsevier.com/locate/jcou

Synergistic effects of CO2 on ex situ catalytic pyrolysis of lignocellulosic T

biomass over a Ni/SiO2 catalyst
Seong-Heon Choa, Sungyup Junga, Young-Kwon Parkb, Yiu Fai Tsangc, Changkook Ryud,*,
Eilhann E. Kwona,*
a
Department of Environment and Energy, Sejong University, Seoul 05006, Republic of Korea
b
School of Environmental Engineering, University of Seoul, Seoul 02504, Republic of Korea
c
Department of Science and Environmental Studies, The Education University of Hong Kong, Tai Po, New Territories, Hong Kong
d
School of Mechanical Engineering, Sungkyunkwan University, Suwon 16419, Republic of Korea

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

Keywords: This work laid emphasis on catalytic pyrolysis of Styrax japonicus to construct a biomass-to-energy conversion
Catalytic pyrolysis platform. CO2 was particularly chosen to enhance the catalytic pyrolysis of the biomass waste, in reference to N2-
Carbon dioxide 挥发性 purged pyrolysis. The specific roles of CO2 on pyrolysis of S. japonicus in line with synergistic effect of Ni-based
Waste-to-energy catalysts was investigated. It was shown that CO2 played as an oxidant for CO formation via homogeneous gas
CO2-to-fuel
phase reaction of CO2 with volatile organic carbons (VOCs) liberated from the thermolysis of S. japonicus. Ni/
Biomass valorization
芳烃性 SiO2 catalyst expedited dehydrogenation (DH) of the VOCs, resulting in significant H2 generation and alteration
Hydrogen
of aromaticity in VOCs. Each CO2 and Ni catalyst independently enhanced CO and H2 formation, respectively,
and their synergistic effects were shown at ≥ 600 °C. Coke deposition on the Ni/SiO2 catalyst was confirmed
after catalytic pyrolysis, while the suppression of coke formation on the catalyst surface was achieved under the
CO2 environment.
独立地 完成

1. Introduction
Global warming caused by diverse anthropogenic activities (i.e.,
greenhouse gases: GHGs) [1,2] has been perceived as significant since it
leads to catastrophic environmental consequence [3]. Among GHGs,
CO2 arising from the heavy use of fossil fuels has been recognized as a
critical contributor for the global warming [4]. 350 billion tons of an-
thropogenic CO2 from the use of fossil fuels have been emitted since
mid-1900s, leading to unprecedent the increase of atmospheric CO2
concentrations from 320 to 400 ppm over the last five decades [5].
Accordingly, a lot of concerns on the sustainable production of re-
newable energy and chemicals has been paid [6,7]. As a measure of
global warming mitigation, the utilization of biomass as a raw material
for energy (biofuel) and chemical (biorefinery) has been spotlighted
due to its intrinsic carbon neutrality [8]. Considering that biomass is
the only carbon-based material among the renewable materials [9], the
production of chemical/energy through the specific synthetic routes
from biomass offers the principle strategy for abating the environ-
mental threats from global warming [10]. In these contexts, the latest
IPCC report offered that bioenergy and carbon capture and storage
could be key studies for delaying catastrophic environmental
消化 发酵
酯基转移 加氢氧化
consequences of global warming [11].
Various technical platforms for biomass conversion into chemical/
energy have been developed, which could be classified into three main 气化
routes: 1) biochemical processes (digestion and fermentation) [12,13],
2) chemical processes (transesterification, hydrodeoxygenation, and
hydrolysis) [14–16], and 3) thermo-chemical process (gasification and
pyrolysis) [17–19]. In reference to the thermo-chemical processes, the
biochemical/chemical processes are economically less viable because
碳基底
the overall yield for the target products from them is readily affected by
the types of carbon substrates and operational conditions [10,20]. In 微生物
addition, their reaction rates are not fast enough for mass energy pro-
duction [21]. More importantly, the microbial growth in line with the 新陈代谢
uncontrollable metabolisms during the process leads to the unwanted
生物乙醇
carbon loss (such as cell growth and CO2 by respiration) [21]. More-
over, producing biofuels, such as bioethanol and biodiesel, is not de-
生物柴油
sirable in terms of carbon utilization since the only single nutritional
element in biomass is converted into biofuels during the conversion
process, thereby resulting in the massive generation of waste [22,23].
In detail, sugary components and lipids extracted from raw biomass
materials are transformed into biofuels, respectively [23,24]. However,
脂
the thermo-chemical processes of biomass offer a route for maximizing

灾难的
⁎
Corresponding authors.
E-mail addresses: cryu@me.skku.ac.kr (C. Ryu), ekwon74@sejong.ac.kr (E.E. Kwon).

