Energy 170 (2019) 497e506

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Energy
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CO2 gasification of woody biomass: Experimental study from a

lab-scale reactor to a small-scale autothermal gasifier
Ye Shen a, b, Xian Li b, Zhiyi Yao a, Xiaoqiang Cui a, c, Chi-Hwa Wang a, b, *
a
Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, 117585, Singapore
b
NUS Environmental Research Institute (NERI), National University of Singapore, #15-02, Create Tower, 1 Create Way, 138602, Singapore
c
Ministry of Education Key Laboratory of Environmental Remediation and Ecological Health, College of Environmental and Resource Sciences, Zhejiang
University, Hangzhou, 310058, China

a r t i c l e i n f o a b s t r a c t

Article history: Rapid depletion of fossil fuel and CO2 mitigation are two major challenges in the modern society. CO2
Received 30 August 2018 gasification of carbon-neutral biomass could be an attractive technology to cope up these two emerging
Received in revised form problems. Replacing conventional gasifying agent air with CO2 could reduce the fraction of undesired N2
6 December 2018
in the gas products because CO2 behaves as inert gasifying agent under low temperature and could be
Accepted 23 December 2018
converted to CO at high temperature range. However, most researches on CO2 gasification are limited at
the lab-scale level due to the endothermic feature of Boudouard reaction. In this work, a feasibility study
of small-scale autothermal gasification using 15% CO2 and 85% air was conducted and compared with
Keywords:
CO2 gasification
traditional air gasification. Prior to that, a lab-scale study of gasification behaviors, under N2, air and CO2
Autothermal gasification agents, were performed. It was found that using CO2 as gasification oxidant could produce comparable
Biochar energy (6.67 kJ/g feedstock) to air gasification (7.45 kJ/g feedstock) at equivalent condition (800
C,
Small-scale gasifier 40 min). The pH of biochar obtained under CO2 condition at 800
C was measured to be 10.63 while the
CO2 mitigation pH of biochar derived by air gasification at the same temperature could reach 12.32. In addition, a small-
scale gasification experiment with 15% CO2 addition was successfully conducted in a downdraft auto-
thermal reactor. The results showed CO production was greatly enhanced while CH4 generation was
suppressed owing to Boudouard reaction and CO2 dry reforming. Cold gas efficiency and carbon con-
version efficiency were both enhanced by 5.8% and 6%, respectively, with CO2 addition. Meanwhile,
particulate matters (PM) emitted from both air gasification and 15% CO2 gasification experiments were
measured. It was found that under the same equivalence ratio (ER), 75.4% less particle number con-
centration was emitted during 15% CO2 gasification compared to air gasification.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction will be re-captured through photosynthesis [5,6]. Furthermore, the

1.1. Background
The explosive energy consumption is one of the critical chal-
lengers throughout the world. Currently the major portion of en-
ergy is generated from traditional fossil fuels, leading to CO2
emission concern [1e3]. To overcome this issue, alternative energy
sources have been widely explored [4]. In contrast to fossil fuels,
biomass is considered to be CO2 neutral because the CO2 produced
during downstream utilizations (i.e. combustion and gasification)
* Corresponding author. Department of Chemical and Biomolecular Engineering,
National University of Singapore, 4 Engineering Drive 4, 117585, Singapore.
E-mail address: chewch@nus.edu.sg (C.-H. Wang).
release of NOx and SOx can be reduced when using biomass as
alternative fuels to avoid acid rain formation [2,5]. Gasification is an
efficient and clean technology to convert waste biomass to syngas
(mainly CO and H2), which can be utilized for chemical synthesis or
power generation [7,8].
Even though carbon-neutral renewable energy sources like
biomass have replaced fossil fuels partially, the problem of CO2
emission still exists. Globally averaged surface molar fraction of CO2
increases 3.3 ppm from 2015 to 2016, larger than any of the pre-
vious records, as reported by World Meteorological Organization
(WMO) [9]. Therefore, CO2 negative solutions are urgently required
to tackle the greenhouse effect. One practical option is to utilize the
captured CO2 as feedstock for valuable products. CO2 has been
widely applied to synthesize chemicals such as methanol and urea

