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Energy Sources, Part A: Recovery, Utilization, and Environmental Effects
Energy Sources, Part A: Recovery, Utilization, and Environmental Effects
To cite this article: Ayhan Demirbas (2006) Production and Characterization of Bio-Chars from Biomass via Pyrolysis, Energy
Sources, Part A: Recovery, Utilization, and Environmental Effects, 28:5, 413-422, DOI: 10.1080/009083190927895
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Energy Sources, Part A, 28:413–422, 2006
Copyright © Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/009083190927895
AYHAN DEMIRBAS
Department of Chemical Engineering
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Selcuk University
Konya, Turkey
This article deals with slow pyrolysis of oak wood and agricultural residues such as
hazelnut shell and wheat straw at high temperature (950–1250 K) in a cylindrical
reactor. 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
and reactivity. When the pyrolysis temperature increased, the bio-char yield decreased.
A high temperature and smaller particles increase the heating rate resulting in a
decreased bio-char yield. The higher lignin content in hazelnut shell results in a
higher bio-char yield in comparison with oak wood and wheat straw. Bio-chars from
hazelnut shell and wheat straw are more reactive in gasification than bio-chars from
oak wood because of the higher ash content. The bio-char obtained are carbon rich,
with high heating value and relatively pollution-free potential solid biofuel.
Active carbons are carbonaceous materials with highly developed internal surface area and
porosity. Activated carbon is widely used as an effective adsorbent in many 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 mechanical strength. The large surface area results in
high capacity for adsorbing chemicals from gases and liquids (Zanzi, 2001).
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 man-
ufactured from virtually any carbonaceous precursor, but the most commonly used ma-
terials wood, coal, and coconut shell (Heschel and Klose, 1995). The development of
activated carbons from agricultural carbonaceous wastes will be advantageous for envi-
ronmental problems. In water contamination, wastewater contains many traces of organic
compounds which are a serious environmental problem. In the development of activated
carbons, agricultural carbonaceous wastes will be used, as this will eliminate the problem
of waste disposal while at the same time societies will derive great economic benefits
from such commercialized products.
This study was financially supported by the Scientific Research Project (BAP in Turkish
initials) of Selcuk University.
Address correspondence to Professor Ayhan Demirbas, Selcuk University, Department of
Chemical Engineering, 42031 Konya, Turkey. E-mail: ayhandemirbas@hotmail.com
413
414 A. Demirbas
1. They can be used as adsorbents for the removal or reduction of gaseous pollutants
from the exhaust gases of industrial sources.
2. They can be used as adsorbents for the removal of volatile organic compounds,
ozone from air, mercury and dioxin emissions from incinerator flue gas, and
hydrogen sulfide emissions from sewage treatment facilities.
3. They can be used to remove chlorine and organic chemicals (such as phenols,
polychlorinated biphenyls, trihalomethanes, pesticides and halogenated hydrocar-
bons), heavy metals and organic contaminants from water.
4. They can be used to extract some harmful elements of cigarette smoke by incor-
poration in filter tips of the cigarettes.
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Pyrolysis can be used for the production of bio-oil if flash pyrolysis processes are
used and these are currently at the pilot stage (EUREC Agency, 1996). 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 (Demirbas and Gullu, 1998).
Pyrolysis of wood has been studied as a zonal process (Goldstein, 1981). Pyrolysis of
biomass is thermal decomposition of the fuel. As with coal, pyrolysis is a relatively slow
chemical reaction occurring at low temperatures. The reaction mechanisms of biomass
pyrolysis are complex but can be defined in five stages for wood.
Pyrolysis proceeds in three steps. In an initial step, there is moisture and some
volatile loss (Eq. 1). Primary bio-char occurs in the secondary step (Eq. 2). The last fast
step follows by a slower step including some chemical rearrangement of the bio-char.
During the third stage, the bio-char decomposes at a very slow rate and a carbon-rich
residual solid forms. The formation of secondary charring (Eq. 3) makes the char less
reactive.
Experimental
In this study, hazelnut shell, oak wood, and wheat straw from the East Black Sea region
in Turkey were used as samples. The samples were ground and sieved to give a particle
size of 0.4–1.2 mm. The pyrolysis experiments were performed in a device designed
for this purpose. The main element of this device was a cylindrical reactor of height
Bio-Chars from Biomass 415
Table 1
Methods of biomass fuel analyses
Table 2
Chemical analysis results of biomass samples (wt% dry basis)
95.1 mm, ID 17.0 mm, and OD 19.0 mm. It was heated externally by an electric furnace
with the temperature being controlled by a thermocouple inside the reactor.
Chemical analyses of the samples were carried out according to the ASTM D1103-
80 and ASTM D1104-56 standard test methods. The methods of biomass fuel analyses
are given in Table 1. The used materials are characterized. Table 2 shows the elemental
compositions of the samples.