https://doi.org/10.1016/j.jcou.2020.101182
Received 1 March 2020; Received in revised form 16 April 2020; Accepted 24 April 2020
Available online 12 May 2020
2212-9820/ © 2020 Elsevier Ltd. All rights reserved.
 S.-H. Cho, et al.
透明的 良性的
carbon utilization of it [25]. Nevertheless, considering that the thermo-
chemical process is an energy-intensive system, the technical develop-
ment in line with the environmentally benign carbon management
should be established with the fully transparent manners [26].
As such, to enhance quantity/quality of pyrogenic products or im-
prove the conversion efficiency, the catalytic thermo-chemical con-
version of biomass has been developed [27,28]. Selective conversion of
biomass into desired pyrolytic oil compounds (biocrude) and synthetic
gas (H2 and CO) is important for their practical uses. In detail, pyrolytic
oils and synthetic gas could be used as fuels and chemical intermediates 沸石 analysis was carried out to determine the organic contents of S. japo-
for value-added chemicals. Various pyrolysis reactors [29,30] and di-
verse classes of the catalysts, such as zeolite, metal, and metal oxides 定制 Germany): 45.4 wt.% (C), 48.6 wt.% (O), 5.8 wt.% (H), 0.2 wt.% (S),
catalysts, have been used widely to tailor pyrogenic products (liquid
and gaseous pyrolysates) [31–33]. Among the broadly used catalysts for
the thermo-chemical biomass conversion, zeolite has been employed to
酸性
upgrade pyrogenic products due to their well-defined cracking ability
imparted from its highly ordered/structured porosity and acidity
[34–36]. Catalytic pyrolysis of biomass over zeolite have been con-
ducted through two different ways; in-situ and ex-situ [37,38]. In re-
ference to ex-situ one, in-situ catalytic pyrolysis of biomass over zeolite
烃类， offered that in-situ mode is effective to the enhanced formation of liquid 结焦
碳氢化合物
hydrocarbons (HCs) and the lower yield of gaseous HCs [37]. Coke
formation during in-situ catalytic pyrolysis of biomass deteriorates an
economic and technical advancement imparted from zeolite. 恶化
It is revealed that the steam reforming or CO2-assisted gasification
(Boudouard reaction: BR: C (s) + CO2 ⇌ 2CO) at high temperature
(800–1400 °C) could help to decompose solid carbons deposited on the
catalyst surface through oxidation reactions [39,40]. However, these
are energy intensive reactions occurring at high temperature region. In
contrast, recovery of a catalyst is technically challenging after catalytic
pyrolysis of biomass in an oxygen-free condition [33]. For the practical
applications of pyrolysis catalysts to produce energy, the continuous
use of highly efficient catalyst is necessary for energy production at
moderate thermo-chemical conditions where no gasification occurs.
Hence, it is desirable to develop an innovative process to prevent the
coke formation during catalytic pyrolysis of biomass at lower tem-
perature regions (200–720 °C) [41,42].
Based on the above, this study laid great stress on catalytic pyrolysis
of a lignocellulosic biomass over supported Ni catalyst (Ni/SiO2).
Specifically, Styrax japonicus was used as a model compound, and dif-
ferent Ni-loaded catalysts (2 wt.% and 5 wt.%) were tested. To offer the
enhanced catalytic capabilities of Ni/SiO2, CO2 was particularly used
because our previous studies proved that CO2 offered the particular
thermolytic routes for biomass [43–45]. In detail, CO2 expedited
thermal cracking of volatile pyrolysates [45]. Also, the gas phase re-
actions (GPR) of CO2 and volatile pyrolysates led to the enhanced for-
mation of CO [44]. Thus, this study particularly explored the synergistic
effects of Ni/SiO2 and CO2 on the thermolysis of S. japonicus. To this
end, catalytic pyrolysis was done in a two-stage fixed bed reactor. The
same experiments in an absence of catalyst were performed as a re-
ference. Accordingly, all the pyrolysates from pyrolysis of a model
biomass compound (S. japonicus) in the two atmospheric (N2 and CO2)
conditions were compared to find the synergistic roles of catalysts and
共进料 CO2. In addition, estimation of energy balance between N2 and CO2- 原料 tubular furnaces with a continuous serial connection were operated
cofeeding pyrolysis in reference to the higher heating value of feedstock
was conducted to prove the energy efficiency and the prospect of this
system. Prior to catalytic pyrolysis of S. japonicus, the thermo-gravi-
metric analysis (TGA) of it in CO2 was carried out. A series of the cat-
alytic pyrolysis tests using S. japonicus was done to understand the
specific roles of CO2, and its mechanistic roles were postulated by ex-
amining the compositional matrix of pyrolysates from pyrolysis S. ja-
ponicus over Ni/SiO2 in both atmospheric conditions. 假设
矩阵&基质
热解物
2
Journal of CO₂ Utilization 39 (2020) 101182
2. Experimental
2.1. Materials
S. japonicus sample was provided from National Institute of Forest
Science (Korea). It was ground and sieved to make a powder sample,
吸水剂
having a uniform size less than 250 μm, and then dried at 95 °C for 48 h.
The dried sample was placed in a desiccator, filled with a water ab-
sorbent (silica gel), to prevent from exposure to moisture. Ultimate
nicus using an elemental analyzer (Vario Micro Cube, Elementar,
and 0.1 wt.% (N). Dichloromethane (Prod. # 400042, Sigma-Aldrich,
USA) was used for collection of volatile organic compounds (VOCs).
Nickel nitrate hexahydrate (Prod. # 5608-4405, Daejung Chemicals,
Korea) and Silica (Prod. # 60741, Sigma-Aldrich, USA) were prepared
for catalyst synthesis.
2.2. Catalyst preparation and characterization
Ni supported on SiO2 catalysts (2 wt.% and 5 wt.% Ni loading) were
prepared using an incipient wetness impregnation method [46,47]. In
short, the Ni precursor solution was prepared in deionized water, and
the precursor solution was added dropwise to SiO2 support until im-
