Bioresource Technology 130 (2013) 345–350

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

Characteristics of biochar produced from slow pyrolysis of Geodae-Uksae 1

Yongwoon Lee a, Pu-Reun-Byul Eum a, Changkook Ryu a,⇑, Young-Kwon Park b, Jin-Ho Jung c,
Seunghun Hyun c
a
School of Mechanical Engineering, Sungkyunkwan University, Suwon 440-746, Republic of Korea
b
Faculty of Environmental Engineering, University of Seoul, Seoul 130-743, Republic of Korea
c
Division of Environmental Science and Ecological Engineering, Korea University, Seoul 136-713, Republic of Korea

h i g h l i g h t s

" Geodae-Uksae 1 (Giant Miscanthus) is a variety of Miscanthus sacchariflorus for energy crop.
" Ideal temperature to produce biochar by slow pyrolysis was 500 °C.
" The biochar had a mass yield of 27 wt.% at 500 °C with a carbon content of 79 wt.%.
" The surface area and large pores of biochar was well-developed at 500 °C for application to soil.

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

Article history: This study investigated producing biochar from Geodae-Uksae 1 for soil applications to sequestrate car-
Received 30 March 2012 bon from the atmosphere and improve the productivity of crops. Using a lab-scale packed bed reactor,
Received in revised form 2 December 2012 pyrolysis products of Geodae-Uksae 1 were produced over a temperature range of 300–700 °C with a
Accepted 5 December 2012
heating rate of 10 °C/min. Pyrolysis at 500 °C was found appropriate for biochar production considering
Available online 13 December 2012
the properties of char and the amount of heat required. It yielded biochar of 27.2 wt.% that contained
approximately 48% carbon in the raw biomass. The surface area of the biochar rapidly increased to
Keywords:
181 m2/g. Large cylindrical pores with diameters of 5–40 lm developed within the biochar due to the
Biochar
Biomass
vascular cell structure of the parent biomass. The byproducts (bio-oil and gases) were also analyzed
Geodae-Uksae 1 for use as fuel.
Miscanthus Ó 2012 Elsevier Ltd. All rights reserved.
Slow pyrolysis

1. Introduction
Geodae-Uksae is the Korean term for giant Miscanthus. Geodae-
Uksae 1 is a variety of Miscanthus sacchariflorus (Amur silvergrass)
recently discovered in Korea (Moon and Koo, 2011) that grows
approximately 4 m tall with an average stalk diameter of 1 cm,
which is approximately twice as tall and thick as common M. sac-
chariflorus. The mass yield of the dry stalk is as much as 30 ton/ha,
which is twice that of common Miscanthus. Due to the superior
yield, Geodae-Uksae 1 is being mass-cultivated in Korea as an en-
ergy crop for bioenergy. Various methods are being considered for
the energy conversion of Geodae-Uksae 1, including hydrolysis and
fermentation for bioethanol production, combustion through pel-
letization and fast pyrolysis for the production of bio-oil.
This study investigates a method for producing biochar from
Geodae-Uksae 1 for the sequestration of carbon in soil and to in-
⇑ Corresponding author. Tel.: +82 31 299 4841; fax: +82 31 290 5889.
E-mail address: cryu@me.skku.ac.kr (C. Ryu).
crease the productivity of various food crops (Lehmann, 2007). Bio-
char is the highly carbonaceous solid product of the pyrolysis of
biomass, which can be used to improve the yield of various agricul-
tural crops as a soil amendment. Due to its strong resistance to bio-
logical decomposition, the carbon in biochar can be removed from
the atmosphere to mitigate climate change. Since carbon originates
from atmospheric carbon dioxide, the application of biochar to soil
may contribute to reductions of CO2 concentration. Biochar has
been used in horticulture and agriculture with its appearance in lit-
erature as early as 1697 (Lehmann and Joseph, 2009). Biochar has
drawn interest from a wider scientific community due to a study
by Lehmann et al. (2003) examining the sustained fertility of Ama-
zonian dark soil, also known as Terra Preta. When applied to soil,
biochar can effectively retain nutrients and water, and therefore
reduce the need for fertilizers. In addition to carbon removal, bio-
char in soil reduces the emissions of other major greenhouse gases,
such as N2O and CH4 (Van Zweiten et al., 2009), which have a glo-
bal warming potential of 298 and 25, respectively, compared to the
greenhouse effect of CO2 over a 100 year period (IPCC, 2007). These

