J. Anal. Appl.

Pyrolysis 72 (2004) 243–248

www.elsevier.com/locate/jaap

Effects of temperature and particle size on bio-char yield

from pyrolysis of agricultural residues
Ayhan Demirbas*
Department of Chemical Engineering, Selcuk University, 42031 Konya, Turkey
Accepted 8 July 2004
Available online 11 September 2004

Abstract

This article deals with slow pyrolysis of agricultural residues such as olive husk, corncob and tea waste at high temperature (950–1250 K)
in a cylindrical reactor batch reactor. The aim of this study was to experimentally investigate how different residues utilizing strategies affect
the treatment conditions such as temperature, particle size, and lignin and inorganic matter contents on bio-char yield and reactivity. When the
pyrolysis temperature is increased, the bio-char yield decreases. The bio-char yield increased with increasing particle size of the sample. A
high temperature and smaller particles increase the heating rate resulting in a decreased bio-char yield. The higher lignin content in olive husk
results in a higher bio-char yield comparison with corncob. Bio-char from olive husk was more reactive in gasification than bio-char from
corncob because of the higher ash content.
# 2004 Elsevier B.V. All rights reserved.

Keywords: Agricultural residue; Slow pyrolysis; Bio-char; Char reactivity

1. Introduction carbon is widely used as an effective adsorbent in many

Bio-char can be obtained from biomass pyrolysis. For a
high bio-char production from biomass pyrolysis, a low
temperature and low heating rate process would be chosen.
The bio-char can be used in the preparation of active carbon
when its pore structure and surface area are appropriate. The
starting materials used in commercial production of
activated carbons are those with high carbon contents such
as wood, lignite, peat, and coal of different ranks or low-cost
and abundantly available agricultural by-products. Active
carbons can be manufactured from virtually any carbonac-
eous precursor, but the most commonly used materials are
wood, coal and coconut shell [1]. The development of
activated carbons from agricultural carbonaceous wastes
will be advantageous for environmental problems. In water
contamination, wastewater contains many traces of organic
compounds, which is a serious environmental problem.
Active carbons are carbonaceous materials with highly
developed internal surface area and porosity. Activated
* Tel.: +90 462 230 7831; fax: +90 462 248 8508.
E-mail address: ayhandemirbas@hotmail.com.
applications such as air separation and purification, vehicle
exhaust emission control, solvent recovery and catalyst
support because of its high specific pore surface area,
adequate pore size distribution and relatively high mechan-
ical strength. The large surface area results in high capacity
for adsorbing chemicals from gases and liquids [2].
Pyrolysis can be used for the production of bio-oil if flash
pyrolysis processes are used and are currently at pilot stage
[3]. Some problems in the conversion process and use of the
oil need to be overcome; these include poor thermal stability
and corrosivity of the oil. Upgrading by lowering the oxygen
content and removing alkalis by means of hydrogenation
and catalytic cracking of the oil may be required for certain
applications [4].
Chemical additives (AlCl3, FeCl3, H3PO4, NH4Cl, KOH
and ZnCl2) slightly affect the first step by inhibiting
hemicelluloses decomposition and accelerating cellulose
decomposition through the dehydration reaction. Phosphoric
acid exhibited the largest influence on the pyrolysis process.
At concentrations higher than 30% H3PO4, the two weight
loss steps ascribed to hemicelluloses and cellulose decom-
position overlapped. Bio-char with an alkaline character of

