Bioresource Technology 249 (2018) 348–353

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Torrefaction of corncob to produce charcoal under nitrogen and carbon T

dioxide atmospheres
⁎
Shu-Xian Li, Chang-Zhou Chen, Ming-Fei Li , Xiao Xiao
Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing 100083, China

G RA P H I C A L AB S T R A C T

A R T I C L E I N F O A B S T R A C T

Keywords: Corncob was torrefied under nitrogen and carbon dioxide atmospheres at 220–300 °C, obtaining solid products
Charcoal with mass yields of 69.38–95.03% and 67.20–94.99% and higher heating values of 16.58–24.77 MJ/kg and
Corncob 16.68–24.10 MJ/kg, respectively. The changes of physicochemical properties of the charcoal was evaluated by
Torrefaction many spectroscopies, contact angle determination, and combustion test. Hemicelluloses were not detected for
Nitrogen
the torrefaction under the hard conditions. As the severity increased, C concentration raised while H and O
Carbon dioxide
concentrations reduced. Combustion test showed that the burnout temperature of charcoal declined with the
elevation of reaction temperature, and torrefaction at a high temperature shortened the time for the whole
combustion process. Base on the data, torrefaction at 260 °C under carbon dioxide was recommended for the
torrefaction of corncob.

1. Introduction from corn processing, is a widely distributed agricultural crop waste in

In response to the environmental issue resulting from the rapid
exhaustion of fossil fuels, biomass, as a renewable and biodegradable
resource, is receiving increased attention. In China, approximate
630 million tons of crop residues is produced annually (Liu et al., 2008);
however, most of them are discarded or directly burnt, in which only a
small proportion served as livelihood energy. Corncob, as a by-product
the world. The main compositions are cellulose, hemicelluloses and
lignin, as well as a minor amount of extractives and ash. The total yield
of corn arrives about 1.2 × 108 t in China annually, and the speculated
production of corncob is 2.16 × 107 t (Zheng et al., 2010). There are
many drawbacks for this agricultural waste, such as the complicated
chemical composition, richness in oxygen and moisture, hydrophilic
characteristics, biodegradation (Chen et al., 2016). Thus, it is difficult

⁎
Corresponding author.
E-mail address: limingfei@bjfu.edu.cn (M.-F. Li).