0960-8524/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.biortech.2012.12.012
346 Y. Lee et al. / Bioresource Technology 130 (2013) 345–350
benefits suggest that the application of biochar from biomass to
soil could be as effective as producing energy from the valuable re-
source. Depending on the type of biomass, the amount of biomass
available for energy production widely varies by location and time
of year. Due to its typically low bulk density, it is sometimes not
economical to collect and transport biomass to a large-scale bioen-
ergy plant. In contrast, biochar that is locally produced by a small-
scale pyrolysis unit can be consumed locally, minimizing transport
needs.
Slow pyrolysis is an ideal technology to produce biochar, which
involves thermal decomposition in an inert atmosphere at a slow
heating rate (10 °C/min) (Mohan et al., 2006). Pyrolysis converts
solid fuels, such as coal and biomass, into char (solid), vapors of
condensable hydrocarbons (called ‘oil’ for use after condensation)
and non-condensable gases (e.g., CO, CO2, H2 and CH4). Biochar,
or char originating from biomass, is typically 20–40 wt.% of dry lig-
nocellulosic biomass. However, the yield and characteristics of the
pyrolysis products are strongly influenced by the operating condi-
tions (e.g., temperature, heating rate, pressure, purge gas and par-
ticle size) and the properties of the feedstock (Antal and Grønli,
2003; Enders et al., 2012). Therefore, the operating conditions of
the pyrolysis process can be adjusted to meet the product require-
ments, however the actual process needs to be carefully designed
and performed.
In this study, Geodae-Uksae 1 was pyrolyzed in a lab-scale reac-
tor to investigate the yield and properties of biochar for applica-
tions to soil. Biochar was produced by slow pyrolysis at a
temperature of 300–700 °C and characterized for elemental com-
position, morphology, surface area and distribution of pore sizes
and volumes. The byproducts of pyrolysis, i.e., bio-oil and gases,
were analyzed for further use as energy sources.
2. Experimental
2.1. Geodae-Uksae 1 samples
Geodae-Uksae 1 samples were provided by the Korean Rural
Development Administration (RDA), which discovered and culti-
vated the strain. Geodae-Uksae 1 was harvested in the second year
of planting, in early spring of 2011. Late winter or early spring is
suitable for harvest since the moisture content of the crop natu-
rally drops at that time (Lewandowski et al., 2000; Fernando
et al., 2008). The nutrients in the plant are transported in winter
and stored in underground rhizomes for the formation of new
shoots (Beale et al., 1996). The harvested samples were maintained
in dry indoor storage. The sample consisted mostly of stalks with a
few leaves, since the leaves of Miscanthus naturally fall in winter
(Beale et al., 1996). The stalks were cut into 4 cm long pieces for
feeding into a pyrolysis reactor. Each piece was cylindrical and hol-
low, with a diameter of 4–12 mm.
2.2. Pyrolysis reactor
The products of slow pyrolysis were produced at final tempera-
tures ranging from 300 to 700 °C using a lab scale reactor. Fig. 1
shows a schematic diagram of the system. The reactor was made
of stainless steel with a diameter of 10 cm and a height of 30 cm.
It was placed inside an electrically-heated furnace with a temper-
ature control. In each test, 20 g of sample was heated within the
reactor from room temperature to the target temperature at a
heating rate of approximately 10 °C/min. Once the temperature in-
side the reactor reached the target temperature, it was maintained
for at least one hour to allow sufficient time for complete pyrolysis.
Nitrogen was continuously supplied at a flow rate of 1.2 min 1 to
purge the pyrolysis vapors from the reactor. The gas flow forced
the pyrolysis vapors to pass through a series of condensers
submerged in coolants at 20 °C (water) and 20 °C (acetone),
respectively, for the separation of condensable (bio-oil) and
non-condensable gases. Past the particulate filter, the gas flow rate
was recorded using a mass flow meter (Tylan, FM-360). The gas