pregnation was done. The sample was dried at 105 °C overnight, fol-
lowed by calcination at 550 °C. The calcined sample was reduced to
produce Ni/SiO2 catalysts. Reduction temperature was 550 °C for 4 h
(ramp rate: 2 °C min−1) under the 20 vol.% H2 (N2 balance). X-ray
diffraction (XRD: PANalytical Empyrean, Netherlands) measurement
was carried out to examine the crystal structure of Ni/SiO2 at 5° min−1
scan rate (10°–90°).
2.3. Thermolytic behavior of S. japonicus
To examine thermal degradation of S. japonicus, TGA (Thermo-
gravimetric analysis) tests were conducted. 20.00 ± 0.01 mg samples
were placed in a TGA instrument (Netzsch STA 449) and thermally
degraded from 25 to 900 °C at 10 °C min−1 ramp rate in N2 or CO2
condition. To offset the buoyancy effect evolved from each purge gas
flow, the empty run was performed prior to TGA experiment with S.
japonicus.
2.4. Pyrolysis of S. japonicus
CO2-cofeeding pyrolysis of S. japonicus was done using a tubular
reactor (TR) in reference to pyrolysis of it in the N2 condition. For lab-
scale pyrolysis of S. japonicus, the TR was constructed with a quartz
tube main body and an external tubular furnace. The Quartz tube was
linked to vacuum fittings and union connectors to make gas flow
without leakage. For one-stage pyrolysis, 1 g of S. japonicus was used a
reactant, loading into the TR center under the flow of N2 or CO2 gas
(100 mL min−1). Temperature of the TR for pyrolysis started from 200
to 720 °C with 10 °C min−1 heating rate. For two-stage pyrolysis, two
independently. The first heating stage ran identically with one-stage
setup, and the continuously connected next heating zone, operated
isothermally (500, 600 and 700 °C). Catalytic pyrolysis was conducted
in the two-stage setup with the loading (1 g) of Ni-based catalyst (1 g)
was placed into the isothermal heating stage. The schematic diagram of
TR used in this study was depicted in Fig. S1.
2.5. Product analysis
Gas products evolved from pyrolysis of S. japonicus were analyzed
by micro-GC (INFICON, 3000A). Two columns (Plot U and molecular
sieve) were equipped with each unit to identify various gas products.
S.-H. Cho, et al.
Fig. 1. Profiles of the major pyrolytic effluents (H2, CH4, and CO) from pyrolysis of Styrax japonicus from the N2 and CO2 conditions.
馏出
物
Prior to the identification and quantification, the calibration curve was
drawn with a standard gas mixture, purchased from Rigas (Korea). The
liquid pyrolysates coming from volatile organic compounds (VOCs)
were condensed in a dichloromethane in a chilled solvent trap,
equipped with a reflux condenser. The collected liquid pyrolysates were
analyzed by gas chromatography (Agilent 7890B, USA) time-of-flight
(TOF) mass spectrometer (ALMSCO Bench TOF-DX, UK).
3. Results and discussion
3.1. Pyrolysis of S. japonicus from the CO2 environment
To scrutinize the mechanistic features of CO2 on pyrolysis of S. ja-
ponicus, its pyrolysis was carried out. Given that pyrolysis is a fuel
processing technique by reassigning carbon especially from a solid
phase carbonaceous material into three phase pyrogenic products, it is
assumed that the effectiveness of CO2 in pyrolysis of it leads to the
subsequent difference in the compositions of pyrogenic products. To
confirm such claims, the evolution trends of gaseous products from S.
japonicus pyrolysis were examined (both the N2 and CO2 environments)
firstly. The concentration profiles of gaseous products were depicted in
Fig. 1.
As plotted in Fig. 1, the major gaseous effluents from S. japonicus
pyrolysis at ≤ 600 °C under two atmospheric conditions are not dif-
ferent. These similar profiles offer that the CO2 influence on the S. ja-
ponicus thermolysis is not effective. Accordingly, the evolution profiles of
the gaseous pyrolysates at ≤ 600 °C from pyrolysis of S. japonicus reflect
the typical thermal behaviors of biomass. In short, CO evolution was
being observed at the lower temperature regime from 300 to 450 °C as
compared with the cases of H2 and CH4. Fig. 1 shows that liberations of
CH4 and H2 were initiated at ≥ 400 and ≥ 540 °C, respectively. Earlier
CO evolution in Fig. 1 is ascribed to deoxygenation (DO) from the
polymeric moiety of S. japonicus due to the lower binding energy of
C−O (358 kJ mol−1) in reference to that of C–H (416 kJ mol−1)
[48,49]. At the temperature regime (≥ 400 °C) giving off CH4 and H2
from pyrolysis of S. japonicus, CO evolution is substantially impeded
since liberation of H2 by dehydrogenation (DH) and CH4 by thermal
cracking lead to enhancement of aromaticity of the sample (S. japo-
nicus) [50,51]. It is inferred that such phenomena suggest the formation
of biochar at ≥ 400 °C. The degree of DH is proportional to pyrolytic
temperature, and such observation is in good agreement with the
thermal behaviors of lignocellulosic biomass associated with DH and
3
Journal of CO₂ Utilization 39 (2020) 101182
the formation of biochar [52].
However, the evolution profiles of the gaseous effluents at ≥ 600 °C
exhibit the salient feature of CO2. The evolution profiles of H2 and CO
from the CO2 condition did not follow the general thermolytic trend of
lignocellulosic biomass (S. japonicus). As reflected at ≥ 600 °C, the
formation of CO from the CO2 condition is interesting. As depicted, the
concentration of CO at 720 °C reached up to 3.53% under the CO2
condition. In comparison to the case of N2 condition (0.22% at 720 °C),
the enhanced formation of CO from the CO2 environment is equivalent
to 1600% enhancement. At ≥ 650 °C, the concentration of H2 from the
CO2 condition is lower that from the N2 condition. Such the suppressed
formation of H2 from the CO2 condition is possibly ascribed to the di-
lution effect by the increased CO formation since quantification of the
gaseous effluent by the GC unit only informs the relative mole fraction.
Accordingly, it is inferred that the enhanced formation of CO does not