0165-2370/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2004.07.003
244 A. Demirbas / J. Anal. Appl. Pyrolysis 72 (2004) 243–248
the surface, tar and gas products are obtained by steam
pyrolysis of biomass (almond shells, nut shells, apricot
stones, cherry stones, grape seeds) [5].
The reaction mechanisms of biomass pyrolysis are
complex but can be defined in three main steps:
Biomass ! Water þ Unreacted residue (1)
Unreacted residue ! ðVolatile þ GasesÞ1 þ ðCharÞ1 (2)
ðCharÞ1 ! ðVolatile þ GasesÞ2 þ ðCharÞ2 (3)
Pyrolysis proceeds in three steps: in the initial step
moisture and some volatile loss (Eq. (1)). In the secondary
step occurred primary bio-char (Eq. (2)). The last fast step
follows by a slower step including some chemical
rearrangement of the bio-char. During the third step, the
bio-char decomposes at a very slow rate and carbon-rich
residual solid forms. The formation of secondary charring
(Eq. (3)) makes the char less reactive.
The char gasification forms an important part of biomass
gasification. The major thermochemical gasification reac-
tions include the following:Carbon char to methane:
C þ 2H2 @ CH4 (4)
Carbon char to oxides:
C þ O2 ! CO2 and C þ CO2 @ 2CO (5)
Carbon char to CO and H2:
C þ CO2 þ H2 O @ CO þ H2 (6)
The hot combustion products (CO2 and H2O) are further
reduced by the char. These endothermic reactions generate
synthetic gas (syngas): CO and H2 (Eq. (6)), and the exit gas
can be utilized as a gaseous fuel. The molecules in the
biomass (primarily carbon, hydrogen and oxygen) and the
molecules in the steam (hydrogen and oxygen) reorganize to
form this syngas. The high reactivity of bio-char is higher
when smaller biomass particle are subjected to pyrolysis.
The reactions of CO2 and H2O with the char to produce CO
and H2 are considerably slower than the drying, pyrolysis or
combustion reactions. The bio-char samples obtained by
rapid pyrolysis at higher temperatures are more reactive in
steam gasification than those obtained at lower pyrolysis
temperatures. This result is of practical interest for
utilization of biomass as a raw material for gasification.
The aim of this work is to study the effect of the treatment
conditions such as temperature, particle size, and lignin and
inorganic matter contents on bio-char yield.
2. Experimental
In this study, olive husk, corncob and tea waste from East
Black Sea region in Turkey were used as agricultural
residues. The samples were ground and sieved to give
particle size of between <0.5 and >2.2 mm. The particle
Table 1
Particle size distributions of agricultural residues
Particle size Dry olive Dry Dry tea
(mm) husk (%) corncob (%) waste (%)
<0.5 6.4 8.5 4.2
0.5–1.0 7.6 12.8 5.7
1.0–1.5 38.6 37.5 32.6
1.5–2.2 27.9 26.3 23.4
>2.2 9.5 14.9 34.1
size distributions of the samples are presented in Table 1.
The pyrolysis experiments were performed in a device
designed for this purpose. The main element of this device
was a cylindrical reactor of height 95.1 mm, i.d. 17.0 mm,
and o.d. 19.0 mm heated externally by an electric furnace
with the temperature being controlled by a thermocouple
inside the reactor.
The chemical analyses of the samples were carried out
according to the ASTM D1103-80 and ASTM D1104-56
standard test methods. The standard test methods for
biomass fuel analyses are: particle size distribution (ASTM
E828), moisture (ASTM E871), ash (ASTM D1102),
volatile matter (ASTM E 872), carbon and hydrogen
(ASTM E 777), nitrogen (ASTM E 778), sulfur (ASTM E
775), chlorine (ASTM E776) and ash elemental (ASTM
D3682, ASTM D2795, ASTM D4278, AOAC 14.7). For
structural analyses, the wood samples were prepared
according to TAPPI standard (TAPPI T 11 m-45). The
ground sample was extracted with ethanol–benzene accord-
ing to ASTM, and lignin was determined as the insoluble
residue after hydrolysis with 72% sulfuric acid. The used
materials are characterized by analytical methods.
The samples were subjected to pyrolize for obtaining bio-
chars at high temperature (450–1250 K) in a cylindrical
reactor batch reactor. The pyrolysis processes were carried
out with 10 K/s heating rate for obtaining the bio-char
products from the samples at different temperatures:
470550, 650, 750, 850, 950 and 1050 K.
All yields were expressed on a dry and ash-free (daf)
basis, and the average yields from three experiments were
presented within the experimental error of <0.5 wt.%.
3. Results and discussion
The chemical analysis results of agricultural residues are
given in Table 2. From Table 2, the corncob has the highest
volatile matter content (84.6 wt.% daf). The structural
analysis results of biomass samples are shown in Table 3. As
seen from Table 3, the lignin content of olive husk was
50.6 wt.% daf.
Fig. 1 shows the effect of temperature on the bio-char yield.
The decrease for the olive husk was 56.4% (from 44.5 to
19.4 wt.% daf) for particle size between 1.5 and 2.2 mm when
the temperature is increased from 450 to 1250 K. The
decrease for the corncob is 81.4% (from 30.6 to 5.7 wt.% daf)