compositions of the main gas species (O2, CO, CO2, H2 and CH4)
were measured using an on-line gas analyzer (A&D System, A&D
9000). The reactor temperatures, gas flow rates and compositions
were logged using a data acquisition system. The gases were also
sampled into Tedlar bags for detailed compositional analysis by a
gas chromatograph (Perkin-Elmer, Clarus 680 GC). After each test,
biochar and bio-oil were collected from the reactor and condens-
ers, respectively, to measure the mass yield and for detailed prop-
erty analyses. The mass yield of gases was calculated by difference.
The pyrolysis tests were repeated at least three times for key target
temperatures (400, 500 and 600 °C). Pyrolysis at 450 °C, 550 °C and
700 °C was tested once in order to check the variations around
500 °C. The average mass yields are presented in this study as
the deviation of the values in each test was less than 1.5 wt.% from
the average, except for 300 °C.
2.3. Characterization of biomass and pyrolysis products
The biomass and biochar compositions were analyzed by prox-
imate analysis based on standard methods (moisture content:
ASTM E871-82, ash: ASTM D1102-84, volatile matter: ASTM
E872-82 and fixed carbon: by difference) and ultimate analysis
using an elemental analyzer (CE Instruments, EA 1108/NA 2000).
The higher heating value (HHV) of biomass was measured using
a bomb calorimeter (Parr-1261, Parr Instrument). Thermo-
gravimetric analysis (TGA) for the biomass was carried out by
using a Labsys. EVO TGA analyzer (Setaram) for 7 mg of powdered
sample at a heating rate of 10 °C/min under nitrogen atmosphere
(30 ml/min). Detailed characteristics of biochar were analyzed
using a scanning electron microscope (SEM, JEOL, JSM-7600F) for
surface morphology, N2–BET (Micrometrics, Tristar 3020) for
surface area, and a porosimeter (Micromeritics, AutoPore 4 9250)
for distribution of pore volumes.
The hydrocarbon compositions in the bio-oil were analyzed by a
GC–MS (Hewlett–Packard, HP5890/HP5972). To determine the ele-
mental composition of bio-oil, it was separated into light and hea-
vy phases in a centrifugal separator (ROTINA, 35R). Then, each
phase was analyzed by an elemental analyzer (CE Instruments,
EA 1108/NA 2000) to determine the C, H, O and N compositions
and Karl-Fisher titration (Metrohm, 870 KF Titrino plus) to assess
the water content. Based on the elemental compositions, the
HHV of biochar and bio-oil were calculated using an empirical cor-
relation proposed by Channiwala and Parikh (2002).
The HHV of the gases was estimated from the net mass yield
and HHV of each gas component. The net mass yield of a gas com-
ponent was acquired by integrating the concentrations history
measured by the gas analyzer over the test duration.
3. Results and discussion
3.1. Properties of Geodae-Uksae 1
The air-dried sample of Geodae-Uksae 1 contained 7.3% mois-
ture, 73.2% volatile matter, 15.9% fixed carbon and 3.6% ash. The
volatile matter to fixed carbon ratio was 4.6, which is in a typical
range for lignocellulosic biomass. The elemental composition on
a dry-ash-free basis was 47.6% C, 5.5% H, 46.1% O and 0.8% N, which
was equivalent to C1.00H1.39O0.73N0.01. Analyses were also con-
ducted to compare different sections of stalks, but no significant
differences were found. The HHV experimentally determined was
 Y. Lee et al. / Bioresource Technology 130 (2013) 345–350
Fig. 1. Schematic diagram of a lab-scale pyrolysis reactor.
17.28 MJ/kg which was similar to the value (17.05 MJ/kg) esti-
mated by the correlation of Channiwala and Parikh (2002). The cel-
lulose and hemicellulose contents were 40.8% and 31.4%,
respectively. The lignin content for the sample was 23.0%, which
was 5–9% higher than the common M. sacchariflorus in Korea
(Kim et al., 2012). Such high lignin content is favorable for biochar
production, since lignin contributes more to the formation of char.
Overall, Geodae-Uksae 1 has a very good quality as a fuel for ther-
mo-chemical conversion to produce heat, electricity or chemical
feedstock.
The TGA analysis of Geodae Uksae 1 exhibited a typical decom-
position trend of lignocellulosic biomass (Yang et al., 2007;