affect the DH mechanisms. Despite of the diluted condition due to the
relatively higher concentration of CO from the CO2 environment, the
evolution profiles of CH4 from both the N2/CO2 conditions are iden-
tical. Under the diluted condition, similar concentration magnitudes of
CH4 from both atmospheric environments highlight another mechan-
istic roles of CO2 during S. japonicus pyrolysis. This result suggests that
CO2 accelerates thermal cracking of volatile organic compounds
(VOCs), thereby leading to the better CH4 formation.
It is imperative to understand the enhanced formation of CO from
pyrolysis of S. japonicus only under the CO2 condition because most
oxygen was depleted. For example, under the N2 environment, there is
no subsequence evolution of CO at ≥ 470 °C due to the source depletion
of oxygen. As noted, most oxygen was liberated as a form of CO due to
the inferior thermal stability (low bonding energy of CeO).
Accordingly, the enhanced formation of CO at ≥ 600 °C only from the
CO2 environment is likely ascribed to CO2. The enhanced formation of
CO also suggests that CO2 acts as an oxygen source for CO evolution.
Nonetheless, it is difficult to elucidate the precise mechanisms leading
the enhanced formation of CO in the presence of CO2. For more fun-
damental understanding of its roles, the thermolysis of S. japonicus from
the CO2 condition was characterized thermo-gravimetrically. The
thermal degradation by mass loss of S. japonicus and its thermal de-
gradation rate was shown in Fig. 2. The same TGA test of S. japonicus in
an inert environment (N2) was done to use data as the reference.
As shown in Fig. 2, at ≤ 731 °C, the thermal degradation of S. ja-
ponicus and DTG (differential thermogram) curves are same from both
the N2/CO2 conditions. Such identical thermal degradation of S.
S.-H. Cho, et al.
Fig. 2. Thermal degradation of Styrax japonicus and its thermal degradation
rate from the N2/CO2 conditions.
japonicus is of great importance because it elucidates the reaction me-
chanisms resulting in the enhanced formation of CO that is identified in
Fig. 1 at ≥ 600 °C under the CO2 condition. For example, the same
thermal degradation of S. japonicus at ≤ 731 °C in Fig. 1 suggests that
the enhanced formation of CO is achieved by means of the GPR rather
than the interactions between solid S. japonicus and CO2. Considering
that a TGA apparatus is an accurate instrument, allowing the sub-mi-
crogram mass change, any heterogeneous reactions between S. japo-
nicus and CO2 spontaneously lead to the different DTGs. However, as
evidenced in Fig. 2, any differences of mass decay and DTG curves
at < 731 °C from the two different atmospheres were not observed.
Hence, it is inferred that the heterogeneous reactions between the
sample and CO2 should be excluded. In addition, the same residual
masses from the TGA test of S. japonicus at ≤ 731 °C under the N2/CO2
Fig. 3. Profiles of the major pyrolytic effluents (H2, CH4, and CO) from two-stage pyrolysis of Styrax japonicus from the N2 and CO2 conditions.
4
Journal of CO₂ Utilization 39 (2020) 101182
conditions strongly offer that the mechanistic influence of CO2 is lim-
ited by means of the GPR of volatile pyrolysates (volatilized bio-oils and
VOCs).
The TGA test of S. japonicus confirms that the major mass change
was completed at 388 °C. Moreover, the thermal degradation rate of it is
substantially retarded at ≥ 388 °C. These results have good agreement
with all discussions in Fig. 1. For example, we claimed that the for-
mation of CH4 started at ≥ 400 °C, while the formation of H2 originated
from the DH was initiated at ≥ 540 °C. Also, we declared that the
evolutions of H2 and CH4 resulted from the formation of biochar (in-
creased aromaticity). The retarded thermal degradation rate in Fig. 2 is
indicative of the formation of biochar. Hence, it can be estimated that
biochar ripening is initiated at ≥ 388 °C. However, the additional mass
change was observed at ≥ 731 °C only from the CO2 environment, and
such the mass change is attributed to the Boudouard reaction (BR). The
initiation of the BR at ≥ 731 °C in Fig. 2 offers that the enhanced for-
mation of CO in Fig. 1 is not attributed to the BR. On the other words, it
is concluded that the enhanced formation of CO at ≥ 600 °C in Fig. 1 is
solely attributed to CO2 in pyrolysis of S. japonicus.
3.2. Two-stage pyrolysis of S. japonicus from the CO2 environment
The TGA test of S. japonicus and the evolution trends of the gaseous
pyrolysates confirmed that the enhanced formation of CO is attributed
to the CO2 capability as an oxidant. The role of CO2 as an oxygen source
for GPR is done by the homogeneous reaction between CO2 and VOCs
from the thermolysis of S. japonicus. Considering the mass change from
the TGA result (Fig. 2) at ≥ 388 °C, there is a continuous provision of
VOCs. Nonetheless, it is necessary to know that why the enhanced
formation of CO by the GPR occurs at ≥ 600 °C since most VOCs are
from the thermolysis of S. japonicus at ≤ 388 °C. Such the consequences
propose that the reaction kinetics of the CO2 GPR with VOCs is slow,
thereby requiring the high reaction temperature (≥ 600 °C). It is ne-
cessary to confirm that the hypothesized GPR is being initiated by VOCs
from pyrolysis of S. japonicus. As such, the experimental setups were
modified. In detail, pyrolysis of S. japonicus was done at a heating ramp
of 10 °C min−1 at ≤ 720 °C, and volatile pyrolysates from the dynamic
temperature conditions (first stage heating zone) were further pyr-
olyzed isothermally at 500 °C (Fig. S1). This temperature was chosen to
confirm why enhanced CO formation was initiated by CO2 only at
≥ 600 °C. In addition, the temperature of 500 °C was considered for the
further investigation into the mechanistic impact of CO2 before
S.-H. Cho, et al. Journal of CO₂ Utilization 39 (2020) 101182