 A. Demirbas / J. Anal. Appl. Pyrolysis 72 (2004) 243–248
Table 2
Chemical analysis results of agricultural residues (wt.% dry basis)
Sample C H N O (diff.)
Olive husk 50.2 6.4 1.0 38.4
Corncob 49.0 5.6 0.5 43.8
Tea waste 48.2 5.5 0.5 44.3
at the same conditions. Corncob has very high cellulose (52%
by weight) and hemicelluloses (32.5% by weight) contents.
The yield bio-char from corncob at lower temperatures
was relatively high. However, the bio-char yield rapidly
decreases with increasing of pyrolysis temperature.
The destructive reaction of cellulose is started at
temperatures lower than 325 K and is characterized by a
decreasing polymerization degree. Thermal degradation of
cellulose proceeds through two types of reaction: a gradual
degradation, decomposition and charring on heating at lower
temperatures, and a rapid volatilization accompanied by the
formation of levoglucosan on pyrolysis at higher tempera-
tures. The degradation of cellulose to a more stable
anhydrocellulose, which gives higher bio-char yield, is
the dominant reaction at temperature <575 K [7]. At
temperatures >575 K, cellulose depolymerizes, producing
volatiles. If the heating rate is very high, the residence time
of the biomass at temperatures <575 K is insignificant.
Thus, a high heating rate provides a shorter time for the
dehydration reactions and the formation of less reactive
anhydrocellulose, which gives higher yield of char [2]. The
result is that the rapid heating of the biomass favors the
polymerization of cellulose and the formation of volatiles
and suppresses the dehydration to anhydrocellulose and char
formation [6]. Hence the effect of heating rate is stronger in
the pyrolysis of biomass than in that coal.
The initial degradation reactions include depolymeriza-
tion, hydrolysis, oxidation, dehydration, and decarboxyla-
tion [7]. The isothermal pyrolysis of cellulose in air and
milder conditions, in the temperature range 623–643 K, was
investigated [8]. Under these conditions, the pyrolysis
reactions produced 62–72% aqueous distillate and left 10–
18% charred residue. After the pyrolysis, the residue was
found to consist of some water-soluble materials, in addition
to char and undecomposed cellulose.
The hemicelluloses undergo thermal decomposition very
readily. The hemicelluloses reacted more readily than
cellulose during heating. The thermal degradation of
hemicelluloses begins above 373 K during heating for
48 h; hemicelluloses and lignin are depolymerized by
Table 3
Structural analysis results of agricultural residues (wt.% dry, ash and
extractive free)
Sample Hemicelluloses Cellulose Lignin
Olive husk 24.2 25.2 50.6
Corncob 32.5 52.0 15.5
Tea waste 23.3 33.2 43.5
245
Ash Volatile matter (wt.% daf) Fixed carbon (wt.% daf)
4.1 72.5 27.5
1.1 84.6 15.4
1.5 83.8 16.2
steaming at high temperature for a short time. The metoxyl
content of wet meals decreased at 493 K [9].
The stronger effect of the heating rate on the formation of
bi-char from biomass than from coal may be attributed to the
cellulose content of the biomass [10]. It is well known that
heating rate has a significant effect on the pyrolysis of
cellulose. Heating rate has a much greater effect on the
pyrolysis of biomass than on that of coal. The quick
devolatilization of the biomass in rapid pyrolysis favors the
formation of char with high porosity and high reactivity [11].
The decreased formation of char at the higher heating rate
was accompanied by an increased formation of tar. The net
effect is a decrease in the volatile fuel production and an
increased yield of bio-char cellulose converted to levoglu-
cosan at above 535 K temperatures [12].
The inorganic properties of biomass samples are
presented in Table 4. The different amount of inorganics
may also affect the results.
The yield of bio-char was calculated according to the
equation (Eq. (7)) below [11]:
Bio-char yield ðwt:% dafÞ
ðAb =Ac Þ  ðAb =100Þ
¼ 100 (7)
1  ðAb =100Þ
where Ab is wt.% ash in dry biomass and Ac is wt.% ash in
dry bio-char.
Fig. 2 shows the effect of particle size on bio-char yield in
the conditions selected for the study. In the experiments with
olive husk at 950 K the bio-char yield decreases 45.5%
(from 35.6 to 19.4 wt.% daf) when the particle size reduced
from 2.2 to 0.5 mm. An increase in particle size from 0.5 to
Fig. 1. Effect of temperature on bio-char yield. Particle size: 1.5–2.2 mm.
246 A. Demirbas / J. Anal. Appl. Pyrolysis 72 (2004) 243–248
Table 4
Inorganic properties of biomass samples (wt.% of the ash)
Sample Si2O Al2O2 Fe2O3 CaO MgO Na2O K2O SO3 P2O5
Olive husk 32.9 8.4 6.3 14.5 4.2 26.4 4.3 0.6
Corncob 52.9 9.1 6.8 9.4 3.3 1.6 5.3 4.9
Tea waste 44.4 7.2 5.2 12.6 3.8 1.8 18.8 1.4
2.2 mm for corncob at 950 K increases the solid residue
from 5.7 to 16.6 wt.% after total pyrolysis, i.e. a 65.7%
increase in amount of bio-char.
Fig. 3 shows the effect of temperature on carbon content
in char. Fig. 4 shows the effect of temperature on oxygen