https://doi.org/10.1016/j.energy.2018.12.176
0360-5442/© 2018 Elsevier Ltd. All rights reserved.
498 Y. Shen et al. / Energy 170 (2019) 497e506
[10,11]. Recently, another appealing carbon capture and utilization
(CCU) method is to gasify renewable biomass using CO2 as the
gasifying agent to produce CO-enriched gas through Boudouard
reaction [12,13].
1.2. Literature review
Most of biomass gasification studies use air, oxygen or steam as
gasifying agent. Among them, air gasification is the simplest tech-
nology due to the availability of the gas agent. However, the dilu-
tion of 78% N2 from air decreases the heating value of gas product
and limits its further applications [14,15]. Oxygen and steam can
enhance the calorific value of syngas. But the cost and energy
consumption of air separation and superheated steam generation
are not negligible [16]. CO2 gasification is drawing attention
recently for its unique advantages over the aforementioned agents
[17]. For instance, replacing inert N2 with CO2 could increase cold
gas efficiency (CGE) and carbon conversion (CC) owing to the in-
crease of total oxidant input [18]. CO2 could behave as inert gas at
low temperature and react with char through Boudouard reaction
or with tar through dry reforming to produce CO-enriched gas for
further applications. This syngas could be further upgraded to
chemicals such as organic acid, methanol and polycarbonates that
requires low H2/CO ratio. In addition, Lee et al. found CO2 could
reduce tar yield by expediting thermal cracking of volatile organic
carbons (VOCs) [19]. Pyrolytic oil fraction decreased from 31.8% to
21.0% when substituting N2 with CO2 as agent. This phenomenon
was also observed in Kwon's study, which illustrated that CO2 not
only accelerated decomposition of VOCs, but also reacted with
VOCs [20]. Furthermore, Parvez et al. conducted energy, exergy and
environmental assessments of conventional, steam and CO2-
enhanced gasification scenarios using ASPEN PLUS. The authors
suggested that CO2-enhanced gasification could lower the envi-
ronmental impacts than conventional air gasification. The sup-
pression of human toxicity and marine ecotoxicity were the main
reasons for the improvements [21].
1.3. Research objectives
Despite the outstanding features of using CO2 as gasification
agent, most researches were performed in thermogravimetric
analyzer, lab-scale reactors or through numerical strategies while
few studies could be found regarding applying CO2 gasification in a
real autothermal reactor. This is because CO2 gasification relies on
highly endothermic reactions such as Boudouard reaction. The
requirement of external heat source limits its commercialization
[22,23]. A high concentration of CO2 input may extinguish the flame
and fault the process in real operations [16,24]. Therefore, to pro-
mote the application of CO2 gasification, more efforts should be put
on its performances under autothermal condition. Previously Gül
and colleagues investigated effects of introducing CO2 to a pilot
scale pressurized bubbling fluidized bed reactor using lignite as
feedstock. Production of H2 was suppressed respect to increasing
CO2 concentration due to the equilibrium of water-gas shift reac-
tion [25]. However, pilot-scale CO2 gasification of biomass has not
been reported to the best of our knowledge. A comprehensive study
from lab-scale to pilot-scale would be useful to fully understand
and promote the application of using CO2 as gasification agent.
Therefore, in this work, a lab-scale reactor was built to investigate
gas and biochar behaviors of gasifying woody biomass under
various gas agents including N2, air and CO2. Based on that, feasi-
bility study of replacing 15% air with CO2 was conducted and
compared with traditional air sole gasification in an 8-kW auto-
thermal downdraft gasifier. In addition, fewer studies have been
conducted to quantify the particulate matter emission from
gasification, and there is still a lack of relevant inhalation exposure
assessment. As a technology that has great potential for decen-
tralized, community-based applications, the pollutant emission
characterization and management is a must. In this work, we
characterized and compared the particulate matters (PM) emitted