http://dx.doi.org/10.1016/j.biortech.2017.10.026
Received 16 August 2017; Received in revised form 5 October 2017; Accepted 6 October 2017
Available online 12 October 2017
0960-8524/ © 2017 Elsevier Ltd. All rights reserved.
S.-X. Li et al.
to support the straightforward way for the efficient utilization. Conse-
quently, large amounts of corncob are utilized in low-value application.
To vitalize this waste, some processes have been developed to convert it
into biofuels, chemicals, and materials. For example, fermentable su-
gars was obtained by acid hydrolysis (Jiang et al., 2017), bioethanol
and xylitol were produced by enzymatic hydrolysis of pretreated
corncob (Itelima et al., 2013; Li et al., 2015; Zhang et al., 2010), and
furfural is produced through hydrolysis of the hemicelluloses in
corncob under acidic conditions at high temperatures (Mao et al.,
2012). In addition, carbon materials such as activated carbon have also
been developed as absorbent (Ding et al., 2013). However, these pro-
cesses are not widely applied due to the high cost for investment as well
as the poor economic efficiency under a turbulent market. Therefore, it
is urgent to develop a more efficient method to convert the renewable
source in a reasonable way.
Biomass is a promising resource to partially replace coal for the
production of sustainable energy in the future. However, the draw-
backs, such as heterogeneity, high transportation cost, great grinding
energy, high moisture content, low energy density, make it used in a
few fields. These limitations can be minimized by applying a thermo-
chemical pretreatment process, referred to as torrefaction, prior to
feeding into coal-fired boilers. Torrefaction is a promising process to
enhance the fuel characteristics of the raw material, which is especially
suitable for a conversion system to enhance the handling efficiency. It is
a mild thermal pretreatment with operating temperatures from 200 to
300 °C from several minutes to several hours. During the process, the
thermal decomposition of a huge proportion of hemicelluloses and ex-
tractives in biomass produces a solid fuel (charcoal) and combustible
volatiles (CO, H2, and CH4) (Wilk et al., 2015). Compared to native
biomass, the charcoal obtained from torrefaction shows many ad-
vantages, such as water resistance, superior calorific value, good
grindability, resistance to biodegradation, as well as easiness for com-
bustion and gasification (Gucho et al., 2015; Strandberg et al., 2015).
After torrefaction, biomass turns into pellets and briquettes with su-
perior bulk energy density, which is a good feedstock for pyrolysis
(Atienza-Martínez et al., 2017). Moreover, it may significantly reduce
the costs of the milling, storage and transportation, and enhance the
storage characteristics of biomass. Another advantage for the thermal
pretreatment is the product can be mixed with coal for power plants.
During the torrefaction process, biomass is heated in an oxygen-free
atmosphere. Conventionally, nitrogen, as an inert gas, has been applied
to processing various biomass, such as pine (Winjobi et al., 2017a,b),
spruce (Anca-Couce et al., 2016; Larsson et al., 2013), switchgrass
(Sarkar et al., 2014), olive mill waste (Benavente and Fullana, 2015).
Although much information on the torrefaction of biomass is
available, there is less knowledge nowadays about the influence of
carbon dioxide, a greenhouse gas released from the combustion process
in many industries, on the torrefaction (Rousset et al., 2012; Thanapal
et al., 2014), in which the report on torrefaction of agricultural crop
wastes is not available. If the carbon dioxide gas from the wasted gases
was used, nitrogen can be saved, thus the process became competitive.
Thus, the objective of the research was to study the effect of reaction
conditions on the charcoal obtained from corncob after torrefaction
under nitrogen and carbon dioxide. The structure and properties of the
charcoal obtained at various temperatures and atmospheres were in-
vestigated to estimate the potential application. The study provides a
comparative estimation of the performance of the conversion of
corncob through torrefaction, which is meaningful for the potential
utilization.
2. Materials and methods
2.1. Materials
Corncob collected from a farm in Henan province (China) served as
the raw material. It was pulverized to obtain the fraction with size of
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Bioresource Technology 249 (2018) 348–353
20–80 mesh, and then it was stored in a sealed bag. Nitrogen (99.999%)
and carbon dioxide (99.998%) were provided by Beijing Special Gas
Company, China.
2.2. Torrefaction process
Torrefaction was carried out using a horizontal tubular quartz tube
reactor heated by a furnace (SK-G08123K, Tianjin, China). In each run,
10 g raw material was loaded into a zirconium oxide boat (length
60 mm, width 51 mm, and height 32 mm), which was put into a quartz
tube reactor. High-purity N2 or CO2 was introduced into the reactor at
100 mL/min to provide a specific reaction atmosphere. After the reactor
was swept 5 min, a certain heating procedure started with heating rate
5 °C/min and the temperature increased from ambient temperature to
the target temperature (220, 260, and 300 °C). As the holding time of
30 min was reached, the reactor was cooled down under the flow rate of
carrier until the temperature was dropped to 70 °C. Then the charcoal
was collected before analysis. Note: S-Temperature-atmosphere denotes
the charcoal produced, i.e., S220-N2, S260-N2, and S300-N2 are in-
dicative of the charcoals obtained after torrefaction at 220, 260, and
300 °C under N2 atmosphere, whereas S220-CO2, S260-CO2, and S300-
CO2 are for the specimens torrefied at 220, 260, and 300 °C under CO2
atmosphere. Each experiment was conducted in triplicate and the ex-
perimental error was less than 3%.
2.3. Characterization of biomass samples
The characterization of the sample was performed in triplicate and
the average value was reported (error was less than 3%). The chemical
components of the sample were identified according to method re-
ported previously (Li et al., 2010). For the torrefied sample, the mate-
rial not soluble in acid water was defined as acid-insoluble material
since it was structurally distinct from Kalson lignin. Elemental analysis
was conducted with a Vario EL III instrument (Elementar, Germany). C,
H, and O contents were weight percentages of the elements based on
ash free sample. Higher heating value (HHV) was calculated as:
HHV(MJ/kg) = 0.3383ZC + 1.422(ZH−Zo/8) (1)
where ZC, ZH, and ZO are the weight percentages of carbon, hydrogen,
and oxygen, respectively (Yuan et al., 2009).
Fourier transform inferred (FTIR) spectra were recorded on a
Thermo Scientific Nicolet iN10 FT-IR Microscope (Thermo Nicolet
Corporation, Madison, WI, USA). X-ray diffractograms of the solid re-
sidues were obtained by using an X-ray diffraction 6000 instrument
(Shimadzu, Japan). The curves were recorded from 5° to 40° (2θ) at 2°/
min. The solid charcoal was observed with a scanning electron micro-
scope (S-3400 N, HITACHI, Japan). The crystallinity index (CrI) was
estimated refereeing to Segal’s method (Kupiainen et al., 2012):
I22.5−I18
CrI =
I22.5 (2)
where I22.5 and I18 are the intensity at 2θ = 22.5° (maximum) and at
2θ = 18° (minimum), respectively.
Contact angle determination of the surfaces of the samples were
conducted using an optical contact angle apparatus (OCA 20 Data
Physics Instruments GmbH, Filderstadt, Germany). The equipment
consisted of a video measuring system, a high-resolution CCD camera,
and a high-performance digitizing adapter. Combustion behavior of the
samples was determined using a thermogravimetric analyzer (SDT
Q600, TA Instrument). Specimens (5–10 mg) were heated from 30 to
750 °C under 50 mL/min air. The heating rate was 10 °C/min.
S.-X. Li et al. Bioresource Technology 249 (2018) 348–353