Sanchez-Silva et al., 2012). The moisture evaporated near 100 °C.
Hemicellulose began to decompose at approximately 200 °C and
reached a peak rate (0.35 wt.%/°C) of mass loss at 290 °C. The hemi-
cellulose peak overlapped with cellulose decomposition which
continued to approximately 380 °C with a peak rate of 1.21 wt.%/
°C appearing at 358 °C. The residual weight at 380 °C was
28.5 wt.%. The pyrolysis above 380 °C was due to lignin, which
slowly decomposes over a wide temperature range. The final
weight of the solid residue was approximately 17 wt.% at 800 °C.
3.2. Product yields of pyrolysis
Table 1 lists the product yields from pyrolysis of Geodae-Uksae
1 in the lab-scale reactor. The solid (biochar) yield decreased with
increasing temperatures up to 500 °C. The decrease in the yield
above 500 °C was very small, since the decomposition of hemicel-
lulose and cellulose was complete.
The mass yield of bio-oil including water condensation was
about 50% at 400 °C and above. A peak in the bio-oil yield appeared
at 550 °C (50.57 wt.%) but was only 2.26 wt.% higher than that at
400 °C. In many studies for pyrolysis of biomass, the maximum
oil yield appears at 500–550 °C for various heating conditions, sizes
and types (Ertasß and Alam, 2010; Heo et al., 2010; Phan et al.,
2008). The slight decrease above 600 °C may be the result of va-
por-phase cracking of heavy hydrocarbon compounds inside the
hot reactor. However, the decrease in the bio-oil yield was not sig-
Table 1
Mass yields (wt.%) of pyrolysis products from Geodae-Uksae 1.
Temperature (°C) 300 400
Biochar 49.54(±1.41) 30.95(±0.32)
Bio-oil 30.70(±2.52) 48.31(±1.05)
Gases 19.75(±2.14) 20.74(±1.36)
347
nificant since the pyrolysis vapors were continuously purged from
the reactor by nitrogen while the reactor was heated.
The gas yield was calculated by the difference, which gradually
increased from approximately 20%, consisting largely of CO and
CO2 at lower temperatures. The detailed composition of the re-
leased gases will be presented later.
3.3. Biochar properties
Table 2 summarizes the key properties of biochar from Geodae-
Uksae 1. As the pyrolysis temperature increased, the fixed carbon
and elemental carbon content gradually increased. The carbon con-
tent of biochar at 500 °C was 79.42 wt.% on a dry basis, represent-
ing 48.36 wt.% carbon in the raw biomass. Therefore, biochar is the
preferred product of pyrolysis in terms of carbon. Although the dif-
ference in its mass yield between 500 °C and 700 °C was less than
2 wt.%, the increase in elemental carbon content was about
6.5 wt.% dry. This implies that the biochar became increasingly car-
bonaceous at high temperatures, releasing H and O.
One of the main purposes of biochar production is to remove
carbon in soil. Therefore, the high carbon content of biochar is ben-
eficial in terms of maximizing the amount of carbon storage. The
weight of carbon in the biochar from 500 °C corresponds to
21.56 wt.% (=0.7942  27.15%) of the weight of the raw biomass.
The equivalent amount for CO2 becomes 79.1 wt.% (=21.56  44/
12) of the raw biomass, if all of the carbon remains in the soil in
the long term. Note that biochar can reduce the amount of fertilizer
required and the emission of N2O and CH4 from the soil. Therefore,
the amount of carbon emissions prevented by biochar can be
significant, although it is influenced by many factors (Gaunt and
Lehmann, 2008; Galinato et al., 2011).
Fig. 2 shows a van Krevelen diagram of biochar to illustrate the
changes in its elemental composition. As pyrolysis progressed, H
and O were depleted in the biochar and it became carbon-rich.
The decrease in the H/C and O/C ratios was approximately linear,
approaching the origin (pure carbon) as the pyrolysis temperature
increased. This trend coincided well with other types of biomass,
such as pine and straw (Karaosmanoğlu et al., 2000; Keiluweit
et al., 2010), also plotted in the figure.
450 500 550 600 700
29.42 27.15(±0.23) 26.21 25.92(±0.76) 25.10
49.01 50.03(±1.11) 50.57 49.78(±1.13) 48.24
21.56 22.82(±1.23) 23.23 24.30(±1.05) 26.66
348 Y. Lee et al. / Bioresource Technology 130 (2013) 345–350