from both air gasification and 15% CO2 gasification experiments.
The objective of this study is to investigate the feasibility of intro-
ducing CO2 into a practical autothermal gasifier as a novel carbon
negative approach.
2. Material and method
2.1. Materials
Waste wood pellets from sawmill were used as feedstock in this
study. Dimensions of wood pellets are 3 mm in length and 1 mm in
diameter. Methods for characterizing feedstock are presented in
Table 1 using ASTM International standards. Ultimate analysis was
performed to determine the weight percentage of carbon,
hydrogen, nitrogen and sulfur content in the biomass. Proximate
analysis was used to determine moisture, fixed carbon and ash
content in the sample. Oxygen content and volatile matter were
obtained by subtracting the contents of all the other components
from one hundred percent in the results of elemental analysis and
proximate analysis, respectively.
2.2. A lab-scale fixed-bed reactor
Lab-scale pyrolysis/gasification experiments were conducted in
a fixed-bed stainless tube reactor as shown in Fig. 1. The dimension
of the reactor is 1.1 m in height and 46 mm in diameter. Prior to
experiment, 15 g (±0.3 g) of wood samples were placed on a porous
ceramic plate at 15 mm height from the top of the reactor. Three
kinds of reaction gas, including N2, air and CO2 were purged into the
reactor from top. The flow rate of the gas input was controlled at
300 mL/min through mass flow controller (MFC). A thermocouple
was inserted above the samples to capture the real temperature of
reactant during operations. The stainless tube reactor was sur-
rounded by an electrical thermal heater for external heating and
precise temperature control. For each run of experiment, the
reactor was heated at the rate of 50
C/min and hold at the desired
point (700/800
C) for 40 min (counting from the beginning of
experiment including heating period). The produced gas would go
through a cold trap to condense liquid products (i.e. tar and water)
and clean up the gas product before it was collected through gas
bags at certain time intervals. The collected gas would be analyzed
through a gas chromatography (GC) (PerkinElmer, model 4016),
equipped with thermal conductivity detector (TCD), to quantify the
amount of CO, CO2, H2 and CH4 in the mixture. The gas energy
output was calculated based on the following equation:
Table 1
Characterizations of feedstock.
wt % Method
Elemental analysis (wt%) C 47.26 ASTM D 5373-14
H 6.14 ASTM D 5373-14
N 0.11 ASTM D 5373-14
S ND ASTM D 4239-14
O 44.99 By difference
Proximate analysis (wt %) Moisture 6.3 ASTM D 3173-11
Fixed carbon 14.9 ASTM D 3172-13
Ash content 1.5 ASTM D 3174-12
Volatile matter 77.3 By difference
Gross Calorific Value (MJ/kg) 19.05 ASTM D 5865-13
 Y. Shen et al. / Energy 170 (2019) 497e506
Fig. 1. Schematic diagram of a fixed-bed lab scale reactor. 1 Gas cylinder, 2 Mass flow
controller, 3 Valve, 4 Gas mixer, 5 Gasifier reactor, 6 Heater, 7 Gas washing bottle, 8 Gas
collection bag.
Gas energy output ¼ VCO  HHVCO þ VH2  HHVH2 þ VCH4
 HHVCH4
VCO, VH2 and VCH4 represent for volume production of CO, H2 and
CH4 while HHVCO, HHVH2, and HHVCH4 stand for higher heating
value of CO, H2 and CH4, respectively. HHV values of the gas com-
ponents were obtained from the literature [26] (CO: 12.633 MJ/m3;
H2: 12.745 MJ/m3; CH4:39.819 MJ/m3).
For the cases of air gasification and CO2 gasification, supplied gas
was switched to inert nitrogen during cooling stages. Biochar
samples were obtained and further analyzed after cooling to room
temperature.
2.3. A small-scale autothermal gasifier
2.3.1. Experimental setup
The schematic of a small-scale downdraft gasifier is depicted in
Fig. 2. Schematic of a small-scale downdraft gasifier fed with biomass and CO2-and-air agent.
499
Fig. 2. The gasifier experimental system consists of an automatic
feeding sub-system i.e. hopper and screw feeder, downdraft auto-
thermal gasifier with the biochar and ash removal device, cyclone,
producer gas cleaning device (i.e. filter), gasifying agent control
sub-system, producer gas burner, and the measurement and data
acquisition subsystem. Specifically, the hopper is capable of storing
0.33 m3 wood pellets with moisture content of 5e30% dry basis.
The screw feeder is used to automatically feed wood pellets into the