The mass yield and HHV of charcoal obtained from torrefaction

under N2 and CO2 are shown in Fig. 1. As the reaction temperature
raised, the mass yield of charcoal decreased. Compared to the dry
weight of the raw material, the mass loss for S220-N2 and S220-CO2
were only about 5%, which was caused by the removal of low mole-
cular weight aromatic compounds, and partial degradation of lignin
(Berthet et al., 2016). When the processing temperature increased to
260 and 300 °C, an obvious mass loss of the samples was observed re-
gardless of the carrier gas used. This was caused by the decomposition
of hemicelluloses and partial decomposition of cellulose and lignin as
well as the release of the corresponding products (Zheng et al., 2013).
Moreover, the mass loss for S260-N2 (76.95% of mass yield) was larger
than that for S260-CO2 (87.62% of mass yield), and S260-N2 showed a
lower HHV (19.21 MJ/kg) as compared to that of S260-CO2 (20.34 MJ/
kg). At the torrefaction temperature of 300 °C, the yield of char and
HHV of S300-N2 were 69.38% and 27.77 MJ/kg, which were higher
than that of S300-CO2 (67.2%, 24.1 MJ/kg). As compared to the sam-
ples torrefied in CO2, when the reaction temperature raised to 260 °C,
the samples torrefied in N2 atmosphere showed a higher rate of thermal
degradation of volatile matters thus produced lower yield of charcoal.
On the contrary, a higher rate of thermal degradation was observed in
the samples torrefied in N2 atmosphere at 300 °C. The energy yield was
overall 89%, comparable to the charcoal from non-woody biomass re-
ported previously (Chew and Doshi, 2011; Yue et al., 2017). For the
torrefaction at 220 and 260 °C, inert gas was in favor of the degradation
of biomass thus led to lower mass yield.

3.2. Analysis of the chemical components

The change of the chemical component after torrefaction is illu-

strated in Fig. 2. Clearly, temperature had a greater effect than gas on
the decrease of the contents of cellulose and hemicelluloses. For tor-
refaction in N2, as temperature increased from 220 to 260 °C, hemi-
cellulose content drastically declined from 34.69% to 4.22% and cel-
lulose content slightly increased from 42.66% to 45.28% (due to the
loss of hemicelluloses). At the meantime, the content of non-poly-
saccharide organic material (acid-insoluble organic material and acid-
soluble aromatic material) increased progressively from 18.92% to

Fig. 1. Mass yield (a), HHV (b) and energy yield (c) of charcoals obtained from torre-
faction under nitrogen and carbon dioxide.