Table 2
Key properties of biochar from Geodae-Uksae 1.

Temperature (°C) 300 400 450 500 600 700

Fixed carbon content (wt.% dry) 53.34 73.89 78.48 82.59 88.07 91.66
C content (wt.% dry) 66.19 74.69 78.29 79.42 83.67 85.93
C yield (wt.% dry of C in raw biomass) 73.55 51.86 51.67 48.36 48.65 48.38
N2–BET surface area (m2/g) 0.49 3.11 21.93 180.96 293.04 368.98

2.0
Geodae-Uksae #1 (a) 500
Goedea-Uksae #1
Brassica napus L Straw-stalka Ponderosa Pinea
1.6

N2-BET surface area (m /g)

Ponderosa Pineb Tall Fescue Strawa
400

2
Tall Fescue Strawc Alderb
H/C atomic ratio

Beechb
1.2
Raw 300
biomass

0.8
400o C 200

500o C
0.4
600o C 100
700o C
0.0
0.0 0.2 0.4 0.6 0.8 0
300 400 500 600 700
O/C atomic ratio o
Temperature ( C)
Fig. 2. Van Krevelen diagram of biochar at different pyrolysis temperatures (a: data
taken from Karaosmanoğlu et al., 2000; b and c: data taken from Keiluweit et al.
(2010)).
(b) 6
o
300 C
Log differential intrusion (mL/g)

Fig. 3a compares the N2–BET surface area of biochar to that of
other lignocellulosic biomass with a pore size range of 2–50 nm.
The surface area determines the nutrient adsorption capability of
biochar in soil. Biochar with a large surface area can fix nutrients,
preventing them from being washed away by water and therefore
reducing the need for fertilizers. The biochar produced using
Geodae-Uksae 1 exhibited a rapid increase in surface area to
approximately 180 m2/g at 500 °C, which was one order of magni-
tude greater than at 450 °C. The surface area gradually increased at
higher temperatures, and became similar to that of a soft wood,
ponderosa pine (Keiluweit et al., 2010), also plotted in Fig. 3a. In
contrast, two hard woods, alder and beech (Gray et al., 1985),
exhibited greater surface areas from low temperatures, while the
increases in surface area were smaller at higher temperatures.
The surface area of the wood samples and Geodae-Uksae 1 con-
verged at 700 °C. In contrast, the straw sample (tall fescue straw)
(Keiluweit et al., 2010) had a very low surface area, even at 700 °C.
Fig. 3b shows the distribution of pore volumes in biochar rang-
ing from 10 nm to 100 lm. Compared to the biochar at 300 °C, the
pore volume significantly increased at 500 °C over the entire size
range. When the surface morphology of biochar was examined
using SEM, the char from 300 °C was filled with tissue that was
not devolatilized and therefore the pores were not fully developed.
Once the cellulose and hemicellulose were decomposed at 500 °C,
the char became honeycomb-like with large cylindrical holes of 5–
40 lm in diameter interconnected by thin walls. These holes orig-
inated from the pith and vascular system of the parent plant. The
pore volumes of mesopores and macropores up to 1 lm, which
developed on the cell walls, were also significant. When biochar
is applied to the soil, the roles of the pores depend on their sizes.
Micro and mesopores up to 50 nm in diameter adsorb nutrients
(e.g., NH4+, HPO42 , H2PO4 and dissolved organic carbon) and
gases (e.g., O2 and CO2), while large pores (10 lm) provide habi-
o
5 500 C
o
600 C
4
3
2
1
0
0.01 0.1 1 10 100
Pore diameter (µm)
Fig. 3. N2–BET surface area (a) and pore volumes distribution (b) of biochar (a: data
taken from Keiluweit et al. (2010), b: data taken from Gray et al. (1985)).
tats for symbiotic microorganisms, such as bacteria (0.3–3 lm),
fungi (2–80 lm) and protozoa (7–30 lm) (Thies and Rillig, 2009).
Biochar becomes less hydrophobic and its capacity to hold water
also increases at 500 °C (Kinney et al., 2012).
Based on the properties of biochar presented in this study, an
appropriate temperature for biochar production by slow pyrolysis
would be 500 °C. The mass yield of biochar was higher at 300 °C
(Table 1), but the high volatile matter content at the temperature
inhibits plant growth and reduced N uptake in soil (Deenik et al.,
2009). At 500 °C, the macro- and micropores rapidly develop to in-
crease the pore volumes and surface area. Temperatures above
500 °C further increased the surface area of biochar, but required
a larger amount of heat supply. Furthermore, the bio-oil, an impor-
tant byproduct of biochar production, had a decrease in its mass
yield at higher temperatures. Evaluating the performance of the
 Y. Lee et al. / Bioresource Technology 130 (2013) 345–350 349