gasifier, accompanied by adjustable feeding rate according to the
equivalence ratio (ER). The gasifier is a representative type of
downdraft autothermal structure. The details, in terms of the
configuration and operation parameters, are given in Table 2. The
particles in the producer gas generated from the gasifier is then
separated by the cyclone and collected in a fly ash container. The
hot producer gas exiting the cyclone is further cooled down with
the gas temperature from ~300
C to ~70
C via air-gas heat
exchanger to remove partial steam and tar. The ultimate stage of
the stream is to refine the producer gas by physical adsorption
approach in the fix-bed filter with washable foam elements. In this
work, the purified producer gas is connected to an internal com-
bustion engine (ICE) to produce 8 kW of electricity. CO2 flow rate is
controlled by a mass flow controller (MFC) connecting a CO2 gas
storage tank. The objective of this experiment is to conduct
comparative study on the effects of sole air gasification and air-CO2
co-gasification on the producer gas composition and yield, as well
as corresponding biochar characteristics. Therefore, we only
(1) measured the combustion temperature, reduction temperature,
producer gas composition, and air/CO2/wood feeding rate. The
portable infrared syngas analyzer Gasboard-3100P was used to
Table 2
Specifications of the small-scale downdraft autothermal gasifier.
Specification Parameter
Type Thermally integrated downdraft
Woody pellets feeder Automated
Ash removal Automated
Base diameter of reduction cone 152.4 mm
Top diameter of reduction cone 76.2 mm
Reduction cone height 152.4 mm
Combustion temperature (
C) 800e850
Pressure (bar) 0.85e1.0
500
Table 3
Uncertainties of key measurement instruments.
Parameters
Temperature (K-type thermocouple)
Air feeding rate (thermal mass flow meter,
Sierra Instruments 620S, USA)
CO2 feeding rate (Bronkhorst MFC)
Producer gas composition (Gas analyzer Gasboard-3100P)
measure lower heating value of the cold producer gas (LHVg)
within a sampling interval of 30 s. The K-type thermocouples were
located at the measurement points shown in Fig. 2. The un-
certainties of main measuring instruments aforementioned are
listed in Table 3. The thermocouples were calibrated with a relative
deviation of 0.1 K. A Process Control Unit (PCU) monitors and re-
cords temperatures and flow rates. In addition, during the gasifi-
cation experiments, temporal variation of airborne PM was
monitored using aerosol spectrometers (GRIMM 1.109). One sam-
pling station was placed in front of the control panel to monitor the
PM emissions, which were assumed to be inhalation hazard of the
operators. Another sampling station was placed 3 m away from the
gasifier to monitor PM emissions, which were assumed to be
Fig. 3. Transient gas composition file under N2/air and CO2 conditions: (a) N2, 700
C; (b) N2, 800
C; (c) Air, 700
C; (d) Air, 800
C; (e) CO2, 700
C; (f) CO2, 800
C.
Y. Shen et al. / Energy 170 (2019) 497e506
inhalation hazard for people around the gasifier. The probes of the
aerosol spectrometers are at a height of 1.5 m above the ground.
uncertainties
±0.1 K
2.3.2. Experimental method
±1% In this test, 60 kg wood pellets were loaded and stored in the
hopper. Air feeding rate of 160 L/min (9.6 m3/h) was kept constant
±0.5% in both air gasification and air-CO2 co-gasification experiments.
±2%
From ignition stage (startup) to the steady state (i.e., the fluctuance
of combustion and reduction temperatures is within the span of
±2
C), it ordinarily takes 1 h. All monitoring data were recorded at
the steady state. In air-CO2 co-gasification, the CO2 feeding rate was
controlled by the CO2-MFC with a constant of 32 L/min (1.92 m3/h).
The feeding rate of wood pellets was measured as the consumption
rate in the hopper during the steady state operation. Considering
the complex and time-varying gas composition, it is difficult to find
a reasonable and accurate flow meter for such producer gas
generated from wood gasification. The yield of cold producer gas
was estimated based on mass conservation of input N2 and N2
content of producer gas.
2.4. Sample analysis methods
The pH of the biochar was measured with a pH meter by
 Y. Shen et al. / Energy 170 (2019) 497e506 501