Fig. 4. (a) Overall mass balance of pyrogenic products (solid biochar, oil, and gas), (b) chromatogram of liquid pyrolysates from two-stage pyrolysis of Styrax
japonicus under the N2/CO2 conditions.

initiating the enhanced formation of CO through the noted GPR.
As depicted in Fig. 3, the evolution trends of the gaseous pyrolysates
in two-stage pyrolysis of S. japonicus are similar with those in Fig. 1.
Under the isothermal temperature of 500 °C, the more H2 and CH4 are
evolved under the N2/CO2 conditions, but their concentrations are not
substantially improved. On contrary to the cases of H2 and CH4, Fig. 3
shows that the more CO is formed. Such the observation agrees with the
earlier discussions of bonding energies (CeO and C–H). However, the
identical concentration levels of the gaseous pyrolysates from two-stage
S. japonicus pyrolysis strongly suggests that the enhanced formation of
CO through the GPR should be initiated only at ≥ 600 °C.
Such the ineffectiveness of CO2 on pyrolysis of S. japonicus under the
N2/CO2 conditions are reflected in the overall mass balance in Fig. 4(a).
As evidenced, the overall mass balances by weighting mass of biochar
and bio-oil from the two environments are similar. Thus, as evidenced
in Fig. 4(b) and Table 1, the constituents of chemical species in pyr-
olytic oil and their compositional matrixes from the two different at-
mospheres are not much different. Such the facts offer that the effec-
tiveness of CO2 to enhance the formation of CO by the GPR is limited
only at ≥ 600 °C. Alternatively, no differences in the compositional
matrix of pyrolysates from the two different atmospheres at ≥ 600 °C
suggest that the reaction kinetics of the GPR is not fast.
3.3. Catalytic pyrolysis of S. japonicus on Ni/SiO2 catalysts from the CO2
environment
In the earlier sections, it was experimentally confirmed that the
effectiveness of CO2 on pyrolysis of S. japonicus led to the enhanced
formation of CO by the GPR, which was observed only at ≥ 600 °C.
Also, we hypothesized that the DH was not affected by CO2 even under
the condition of the enhanced CO formation. In these respects, it is
technically beneficial to produce H2 from catalytic pyrolysis of S. ja-
ponicus under the CO2 environment. On the assumption that the DH is
not affected by CO2, employing a Ni-based catalyst to produce H2 [53]
is a technically viable approach in catalytic pyrolysis of S. japonicus
since the enhanced formation of CO by CO2 may offer an innovative
means for the prevention of coke formation. For instance, the formation
of H2 from a carbonaceous material follows the DH mechanisms, and
the DH spontaneously leads to coking problem on the surface of a
catalyst [50,54]. To prevent the coke deposit onto the surface of a
catalyst, carbon in a carbonaceous material, such as biomass, must be
dedicated into CO2 during the production of H2 in catalytic pyrolysis of
S. japonicus. However, controlling the oxidation state through the GPR
of CO2 with VOCs offers a durable/reliable route in H2 production from
catalytic pyrolysis of S. japonicus. Accordingly, Ni/SiO2 catalysts with