3. Results and discussion

3.1. Mass and energy yields

The mass yield (MY) and energy yield (EY) of the charcoal were
estimated on a dry raw material based on:

MY = mbiochar /mfeedstock × 100% (3)

EY = MY × (100−A) × (HHVbiochar/HHVfeedstock) × 100% (4)

where mbiochar and mfeedstock are the mass of corncob after torrefaction
and the original corncob, HHVbiochar and HHVfeedstock are higher Fig. 2. Chemical components of charcoals obtained from torrefaction under nitrogen and
carbon dioxide.
heating value of the charcoal and feedstock; and A is ash content.

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S.-X. Li et al.
Fig. 3. C, H and O components of charcoals obtained from torrefaction under nitrogen
and carbon dioxide.
43.63%. The torrefaction in CO2 showed a similar trend. At the high
temperature of 300 °C, no hemicelluloses were detected, and the cel-
lulose content decreased to 0.39% and 0.45%, but the content of non-
polysaccharide organic material steadily increased to 89.88% and
86.56% for S300-N2 and S300-CO2, respectively. This was in ac-
cordance with the previous research that hemicelluloses were the most
reactive compounds among carbohydrates in biomass (Sarvaramini
et al., 2013; Zhang et al., 2016).
3.3. Elemental analysis
Fig. 3 shows the elemental analysis of the samples before and after
torrefaction. The arrow represents the direction of the changes of the
elemental components as the temperature elevated. The C, H and O
contents of the raw material were determined to be 46.76%, 6.30% and
46.94%, respectively. The direction of arrow paralleled to the C axle
confirmed the increase of C content (Benavente and Fullana, 2015). As
the temperature increased, the hydrogen and oxygen contents of all
torrefied samples decreased, resulting in low H/C atomic ratio and O/C
atomic ratio after torrefaction in both N2 and CO2 atmospheres. During
the torrefaction of the samples in N2 atmosphere, with the elevation of
reaction temperature from 220 to 260 °C, the C contents of the samples
increased from 48.15% to 53.97%, whereas the H and O contents de-
creased from 5.94% to 5.70% and from 45.91% to 40.33%, respec-
tively. For the torrefaction of the sample in CO2 atmosphere, some
elements released resulted in the vibration of the elemental contents.
When the temperature elevated from 220 to 260 °C, the C contents of
the samples raised from 48.52% to 55.47%, whereas the H and O
contents reduced from 5.92% to 5.89% and from 45.60% to 38.61%,
respectively. When the temperature elevated to 300 °C, the C, H and O
contents of the charcoal were 67.12%, 4.92%, 27.96% for torrefaction
in N2 and 65.81%, 4.93%, 29.36% for torrefaction in CO2, respectively.
Clearly, O/C atomic ratio reduced notably as temperature elevated,
suggesting that the compounds containing oxygen were more volatile as
compared to those containing hydrogen and carbon elements and that
the primary reaction of the corncob during torrefaction process was
deoxygenation.
3.4. X-ray diffraction analysis
As a useful approach to analyze the crystalline structure of lig-
nocellulose, X-ray diffraction was adopted to study the crystallinity of
the products. When the reaction temperature increased from 220 to
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Bioresource Technology 249 (2018) 348–353
300 °C, a similar trend of the change in the X-ray diffraction curve was
found in both torrefaction in N2 and CO2. The diffraction angles (2θ)
around 18.0 ° and 22.5 ° were attributed to the diffraction plane of 101
and 002 of the cellulose I and cellulose II, respectively. The crystallinity
index (CrI) of the original corncob was 30.0%, whereas those of the
charcoal decreased with the rise of the torrefaction temperature. In N2,
the CrI of the torrefied samples raised from 16.2% to 20.8% (due to the
loss of amorphous components) and then decreased to 0, which in-
dicated no crystalline structure in the croncob charcoal obtained from
torrefaction at 300 °C. The sample torrefied in CO2 showed a similar
change tend to the sample torrefied in N2. However, the CrI of S220-
CO2 was 14.9%, which was lower than S200-N2, while the S260-CO2
show a higher CrI (28.6%) than S260-N2. In a previous report on tor-
refaction of bamboo, willow, coconut shell, and wood at 240 °C, it was
observed an almost complete degradation of hemicelluloses without
any degradation of cellulose or lignin (Chen and Kuo, 2011), while it
was found that the degradation of hemicelluloses started at 180 °C
(Kamdem et al., 2002). Hemicelluloses were notably degraded while
cellulose was relatively stable, which caused the increase in the content
of cellulose in charcoal. As a result, the CrI of the charcoal torrefied at
260 °C was larger than that of the sample torrefied in 220 °C. As tem-
perature increased from 260 °C to 300 °C, the CrI of charcoal reduced to
0 due to the severe degradation of cellulose including both amorphous
and crystalline parts, as evidenced by the fact that only less than 1%
cellulose was detected and no hemicelluloses were found in chemical
analysis.
3.5. FTIR analysis
During torrefaction, the major components in biomass (cellulose,
hemicelluloses, and lignin macromolecules) are affected, depending on
their respective chemical reactivity. The structural change of the
sample was analyzed using FTIR. The characteristic bands of the sam-
ples were assigned according to the published data (Yan et al., 2017;
Zheng et al., 2013). As can be seen, there were some structural mod-
ifications in the corncob samples after the treatments by the separate
torrefaction in N2 and CO2. The samples torrefied in N2 and CO2 showed
a similar change trend with the increase of temperature. All sample
showed a broad band around 3400 cm−1 due to the –OH groups. The
peaks around 2930 cm–1 indicating that aliphatic and aromatic groups
were present in both corncob and charcoal samples. For the spectra of
the charcoal obtained from both N2 and CO2 atmosphere, the signal at
1735 cm−1 corresponding to unconjugated C]O vibration reduced as
the increase of torrefaction temperature, since acetyl groups were re-
moved. In addition, the signals attributed to aromatic skeletal vibration
at 1600, 1510, and 1420 cm−1 became relatively strong compared to
those of carbohydrates, suggesting the aromatization of the feedtock.
The signal at 1254 cm−1 (syringyl ring and CeO stretch) reduced in the
spectra of the samples torrefied at 220 and 260 °C and the signal van-
ished in the spectra of the samples torrefied at 300 °C. The signal at
899 cm−1 was due to CeH deformation in cellulose. The peak at
1162 cm−1 (CeO stretching) was from aliphatic ether in carbohydrates.
When the samples were torrefied at 260 and 300 °C, the signal of CeO
decreased since carbohydrates degraded by dehydration and dec-
arboxylation. The ratio of the signal at 1514 cm−1 to that at 1375 cm−1
raised as temperature elevated, suggesting that the aromaticity of the
sample increased.
3.6. Effect of torrefaction on the contact angle
As temperature increased from 220 to 300 °C, corncob changed from
light to black. Contact angle was applied to evaluate the possible
wettability of the surface of charcoal (Table 1). From the data, θ < 90°
indicated the solid surface was hydrophilic, whereas θ > 90° suggested
that the surface was hydrophobic. The water contact angle of the raw
material was lower than 90°, indicating the hydrophilic characteristic.
S.-X. Li et al. Bioresource Technology 249 (2018) 348–353