suspending 0.5 g of biochar in 10 mL DI water for 5 h according to a also enhanced in CO2 gasification compared with N2 and air gasi-
previous study [27]. Inductively coupled plasma optical emission fication. A possible reason is that CO2 could react with decomposed
spectrometry (ICP-OES) test was conducted to test concentrations tar to generate small molecules such CO and H2. This CO2 dry
of B, Ca, Cu, Fe, Mg, Na, P and K using a Perkin Elmer Optima reforming process (eq (3)) would convert the tar compounds to
5300DV machine. useful gas product. When oxygen was presented in the agent dur-
ing air gasification, constant CO and CO2 concentrations were
observed, owing to combustion (eq (4)) and partial combustion of
3. Results and discussion
char (eq (5)) after the completion of pyrolysis. The tendency of the
two competitive reactions varied with reaction temperature. For
3.1. Lab-scale study
instance, at 700
C, the major product was CO2, accounting for 15%
of total produced gas while CO only occupied 5% during air gasifi-
Fig. 3 shows transient gas composition of woody biomass gasi-
cation. However, when temperature increased to 800
C, CO frac-
fication under different gas agent and temperature conditions.
tion rose to 17% and CO2 concentrations dropped to 12%. The shift of
Concentration distributions of CO, H2, CO2 and CH4 are presented
CO/CO2 ratio could be attributed to the occurrence of Boudouard
respect to reaction time at reaction temperature of 700
C and
reaction (eq (6)) which is highly endothermic and requires high
800
C. To capture the real temperature during the reactions, the
temperature (typically >700
C) [13]. The dynamic concentration
reading of thermocouple is also recorded and presented together
profile of CO in CO2 gasification exhibited similarly with that of air
with gas composition.
gasification. As can be seen in Fig. 3(f), there were two major zones
The evolutions of H2 and CH4 showed typical parabolic patterns
when reaction temperature was set at 800
C. The first peak during
during pyrolysis from 300 to 800
C, similar with findings in pre-
10e15 min was responsible for the pyrolysis. It is worth noting that
vious studies [27,28]. Feedstock started to decompose at 400
C
when CO concentration reached its peak, temperature of the
where primary pyrolysis of lignin, cellulose and hemicellulose
reactor was 650
C, at which Boudouard reaction was rather weak.
initiate [29]. CH4 concentration increased from 400
C to 650
C and
Thus, CO fraction showed a declined trend while reactor temper-
declines afterwards. The release of CH4 is mainly due to the
ature kept rising. Secondary increase of CO was observed when
cracking of methoxy (eOeCH3) at temperature lower than 600
C.
temperature further reached 750
C to enhance Boudouard reac-
According to literature, lignin, cellulose and hemicellulose would
tion. Comparing Fig. 3(e) and (f), it can be concluded that temper-
release CH4 during primary and secondary pyrolysis varying from
ature was the major factor for CO production as its concentration
200
C to 600
C and lignin dominate this process because of its
rose from 20% at 700
C to 40% at 800
C.
highest OeCH3 content [30]. It is also worthy to note that CH4
evolution profiles exhibited similarly at 700
C and 800
C, indi-
Dry tar reforming : Cx Hy þ xCO2 /2xCO þ 0:5yH2 (3)
cating the decomposition reactions occurred under 700
C [31].
However, as the reaction rate of pyrolysis is much faster than other
reactions [32], CH4 peaks was relatively sharp and narrow. The Char combustion : C þ O2 /CO2 (4)
production of CH4 lasted around 10e15 min, varying with different
gas suppliers. H2 reached the highest proportion slightly later than
Char partial combustion : C þ 0:5 O2 /2 CO (5)
CH4 at higher temperature (700
C or 800
C). It is because that H2
is not only produced through decomposition of polymers, but also
released from cracking and deformation of aromatic CeH and C]C Boudouard reaction : C þ CO2 /2CO (6)
bonds [30]. In contrast to CH4, production of H2 lasted for 30 min. It
Cumulative gas production and energy output of wood gasifi-
is worth to notice that temperature plays a significant role in H2
cation at 800
C under N2, air and CO2 gasification for 40 min were
production. H2 concentration could achieve as much as 17% in
shown in Fig. 4. Under N2 pyrolysis, gas production is limited
produced gas at 800
C under N2 atmosphere while it could only
because major products are char and bio-oil. As a result, 3200 mL
reach 7% at 700
C. This phenomenon could also be observed in air
syngas including 1700 mL CO, 900 mL H2 and 600 mL CH4 was
gasification at 800
C, where the highest H2 fraction doubles that of
generated. The cumulative volumes of CO and CH4 remained stable
700
C. It is because that carbon-hydrogen bond is very stable and
after 20 min when temperature just reached 800
C, indicating
can be broken at high temperature [33]. However, H2 evolution
these components were decomposed from pyrolysis. For traditional
during CO2 gasification was suppressed, which is different from air
air gasification, gas yield was greatly enhanced comparing with
and N2 gasification. There was no significant enhancement of H2
pyrolysis. 3700 mL CO together with 2000 mL H2 and 1000 mL CH4
production when temperature rose, as demonstrated in Fig. 3 (e)
were release after 40 min at this atmosphere, around two times as
and (f). This is due to the occurrence of reversed water gas shift
much as the gas yield at N2 conditions. The doubled syngas yield
reaction (RWGS, eq (2)) that converts H2 to CO and water [34]. High
and energy output suggest utilizing air as gasification agent could
temperature and high CO2 concentration favor this conversion.
promote cracking of large molecules into desired calorific products.
Reversed water  gas shift reaction : CO2 þ H2 4CO þ H2 O As for CO2 gasification, CO became the dominate gas product,
attributing for 4400 mL production while H2 yield declined to
(2)
1000 mL. The CO/H2 ratio increased from 1.8 to 4.4 due to Bou-
The transient evolution patterns of CO and CO2 varied under douard reaction and reversed water-gas shift reaction. It is worth
different gas agents. While supplying N2 as the gas agent, pyrolysis noting that the total calorific gas (CO, H2 and CH4) volume and
is the dominate step. Among all the pyrolysis products, CO occupied energy output were slight lower (6200 mL and 98.7 kJ) than that
the highest fraction, accounting for 40% at most. The production of from traditional air gasification (6700 mL and 112.5 kJ). This proves
CO during this period is mainly attributed to the cracking of ther- that it is feasible to use CO2 as gasification oxidant to replace air for
molabile carbonyl group and ether bridges from lignin. Apart from nitrogen free syngas production.
that, secondary cracking of volatiles could also contribute to CO Another key byproduct during gasification is biochar, which
production. Meanwhile, the release of CO2 during pyrolysis comes could be further applied as catalyst [37], absorbent [38,39] or soil
from the breaking of carboxyl group of hemicellulose [29,35,36]. It conditioner [40]. pH values of biochar obtained from N2, air and CO2
can be noticed that during this period, the concentration of CO was pyrolysis/gasification were measured. The pH values of biochar
502 Y. Shen et al. / Energy 170 (2019) 497e506