Table 3
Composition of bio-oil and the estimated heating value.

Temperature (°C) Phase (wt.%) Water content (wt.%) Elemental composition (wt.%) HHV (MJ/kg)
Aqueous Heavy oil C H O N
300 91.29 8.71 59.77 19.17 9.97 70.34 0.51 11.14
400 67.76 32.24 42.39 29.55 8.47 61.41 0.58 13.92
500 57.16 42.84 36.93 32.24 9.07 57.74 0.96 15.94
600 47.31 52.69 36.18 38.51 9.03 51.54 0.92 18.72

biochar for improving crop productivity requires further extensive

studies. Enders et al. (2012) suggested that the most effective
35 600
approach is to define the limiting factors of a particular soil-
Temp.

Gas concentration (vol.%)

crop-climate condition and apply biochar tailored to address the 30 CO2 500
growth constraints.

Temperature ( C)
25
400
3.4. Bio-oil properties 20
CO 300
Bio-oil is a pyrolysis byproduct of biochar production. The prop- 15
erties of bio-oil have been widely reported in the literature, and 200

o
therefore only a summary of the key properties is presented here 10
for the bio-oil derived from Geodae-Uksae 1. Table 3 describes CH4
5 100
the composition of bio-oil and the estimated HHV. The bio-oil
has two strata of light aqueous and heavy oil fractions. At lower H2
0 0
temperatures, the oil is mostly the light fraction with approxi- 0 1000 2000 3000 4000 5000 6000
mately 60 wt.% overall water content. With increasing tempera-
tures, the proportion of heavy oil fraction and carbon content Time (s)
increases. At temperatures greater than 500 °C, the water content Fig. 4. Concentration of non-condensable gases and the reactor temperature for the
in the bio-oil was approximately 37 wt.% and the carbon content pyrolysis test up to 500 °C.
was 32 wt.%. The bio-oils produced at 500 °C and 600 °C were not
very different, since the pyrolysis vapors were continuously purged
from the reactor into the condenser. The HHV estimated from the
elemental composition was 15.94 MJ/kg, while commercial heavy Table 5
oil is approximately 45 MJ/kg (Turns, 2011). This low HHV is due Composition of non-condensable gases and estimated heating values.
to the high water content and large concentration of oxygenated
Temperature (oC) 300 400 500 600
hydrocarbon compounds in the bio-oil.
Mass yield (wt.%) 19.75 20.74 22.82 24.30
Table 4 lists the key compounds identified by GC–MS in the bio-
oil produced at 500 °C. The bio-oil contained numerous hydrocar- Species mass fraction (wt.%)
CO 38.27 25.14 26.40 26.81
bons, which were primarily acids and phenols, typical of lignocel-
CO2 60.13 62.47 57.65 53.44
lulosic biomass bio-oil both from slow and fast pyrolysis (Phan CH4 1.59 12.38 15.82 19.03
et al., 2008; Heo et al., 2010). H2 0.01 0.01 0.13 0.72
Overall, the quality of the bio-oil was not high enough for use as Elemental composition (wt.%)
primary fuel due to the high water content, inhomogeneity and C 33.99 37.10 38.90 40.34
low energy content. Bio-oil is also acidic, corrosive, viscous, repoly- H 0.41 3.10 4.09 5.47
merizes to form heavier compounds and causes delayed ignition O 65.60 59.80 57.01 54.19

when combusted (Oasmaa and Czernik, 1999; Mohan et al., HHV(MJ/kg) 4.76 9.42 11.64 14.30
2006; Chiaramonti et al., 2007). Such properties of bio-oil require
caution during handling, storage and use. Therefore, a simple