Table 1
Combustion parameters and contact angle of charcoal obtained from TG analysis.

Sample Ignition temp. Max. combustion rate Peak temp. (°C) Burnout temp. (°C) Residual weight at 750 °C Reactivity Contact angle (°)
(°C) (%/min) (%) (%/(min·K))

Raw 228 ± 1 14.5 ± 0.2 302 ± 0.3 462 ± 1 1.4 ± 0.2 2.5 ± 0.3 74.2 ± 0.4
S220-N2 235 ± 1 11.9 ± 0.4 301 ± 0.4 443 ± 2 1.8 ± 0.3 2.1 ± 0.6 95.2 ± 0.1
S260-N2 247 ± 2 16.0 ± 0.3 303 ± 0.2 438 ± 1 3.7 ± 0.3 2.8 ± 0.2 102.1 ± 0.3
S300-N2 255 ± 2 6.5 ± 0.3 289 ± 0.4 425 ± 2 5.2 ± 0.4 1.2 ± 0.1 119.8 ± 0.1
S220-CO2 238 ± 1 12.2 ± 0.5 301 ± 0.3 460 ± 1 1.9 ± 0.1 2.1 ± 0.3 99.8 ± 0.2
S260-CO2 250 ± 1 13.3 ± 0.3 302 ± 0.5 458 ± 0.1 3.9 ± 0.3 2.3 ± 0.3 109.7 ± 0.2
S300-CO2 258 ± 2 6.1 ± 0.1 290 ± 0.4 447 ± 0.5 4.1 ± 0.2 1.1 ± 0.4 114.2 ± 0.3