Fig. 4. Cumulative gas production under (a) N2, (b) Air, (c) CO2 agent at 800
C.

showed a rising trend under all three gas agents with increasing
temperature due to the decomposition of acid functional group and
separation of ash which contain high alkali salts such as calcium,
potassium and sodium [27]. Meanwhile, it was observed that bio-
char produced under CO2 agent had a lower pH than that from
traditional air gasification. This behavior was even more notable
when the reaction temperature increases to 800
C. pH of biochar
derived from air gasification could reach as high as 12.32 while
using CO2 as agent it would reduce to 10.63 at this temperature.
One possible explanation is that as listed in Table 4, the ash content
of biochar derived from air gasification (17.83 wt%) was much
higher than that produced from CO2 gasification (11.77 wt%). The
accumulation of alkali salts could be responsible for the increase of
pH.
3.2. Small-scale autothermal gasification
With the knowledge from lab-scale gasification study, feasibility
investigation of CO2 gasification was further conducted in an
autothermal downdraft gasifier. As CO2 could extinguish the flame
in the reactor, 100% replacement of air with CO2 is not practical.
Thus, gasification using 15% CO2 and 85% air as gas agent was
performed to compare with sole air gasification.
In the experiments, the continuous recording period of the
temperature, flow rate and gas composition were 10 min at the
steady state for both air and air-CO2 gasification processes. Table 5
lists the key parameters monitored in the experiment. Compared to
conventional air gasification, air-CO2 gasification has comparable
feedstock feeding rate and ER value. Notably, the addition of CO2
input reduced both combustion and reduction temperatures,
where a reduction of 27
C was observed from 797
C to 770
C.
Meanwhile, a higher reduction of 93
C was found in the reduction
region of the gasifier. It is mainly attributed to the promotion of
endothermic reactions (e.g., Boudouard reaction, steam gasifica-
tion, dry tar reforming, etc.) with the presence of CO2.
Cold gas composition was measured within a 15 s interval dur-
ing the steady state by the in-situ gas analyzer. Fig. 5 indicates the
evolutions of CO, CO2, CH4, and O2 yield, accompanied by lower
heating value evolution. The cold gas compositions of the two types
of gasification are depicted in Fig. 6. In air-CO2 gasification, a
significantly larger yield of CO and CO2 and lower yield of CH4 were
observed. This can be attributed to the reactions of methane
reforming (eq (7)) and dry tar reforming (eq (3)). The CO2 yield
increased, while there was a slight reduction of CO composition. In
contrast, H2 was increasing. It is mainly owing to the water-gas shift
reaction. H2 content declined from 18.6% to 16.6% when adding CO2
into the gasifier, however, the average yields of H2 during the test
periods are comparable. It is attributed to two factors: (1)