Table 1
Identification of the chemical species in liquid pyrolysates from two-stage pyrolysis of Styrax japonicus under the N2/CO2 conditions.
Label Retention time, [min] Chemical species Chemical formula Area in N2 Area in CO2 Ratio of area (CO2/N2)

1 12.5551 Vinyl acetate C4H6O2 37,153,940 38,337,640 1.03

2 14.3276 Glycolaldehyde C2H4O2 58,915,540 81,975,133 1.39
3 15.7556 Crotonaldehyde C4H6O 7,715,485 7,921,023 1.03
4 16.3689 Acetic acid C2H4O2 436,442,987 388,958,979 0.89
5 17.2677 Hydroxyacetone C3H6O2 207,434,000 210,953,526 1.02
6 20.7708 Pyrrole C4H5N 1,739,303 6,448,463 3.71
7 21.2412 1-Hydroxy-2-butanone C4H8O2 36,953,999 35,180,187 0.95
8 22.3752 Butanedial C4H6O2 42,064,758 31,196,016 0.74
9 23.4757 Furfural C5H4O2 50,332,404 55,719,371 1.11
10 25.1474 Furfuryl alcohol C5H6O2 58,160,172 20,134,752 0.35
11 25.517 2-butanone C4H8O 9,425,136 12,511,030 1.33
12 26.7519 γ-butyrolactone C4H6O2 28,368,669 33,431,815 1.18
13 31.3302 Phenol C6H6O 28,972,257 33,252,564 1.15
14 32.0106 4-methoxyphenol C7H8O2 2,577,104 7,120,427 2.76
15 32.8002 2-methylphenol C7H8O 9,615,681 8,597,229 0.89
16 34.2871 3-methylphenol C7H8O 7,195,167 8,368,731 1.16
17 34.6148 4-methylphenol C7H8O 3,207,172 6,054,107 1.89
18 39.4198 2-butynol C4H6O 12,565,516 14,354,298 1.14

5
S.-H. Cho, et al. Journal of CO₂ Utilization 39 (2020) 101182

H2 + CO2 ⇌ CO + H2O) reaction for conversion of H2/CO2 into CO.