content in char. Fig. 5 shows the effect of temperature on
hydrogen content in char. The results of the elemental
analysis (Figs. 3–5) indicate that contents of carbon increase
with pyrolysis temperature while these corresponding to
hydrogen and oxygen decrease. Losses in hydrogen and
oxygen correspond to the scission of weaker bonds within
the bio-char structure favored by the higher temperature
[13].
Fig. 6 shows relationships between the content of lignin
and the bio-char yield from the samples. The higher lignin
content in olive husk (Table 3) gives a higher bio-char yield
comparison with oak wood and wheat straw. Lignin gives
higher yields of charcoal and tar from wood although lignin
has 3-fold methoxyl than that of wood [14–16].
If the purpose were to maximize the yield of liquid
products resulting from biomass pyrolysis, a low tempera-
ture, high heating rate, short gas residence time process
would be required. For a high char production, a low
temperature, low heating rate process would be chosen. If
the purpose were to maximize the yield of fuel gas resulting
from pyrolysis, a high temperature, low heating rate, long
gas residence time process would be preferred.
Phenolics are derived from lignin by cracking of the
phenyl–propane units of the macromolecule lattice. Pyrolysis
Fig. 2. Effect of particle size on bio-char yield. Final temperature: 950 K.
2.5
6.6
4.8
Fig. 3. Effect of temperature on carbon content in bio-char. Particle size:
1.5–2.2 mm.
seems to produce the most substituted phenols on a selective
basis. This phenomenon can be explained by the fact that the
syringyl–propan units are not so linked to the lignin skeleton
as the less substituted: gaiacyl–propane and phenyl–propane
[17]. It has been compared to the DTA curves of different
lignin preparations in vacuo and concluded that the
degradation pattern was virtually the same, an endotherm
extending from about 373–453 K and followed by an
exotherm at about 675 K, as the results of thermal analysis
of individual types of lignin made by many other investigators
[18,19]. Lignin is broken down by extensive cleavage of
b-aryl ether linkages during steaming of wood less than 488 K
[20]. It has been found that on analysis of the metoxyl groups
after isothermal heating of dry distilled wood, lignin
decomposition begins at about 550 K with a maximum rate
occurring between 625 and 725 K and the completion of the
reaction occurs at 725 and 775 K [9].
Fig. 4. Effect of temperature on oxygen content in bio-char. Particle size:
1.5–2.2 mm.
 A. Demirbas / J. Anal. Appl. Pyrolysis 72 (2004) 243–248
Fig. 5. . Effect of temperature on hydrogen content in bio-char. Particle
size: 1.5–2.2 mm.
The formation of char from lignin under mild reaction
conditions is a result of the breaking of the relatively weak
bonds, like the alkyl–aryl ether bond(s), and the
consequent formation of more resistant condensed
structures, as has already been noted by Domburg et al.
[21]. One additional parameter, which may also have an
effect on the char formation is the moisture content of the
kraft lignin used. It has been found that the presence of
moisture increased the yield of char from the pyrolysis of
wood waste at temperatures between 660 and 730 K, while
Stray et al. [22] found only a slight effect for water added
on the hydrogenolysis of both hardwood and softwood
lignins at temperatures between 470 and 675 K. The
thermolysis reactions of the kraft lignin is comprised
mainly of breaking the most reactive bonds like the methyl
C–O bond of the methoxyl group and the condensation
reactions to high molecular weight products (char) that
follows.
Fig. 6. Effect of lignin content on yield of bio-char at 950 K final tem-
perature. Particle size: 1.5–2.2 mm.
247
4. Conclusion
Bio-char can be obtained from biomass pyrolysis. If the
purpose were to maximize the yield of bio-char resulting
from pyrolysis, a low temperature, low heating rate process
would be chosen. When the pyrolysis temperature increased
the bio-char yield decreased. The bio-char yield increased
with increasing particle size of the sample.
The higher lignin content in olive husk results in a higher
bio-char yield comparison with corncob. Bio-chars from
olive husk are more reactive in gasification than bio-chars
from corncob because of the higher ash content.
Biomass converts by pyrolysis into liquid (bio-oil), bio-
char and gasses by heating the biomass to about 850 K in the
absence of air. The process can be adjusted to favor bio-char,
pyrolytic oil, gas, or methanol production with a 95.5% fuel-
to-feed efficiency. The heat flux is proportional to the driving
force, the temperature difference between the particle and
environment. At higher temperature, the heat flux is higher.
The size of the particles affects the heating rate. The heat
flux and the heating rate are higher in small particles than in
large particles. The higher heating rate favors a decrease of
the char yield [2].
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