Table 4 Table 5
Ash content and pH of biochar produced under N2, air and CO2 conditions at 700
C Experimental data of monitoring temperatures, ER, and flow rates at the steady
and 800
C. state.

Gas agent Temperature (ºC) Ash (wt%) pH Parameters 100% Air 85% Air þ15% CO2

N2 700 5.66 ± 0.14 10.66 ± 0.01 mf (kg/h) 10.5 ± 0.8 10.5 ± 0.8
800 7.15 ± 0.07 10.83 ± 0.03 Va (Nm3/h) 10.8 ± 0.1 10.8 ± 0.1
Air 700 13.79 ± 0.08 10.48 ± 0.04 VCO2 (Nm3/h) e 1.92 ± 0.01
800 17.83 ± 0.11 12.32 ± 0.01 ER 0.24 ± 0.04 0.24 ± 0.04
CO2 700 6.45 ± 0.07 10.39 ± 0.02 Tcombustion (
C) 797 ± 2.0 770 ± 1.0
800 11.77 ± 0.10 10.63 ± 0.00 Treduction (
C) 654 ± 1.0 561 ± 1.0
 Y. Shen et al. / Energy 170 (2019) 497e506 503

including CO, H2 and CH4 increases.

Methane reforming:CH4 þ CO2 /2CO þ 2H2 (7)

Char  Steam gasification: H2 O þ C/CO þ H2 (8)

As shown in Fig. 7, it is prospected that total gas yield of air-
gasification was slightly lower than that of air-CO2 gasification,
accompanied by a reduction of 2.44 m3/h, owing to the addition of
CO2 agent. In addition, the addition of CO2 promoted the dry tar
reforming, leading to increments of around 6% and 5.8% in terms of
carbon conversion efficiency and cold gas efficiency, respectively.
The enhanced carbon conversion efficiency and cold gas efficiency
suggest that replacing air with CO2 partially could enhance the
energy performance of the biomass gasification process despite a
decrease in reaction temperature. The results show a successful test
run of air-CO2 gasification as a feasibility trial.
Table 6 presents the elemental analysis results of the biochar
obtained from sole air-gasification and air-CO2 gasification corre-
sponding to the operation conditions aforementioned. It was found
that the carbon content produced from air-gasification process is
Fig. 5. Time-varying evolutions of lower heating value and gas yield of producer gas.
slightly lower than that produced from air-CO2 gasification. It can
be justified that, the high CO2 concentration promoted the pore
volume and specific surface area of char in the reduction region,
which enhanced char gasification. The high producer gas flow rate
reduced the residence time, which leads to incomplete reactions.
Similar with the results obtained from lab-scale reactor, biochar
generated from air-CO2 gasification has a lower pH value and ash
content.
The particulate emissions of gasification were measured at two
different locations. One sampling station was placed in front of the
control panel to monitor the PM emissions, which were assumed to
be inhalation hazard of the operators. Another sampling station
was placed 3 m away from the gasifier to monitor PM emissions,
which were assumed to be inhalation hazard of people nearby. The
results are shown in Fig. 8. Generally, there are four stages during
each run: before ignition, ignition, unsteady state, and steady state.
For these four cases, the particulate emission profile reached its
peak during ignition stage, corresponding to 2.66  106 #/L, 5.9 

Fig. 6. Comparison of cold gas composition between sole air gasification (100% air) and
air-CO2 gasification (85% air þ 15% CO2) under the identical feeding rates of air and
wood pellets.

Production of H2 from CO2 dry reforming. In the lab-scale reactor,

the heating zone is relatively short. The decomposed tar would
quickly condense in the cold trap. However, in the small-scale
reactor, the retention time for tar is much longer. Thus, it could
react with CO2 more completely. (2) The high CO2 concentration
promotes the pore volume and specific surface area of char in the
reduction region, which enhanced char-steam gasification (eq (8))
[41]. According to previous studies, presence of CO2 during gasifi-
cation could greatly improve the surface area of biochar [34,42].
This unique feature could also widen its further applications such as
absorbent or soil conditioner. It is also worth noting that the frac-
tion of nitrogen in the produced gas reduced by 6% with the Fig. 7. Comparison of overall gas yield, carbon conversion efficiency (Xc), cold gas
efficiency (hCGE) between sole air gasification (100% air) and air-CO2 gasification (85%
replacement of CO2. As a result, total volume of calorific gas
air þ 15% CO2) under the identical feeding rates of air and wood pellets.
504 Y. Shen et al. / Energy 170 (2019) 497e506

Table 6
Elements in biochar from air and air-CO2 gasification.

Ash (wt%) pH Elemental analysis (wt%)

C H N S Ca Cu Fe Mg Na P K

100% Air 18.88 ± 0.66 10.73 ± 0.02 72.37 ± 0.21 0.64 ± 0.17 ND ND 3.54 ± 0.65 ND 0.04 ± 0.01 1.23 ± 0.18 0.41 ± 0.18 0.25 ± 0.05 4.91 ± 0.14
85% Air þ 15% CO2 17.23 ± 0.73 10.24 ± 0.03 74.33 ± 0.57 0.51 ± 0.05 ND ND 2.94 ± 0.75 ND 0.03 ± 0.01 1.01 ± 0.29 0.53 ± 0.17 0.19 ± 0.06 5.43 ± 0.23

105 #/L, 4.98  106 #/L, and 1.75  106 #/L of PM0.25-0.5 (particulate
matters with sizes ranging from 0.25 mm to 0.5 mm) for the case of
inhalation by operator during air gasification, inhalation by people
nearby during air gasification, inhalation by operator during 15%
CO2 gasification, inhalation by people nearby during 15% CO2
gasification, respectively. The results suggest a potential exposure
risk to fine particles for both operators and people nearby during
the ignition stage in the gasification experiments. For all the cases,
the particle number concentration (PNC) profiles showed similar
trends in both unsteady state and steady state, which indicated that
the existing particle removal system in the gasifier exhibited stable
performance after the ignition.
In addition, there was a slight increase of PNCs during the steady
state as compared to that of the period before ignition. By sub-
tracting the PNCs during the period before ignition from the PNCs
during the steady state, the increased PNCs during gasification
experiments were obtained, as shown in Fig. 9. For these four cases, Fig. 9. Normalized particulate number concentrations during steady state operation.
the particulate emissions from the gasification experiments were
mainly PM0.25-1.0, which indicated a potential exposure risk to
intermediate-mode particles (particles with sizes ranging from suggested that operating the gasifier may pose a higher exposure
0.1 mm to 1.0 mm [43]). The results are consistent with our group's risk to PM pollution and related personal protective equipment
previous study and most of the particles emitted from the gasifi- (PPE), such as protective goggles and safety masks should be wore
cation of biomass were found to be less than 1 mm [44]. It was during the operation of the gasification process. In addition, the
worth noting that in the cases of air gasification and 15% CO2 total PNC during 15% CO2 gasification was 47.1% and 75.4% less than
gasification, the PNCs in front of the control panel were signifi- that during air gasification, in the location that is in front of the
cantly higher than the PNCs 3 m away from the gasifier, which control panel and 3 m away from the gasifier, respectively. This was