To confirm the occurrence of RWGS, two-stage catalytic pyrolysis
setup (2 wt.% Ni/SiO2) was constructed using H2 and CO2 as reactants.
The initial volumetric flow rates of H2 and CO2 were 11 and
100 mL min−1, respectively, to make volumetric flow ratio 1/9. The
concentration changes of H2 and CO from RWGS were plotted as a
function of the first heating zone temperature (Fig. S2). The conversion
of H2 was 31 ± 2% with a same yield of CO. This means that 1:1
conversion of H2 into CO was occurred under CO2 condition via RWGS.
The RWGS reaction is a reversible and resulting steam could be in-
volved in further catalytic steam reforming reaction over Ni catalyst
[55–57]. It should be also noted that the increased amount of CO was
higher than the decreased amount of H2 from CO2-mediated catalytic
pyrolysis. This offers that the enhanced CO formation was not solely
ascribed to the RWGS reaction (Fig. 7).
Energy balance and control of H2/CO ratio after the catalytic pyr-
olysis was calculated to compare the energy efficiency and importance
of biomass pyrolysis under both the CO2 and N2 conditions. 2 wt.% Ni/
Fig. 5. XRD patterns of 2 wt.% and 5 wt.% Ni-loaded catalysts. SiO2 catalyst at 600 °C (second stage) was selected as a reaction con-
dition for the energy balance calculation because this was an efficient
reaction condition (low catalyst loading with more syngas formation).
various metal loading (2 wt.% and 5 wt. %) were synthesized and
To estimate the weight percentage of gaseous products generated, mass
adopted in pyrolysis of S. japonicus. Prior to catalytic pyrolysis of S.
balance of three pyrogenic products was constructed. 21.3 wt.% of
japonicus over Ni/SiO2, XRD analysis of Ni/SiO2 catalysts was done.
biochar was obtained from the catalytic two-stage pyrolysis, which is
XRD spectra in Fig. 5 exhibit Ni peaks (JCPDS No. 04-0850).
consistent with non-catalytic two-stage pyrolysis (Fig. 4) because cat-
Except for 1 g of catalyst loading in the isothermal zone (500 °C),
alyst does not impact to the pyrolysis in the first-heating zone. How-
other parameters in catalytic pyrolysis over Ni/SiO2 were the same as
ever, bio-oil was significantly converted into gaseous products in the
two-stage pyrolysis in Fig. 3. The concentration levels of the gaseous
presence of 2 wt.% Ni/SiO2 catalyst through the second-heating zone,
pyrolysates from catalytic pyrolysis over 2 wt.% and 5 wt.% Ni-loaded
showing 77.2 wt.% of gaseous products and 1.5 wt.% of bio-oil residue
catalysts under two atmospheric conditions were shown in Fig. 6.
(data not shown) from 1 g conversion of initial biomass reactant.
As expected, the enhanced formation of H2 was achieved in catalytic
As aforementioned, micro-GC measurement provides relative con-
pyrolysis of S. japonicus over a Ni/SiO2 catalyst. Also, Fig. 6 shows that
centration of gaseous effluents, and our study investigated the pro-
the effectiveness of CO2 resulting in the enhanced formation of CO even
duction of pyrolytic gases with temperature dynamics. Therefore, the
in the presence of Ni/SiO2 catalysts was not observed at ≤ 600 °C of the
observation of the amount of each gaseous product at specific tem-
first heating zone temperature. It is inferred that the expected CO2
perature was not available. In this regard, the cumulative molar pro-
capability is not catalyzed. Nonetheless, the suppressed DH was ob-
duction of H2, CO and CH4 was calculated assuming that the N2 or CO2
served in catalytic pyrolysis of S. japonicus over a Ni/SiO2 catalyst from
(purge gas) is fully separated. Then, the molar concentration of each gas
the CO2 condition. Furthermore, the concentration levels of the gaseous
product was converted into weight concentration using molecular
products from catalytic pyrolysis over 2 wt.% and 5 wt.% Ni-loaded
weight. The amount (g) of gaseous effluents generated was further
catalysts were nearly identical. Such the results strongly support that
calculated multiplying both weight concentration and total amount of
catalytic capability over 2 wt.% Ni-loaded catalyst is fully saturated.
gas produced (0.772 g).
Accordingly, it is a better approach to investigate catalytic pyrolysis of
Higher heating value (HHV: 16.0 kJ g−1) of dry basis S. japonicus
2 wt.% Ni-loaded catalyst under the different temperatures of the cat-
was analyzed following the broadly used equation for HHV of biomass
alyst loading zone. As such, catalytic pyrolysis of S. japonicus over 2 wt.
feedstocks with the result of ultimate analysis [58]. HHV (heat of
% Ni-loaded catalyst under the N2/CO2 conditions was carried out at
combustion) of H2 (141.9 kJ g−1), CH4 (55.5 kJ g−1) and CO
500, 600, and 700 °C, and their concentration levels were plotted in
(10.2 kJ g−1) was adapted from another literature [59]. It is well-
Fig. 7.
known that the HHV of biochar is 20%–30% higher than its initial
As postulated in Fig. 7, the enhancement of CO formation was
biomass feedstock because carbonization through pyrolysis decreases
achieved as the temperature of catalyst loading zone increased. This
the oxygen content [60]. Thus, it can be estimated that the HHV of
remarkable CO evolution profile in the CO2 environment at ≥ 600 °C
pyrogenic biochar is between 19 and 21 kJ g−1. Because the HHV of
(catalyst bed) indicates that both Ni catalyst and CO2 synergistically
biochar is changed in different pyrolysis temperature, HHV of biochar
promoted homogeneous reactions between CO2 and gaseous VOCs. In
was assumed as 20 kJ g−1 (Table 2), and bio-oil content was ignored in
detail, the dedication of O in CO2 to the homogeneous reaction with
this calculation due to its small quantity.
VOCs contributed to the much more CO generation over catalytic
Comparison of the HHV of biomass feedstock with HHV for direct
pyrolysis, in comparison to the CO formation in the N2 condition. Be-
combustion of resulting pyrolysates showed that the HHV of initial
cause CO2 is the only additional source of oxygen in this setup, addi-
feedstock (16.0 kJ) was improved to 27.0 kJ (N2) and 16.4 kJ (CO2),
tional CO generation between 300 and 500 °C is a result from the
respectively. Due to the more production of CO in the presence of CO2,
homogeneous reaction. Such the synergistic effect of CO2 and Ni cata-
the HHV of pyrolysates after CO2-cofeeding pyrolysis was not re-
lyst was not shown at 500 °C of catalyst bed, because CO formation in
markably improved in comparison with HHV of biomass feedstock.
both the N2 and CO2 was identical as depicted in the Fig. 6.
However, significant change of H2/CO ratio was shown from CO2-co-
At ≥ 600 °C of catalyst bed, relatively lower concentration of H2 in
feeding catalytic pyrolysis. In addition to better HHV after biomass
the CO2 condition was shown in comparison with N2 condition, when
pyrolysis, such the variation of H2/CO ratio using different purge gases
relatively higher production of CO was shown at same temperature
(N2 or CO2) indicated the importance of this work. CH4 can be directly
range (Fig. 7). In the presence of Ni catalyst, two hypotheses for lower
used as a fuel in broad industries due to its abundance and relatively
concentration of H2 could be made: (a) a dilution effect without the
high HHV per mole than other gaseous products [59]. In contrast, H2
suppression of H2, and (b) reverse water gas shift (RWGS:
and CO have been used as reactants for hydrocarbon formation such as