method of utilizing bio-oil as a renewable fuel may be to co-com-

Table 4
bust it with conventional fuels in an existing furnace. A solvent,
Key compounds identified in bio-oil by GC–MS for pyrolysis at 500 °C.
such as methanol and ethanol, could be mixed into the bio-oil to
Retention time (min) Compounds Area (%) prevent repolymerization during storage and decrease its viscosity
2.44 Acetic acid 10.7 for easier handling (Oasmaa and Czernik, 1999; Mohan et al.,
4.77 2-Furan carboxaldehyde 5.53 2006).
10.43 Phenol 4.42
12.39 2-Methoxy phenol 5.95
13.95 2-Ethyl phenol 5.67
14.86 2,3-Dihydro benzofuran 7.89 3.5. Properties of non-condensable gases
15.53 4-Ethyl-2-methoxy phenol 4.90
16.03 2-Methoxy-4-vinyl phenol 3.45
16.64 2,6-Dimethoxy phenol 6.32
Fig. 4 shows the gas release profiles from a pyrolysis test at a final
17.80 4-Hydroxy-3-methoxy benzoic acid 4.17 temperature of 500 °C measured by an on-line gas analyzer. CO2 and
18.77 2,3,5-Trimethoxy toluene 1.62 CO were the two dominant species in the early stage of pyrolysis,
19.71 2,4-Hexadienedioic acid 1.17 mainly due to the presence of cellulose and hemicellulose. Release
20.77 2,6-Dimethoxy-4 phenol 1.66
of CH4 followed with a peak at approximately 460 °C. H2 appeared
23.48 Hexadecanoic acid 0.71
above 470 °C at a low concentration mainly from the decomposition
350 Y. Lee et al. / Bioresource Technology 130 (2013) 345–350
of lignin (Yang et al., 2007) and partially from vapor phase cracking
of heavy hydrocarbons (Morf et al., 2002; Gilbert et al., 2009).
Table 5 summarizes the composition of non-condensable gases
and the HHV. The estimated HHV was approximately 11.64 MJ/kg
at 500 °C, which is not high due to the large proportion of CO2.
However, the gases can be burned to provide the heat required
for pyrolysis. The heat required to increase the biomass tempera-
ture from 25 °C to 500 °C is 0.89 MJ/kgbiomass for a specific heat of
1.4 kJ/kg K (Incropera et al., 2007). The energy content in the pyro-
lytic gases corresponds to 11.64 MJ/kg  (22.82 wt.%) = 2.66 MJ/
kgbiomass. Therefore, 33.5% (0.89/2.66) of the heat exchange effi-
ciency between the pyrolysis reactor and hot combustion gases
of the non-condensable gases is sufficient to maintain the reactor
at 500 °C. However, this is not straightforward to achieve for
small-scale pyrolysis systems. The process requires indirect heat
exchange in the pyrolysis reactor to avoid contamination of the
pyrolysis vapors. The pyrolysis vapors must be quenched to con-
dense bio-oil, and such quenching is often accomplished by spray-
ing already-quenched bio-oil. The remaining gases can then be
burned to generate hot gas. The biochar should be collected and
cooled to prevent contact with the air. Incorporating these features
requires complex design and control, which is difficult for small-
scale systems. Therefore, a careful design of the pyrolysis system
is essential to minimize the requirements for the external heat
supply and efficiently operate the pyrolysis process.
4. Conclusions
This study presented the pyrolysis characteristics of Geodae-
Uksae 1 to produce biochar for soil quality improvement and CO2
sequestration. A pyrolysis temperature of 500 °C was found appro-
priate considering the properties of biochar and the heat supplied.
The biochar yield was of 27 wt.% at the temperature with a carbon
content of 79 wt.% and surface area of 180 m2/g. Large pores of 5–
40 lm developed in the biochar, which is beneficial for symbiotic
micro-organisms in soil. The bio-oil consisted largely of water,
acids and phenols. The energy content in the product gases was
sufficient for use as process heat.
Acknowledgements
This work was performed with the support of the Cooperative
Research Program for Agriculture Science & Technology Develop-
ment (Project No. PJ0079662011), Rural Development Administra-
tion, Republic of Korea. The authors would like to thank Dr. Y-H.
Moon (RDA) for providing Geodae-Uksae 1 samples.
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