Fig. 8. Particulate emissions from air gasification and 15% CO2 gasification (a)particulate emissions that may be inhalation hazard of operators during air gasification, (b)particulate
emissions that may be inhalation hazard of people nearby during air gasification, (c)particulate emissions that may be inhalation hazard of operators during 15% CO2 gasification, (d)
particulate emissions that may be inhalation hazard of people neaby during 15% CO2 gasification.
 Y. Shen et al. / Energy 170 (2019) 497e506
mainly due to the factor that during air gasification, higher reaction
temperature favored higher rate of particle fragmentation, which
would lead to more PM emissions [44]. Hence, another advantage
of CO2 gasification is that under the same ER, there is less PM
emission during CO2-assisted gasification as compared to air
gasification.
4. Biochar application and future work
In one of our previous studies, Yang and colleagues mixed alkali
biochar derived from woody biomass gasification with acidic soil
for a water spinach cultivation study [40]. They found pure biochar
with a high pH was not favored for plant growth and a moderate pH
condition showed positive impact on the growth of water spinach.
Adding biochar as soil conditioner could improve the soil texture to
enhance nutrient availability. As the biochar derived from CO2
gasification is less basic than air gasification, it could be more
applicable in the field of soil conditioner.
In this work, the small-scale autothermal gasification study is a
feasibility trial run. As shown in Table 5, when adding 15% of CO2,
the temperature of the reduction zone dropped 93
C due to the
promotion of endothermic reactions (e.g., Boudouard reaction,
steam gasification, dry tar reforming, etc.) with the presence of CO2.
Meanwhile, the temperature at the combustion zone also
decreased for 27
C. Higher fraction of CO2 ratio could further
decrease the temperature inside the reactor which could lead to
larger amount of tar formation. Meanwhile, if the CO2 addition is
low, its impact would not be significant to be observed. Future work
could be conducted to focus on the impact of different CO2-air
mixtures on gasification temperature, energy efficiency and biochar
characterizations.
5. Conclusions
In this work, a carbon negative pathway using CO2 as biomass
gasification agent was proposed and investigate from-lab scale to
pilot-scale. Lab-scale results showed that using CO2 as gasification
oxidant could generate comparable energy than traditional air
gasification owing to the enhancement of Boudouard reaction and
dry tar reforming reaction. The produced gas have a high CO/H2
ratio due to reversed water-gas shift reaction. Meanwhile, biochar
produced under CO2 condition had a moderate pH than that from
air gasification, indicating its further application as soil conditioner.
Upgrading from lab-scale, feasibility study of replacing 15% air by
CO2 was conducted in an 8 kW autothermal reactor successfully.
CO2-assisted gasification significantly improved CO yield and
reduced CH4 yield. Because of the favorable endothermic reactions
of dry tar reforming and methane reforming in the air-CO2 gasifi-
cation, the reduction temperature was obviously lower than sole air
gasification under the identical air feeding rate. However, carbon
conversion efficiency and cold gas efficiency still improved with
CO2 addition. Meanwhile, particulate matters (PM) emitted from
both air gasification and 15% CO2 gasification experiments were
measured. It was found that under the same ER, there was less PM
emission during CO2-assisted gasification as compared to air
gasification.
Acknowledgements
This research program is funded by the National Research
Foundation (NRF), Prime Minister's Office, Singapore, under its
Campus for Research Excellence and Technological Enterprise
(CREATE) program, grant Number R-706-001-101-281, and also the
2nd Intra-CREATE Seed Collaboration Grant (NRF2017-ITS002-013).
Ye Shen acknowledges China Scholarship Council (CSC) for his Ph.D.
505
scholarship. Xiaoqiang Cui acknowledges Shanghai Tongji Gao
Tingyao Environmental Science & Technology Development
Foundation.
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