The degradation of hemicelluloses as well as cellulose resulted in the
removal of hydrophilic groups, thus the raw material became hydro-
phobic (Acharya et al., 2015; Berthet et al., 2016; Strandberg et al.,
2015). After the torrefaction, the contact angel of all the torrefied
samples was higher than 90°, suggesting the increase of hydrophobicity.
Furthermore, the contact angel increased as the torrefaction tempera-
ture elevated, indicating that high hydrophobicity of corncobs was
obtained at a high temperature.
3.7. Combustion characteristic
To investigate the combustion characteristic of the charcoal, TG and
DTA curves of the samples were recorded under air atmosphere.
Clearly, both the TG and DTA curves of the charcoal were apparently
different from that of corncob, indicating that the combustion char-
acteristic of the sample notably changed after torrefaction. The com-
bustion process showed highly exothermal as indicated by the DTA
curves. The combustion process of the samples involved dehydration,
volatilization as well as char formation, and mineral decomposition.
The dehydration included removal of free water and crystal water. The
combustion parameters were calculated according to the literatures
(Pala et al., 2014) as illustrated in Table 1. As the increase of the re-
action temperature, the burnout temperature deceased from 443 °C to
425 °C during torrefaction in N2, and from 460 °C to 447 °C during
torrefaction in CO2. The data suggested that torrefaction shortened the
time for the whole combustion process. In addition, the residual weight
at 750 °C for the charcoal increased as torrefaction temperature ele-
vated. This was caused by the loss of volatile matter as well as the
enrichment of ash in the charcoal. Reactivity increased first and then
reduced as torrefaction temperature elevated, in which S260-N2 and
S260-N2 showed good reactivity of 2.8%/(min·K) and 2.3%/(min·K),
whereas S300-N2 and S300-CO2 were less half of that of the raw ma-
terial. This was because less volatile content led to low reactivity of the
sample. The less volatile matter in charcoal made the flame more stable
during the combustion process (Bilgic et al., 2016; He et al., 2013).
Overall, considering the reactivity of the samples, torrefaction at 260 °C
under N2 and CO2 produced good fuel products. Since CO2 is gas
available from flu gas, which is cheaper than the pure N2 prepared from
special equipment, CO2 was a better recommendation for use. Despite
torrefaction is a promising approach to improve the quality of lig-
nocellulose fuel, the process requires inert atmosphere as well as en-
ergy. Given the fact that carbon dioxide is an emission gas from the
combustion of fossil fuel, the carbon dioxide recycled was considered to
be an intriguing alternative to nitrogen as a medium for torrefaction. In
addition, the hot gas from boiler exhaust was rich in energy, thus the
energy for heating can be saved to a large extent. For the above eva-
luation, it can be concluded that the benefit of torrefaction using carbon
dioxide was that it saved the costs for medium and energy.
4. Conclusion
Temperature showed more effect on the resulting properties of
charcoal than atmosphere. Torrefaction at a high temperature led to
notable reduction in the carbohydrate content and crystallinity. FTIR
analysis indicated that the aromaticity enhanced but the signals from
carbohydrate groups reduced with the increase of temperature. The
contact angel increased when the temperature elevated, suggesting the
high hydrophobicity of the charcoal. The burnout temperature de-
ceased as torrefaction temperature elevated, and the time for the whole
combustion process shortened after torrefaction. The medium condi-
tions of 260 °C under CO2 atmosphere were recommended for torre-
faction of corncob.
Acknowledgements
This work was financially supported by the Fundamental Research
Funds for the Central Universities (2017PT06), Beijing Key Laboratory
Project (Z161100005016041), Beijing Outstanding Talents Training
Project (2016000020124G044), and the National Natural Science
Foundation of China (31400508).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.biortech.2017.10.026.
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