6
S.-H. Cho, et al.
Fig. 6. Non-catalytic/catalytic pyrolysis of Styrax japonicus over 2 wt.% and 5 wt.% Ni-loaded catalysts from the N2/CO2 conditions at 500 °C (second heating zone).
CH4 through Fischer-Tropsch process [61]. In the process, controlling
the H2/CO ratio is a key value because it decides the resulting hydro-
carbons. To modify its ratio, water−gas-shift and reverse water−gas-
shift reactions are necessarily required [53]. As such, the CO2-cofeeding
pyrolysis can be considered a versatile and sustainable platform for
direct conversion of the H2/CO ratio (from 0.44 to 1.91 in Table 4).
It is also inferred that CO2 application brings technical benefits on
catalytic pyrolysis by elimination of carbon deposition (coke formation)
on catalysts, which can lead to catalyst deactivation. In N2 environ-
ment, the H2 and CO2 evolutions were enhanced in line with the cat-
alytic bed temperature, but there is no expected reaction for carbon
removal on the catalyst. This observation and assumption imply that
more coke formation can be occurred in the N2 environment than the
CO2 environment. To validate this, the temperature-programmed oxi-
dation (TPO) of raw and used catalysts in both the N2 and CO2 en-
vironment. As depicted in Fig. 8, the coke decompositions on catalyst
used in both environments initiated at ∼ 500 °C. The residual mass of
TPO of catalyst used in N2 environment was 96.61 wt.%, while that in
CO2 environment was 98.84 wt.%. These results suggest that the
amount of coke deposition on catalyst used in N2 environment is larger
7
Journal of CO₂ Utilization 39 (2020) 101182
than those of CO2 environment. Conclusively, the exploitation of CO2 as
reaction gaseous medium can provide an innovative way in the cata-
lytic pyrolysis for enhancing H2 generation and preventing coke de-
position on catalyst.
4. Conclusions
This study investigated the catalytic pyrolysis of S. japonicus to va-
lorize the biomass wastes, constructing the biomass-to-energy platform.
To construct sustainable thermolysis platform, CO2 was employed as a
gas medium instead of N2, and the roles of CO2 on the catalytic pyr-
olysis were examined over Ni-based catalysts. It was revealed that CO2
provides an additional oxygen source for CO formation through
homogeneous reaction with VOCs produced from biomass pyrolysis. Ni
catalyst promoted dehydrogenation, resulting in hydrogen formation
with aromaticity change of the VOCs. Each CO2 and Ni catalyst in-
dependently contributed to CO and H2 formation, respectively, when
the catalyst bed temperature was 500 °C, while synergistic effect of both
CO2 and Ni catalyst was shown at ≥ 600 °C. During the catalytic pyr-
olysis of S. japonicus, coke deposition on Ni catalysts was shown, which
S.-H. Cho, et al. Journal of CO₂ Utilization 39 (2020) 101182

Fig. 7. Catalytic pyrolysis of Styrax japonicus over 2 wt.% Ni/SiO2 from N2/CO2 conditions at 500, 600, and 700 °C (second heating zone).

can significantly reduce the catalyst performance in a series of reac-
tions. However, such coke formation was suppressed under the CO2
environment.
CRediT authorship contribution statement
review & editing. Young-Kwon Park: Formal analysis, Resources,
Writing - review & editing. Yiu Fai Tsang: Formal analysis, Writing -
review & editing. Changkook Ryu: Writing - review & editing,
Supervision. Eilhann E. Kwon: Funding acquisition, Supervision,
Writing - review & editing.

Seong-Heon Cho: Investigation, Conceptualization, Writing - ori-

ginal draft. Sungyup Jung: Data curation, Formal analysis, Writing -

Table 2
Energy balance and H2/CO ratio from catalytic pyrolysis of Styrax japonicus at 600 °C with 2 wt.% Ni/SiO2.
HHV per weight (kJ g−1) Weight (g) HHV (kJ) Cumulative amount of gas products (mole%) H2/CO ratio (by mole)

Feedstock 16.0 1.0 16.0 – –

Pyrogenic products
Biochar (N2 and CO2) 20.0 0.213 4.26
Gas products (N2) H2 (141.9) H2 (0.085) H2 (12.09) H2 (61.90) 1.91
CO (10.2) CO (0.658) CO (6.71) CO (32.35)
CH4 (55.5) CH4 (0.070) CH4 (3.90) CH4 (5.75)
Gas products (CO2) H2 (0.023) H2 (3.24) H2 (29.32) 0.44
CO (0.721) CO (7.35) CO (66.13)
CH4 (0.028) CH4 (1.57) CH4 (4.55)

8
S.-H. Cho, et al.
Fig. 8. Temperature-programmed oxidation profiles of raw catalyst (2 wt.% Ni/
SiO2) and catalysts used in N2 and CO2 environments at 600 °C.
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.
Acknowledgement
This study was supported by the National Research Foundation of
Korea (NRF) grant funded by the Korea Government (MSIT) (No. NRF-
2019R1A4A1027795).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jcou.2020.101182.
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