The pyrolysis processes were carried out with 10 K/s heating rate for obtaining
the bio-char products from the samples at different temperatures. Determination of the
oxygen and hydrogen contents in char samples were carried out at 470, 550, 650, 750,
850, 950, and 1050◦ K, and other experiments at 950, 1050, 1150, and 1250◦ 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%.
Table 3
Structural analysis results of biomass samples (wt% daf)
Biomass Extractive
sample Hemicelluloses Cellulose Lignin mattera
Table 4
Proximate analysis results of biomass samples
Figure 1 shows the effect of temperature on the bio-char yield. The decrease for
the hazelnut shell is 84.2% (33.5 wt% daf to 15.3 wt% daf) for particle size between
0.8 mm and 1.2 mm when the temperature is increased from 950 to 1250◦ K. The inorganic
properties of biomass samples are presented in Table 5. The different amount of inorganics
may also affect the results. The oak wood gives more volatiles and less char than the
hazelnut shell on a dry and ash free (daf) basis. Chlorine, which is found in certain
biomass types, such as straw, may affect operation by corrosion. The high chlorine and
alkali content of some biomass fuels raises concerns regarding corrosion. The greatest
concern focuses on high-temperature corrosion of superheater tubes induced by chlorine
on the surface.
Figure 1. Effect of temperature on char yield (wt% daf). Particle size: 0.8–1.2 mm.
Bio-Chars from Biomass 417
Table 5
Inorganic properties of biomass samples (wt% of the ash)
Biomass
sample Si2 O Al2 O2 Fe2 O3 CaO MgO Na2 O K2 O SO3 P2 O5 Cl
Oak wood 48.8 9.6 8.6 18.6 1.2 0.5 9.6 1.6 1.8 0.5
Wheat 48.0 3.5 0.5 3.7 1.8 14.5 21.0 0.9 3.5 3.6
straw
Hazelnut 33.8 3.1 3.8 15.4 7.9 1.5 30.4 0.6 3.2 0.3
shell
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The yield of bio-char was calculated from the ash yields of the bio-char and biomass
(Zanzi et al., 1996):
where ab is wt% ash in dry biomass, and ac is wt% ash in dry bio-char.
Figure 2 shows the effect of particle size on bio-char yield in the conditions selected
for the study. In the experiments with oak wood at 950◦ K the bio-char yield decreases
∼26.0% (from 22.7 wt% daf to 16.8 wt% daf) when the particle size is reduced from
1.2 mm to 0.4 mm. An increase in particle size from 0.4 to 1.2 mm for hazelnut shell
at 950◦ K increases the solid residue from 21.6 to 33.5 wt% after total pyrolysis, i.e., an
∼55.1% increase in amount of bio-char.
Figure 3 shows the effect of temperature on carbon content in char. Figure 4 shows the
effect of temperature on oxygen content in char. Figure 5 shows the effect of temperature
on hydrogen content in char. The results of the elemental analysis (Figures 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
(Della Rocca et al., 1997).
Figure 2. Effect of particle size on char yield (wt% daf). Final temperature: 950◦ K.
418 A. Demirbas
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Figure 3. Effect of temperature on carbon content in char. Particle size: 0.8–1.0 mm.
Figure 4. Effect of temperature on oxygen content in char. Particle size: 0.8–1.0 mm.
Figure 5. Effect of temperature on hydrogen content in char (wt% daf). Particle size: 0.8–1.0 mm.
Figure 6. Effect of lignin content on yield of char at different final temperatures. Particle size:
0.8–1.2 mm.
maximum rate occurring between 625 and 725◦ K and the completion of the reaction
occurs at 725 and 775◦ K (Demirbas and Kucuk, 1994).
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 bonds, and the consequent
formation of more resistant condensed structures, as has already been noted (Domburg
et al., 1974). One additional parameter which may also have an effect on the char forma-
tion 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. (1986) found only a slight effect for water
added on the hydrogenolysis of both hardwood and softwood lignins at temperatures
between 470 and 675◦ K.
cellulose to a more stable anhydrocellulose, which gives higher bio-char yield, is the
dominant reaction at temperature <575◦ K (Shafizadeh, 1985). 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 a higher yield of char (Zanzi, 2001). 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 (Ek-
ström and Rensfeld, 1980). Hence the effect of heating rate is stronger in the pyrolysis
of biomass than in that coal.
The initial degradation reactions include depolymerization, hydrolysis, oxidation,
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The hot combustion products (CO2 and H2 O) are further reduced by the char. These
endothermic reactions generate CO and H2 , and the exit gas can be utilized as a gaseous
fuel. Among the thermochemical conversion processes that take place in a gasifier, the
high reactivity of bio-char is higher when smaller biomass particles are subjected to
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pyrolysis. The reactions of CO2 and H2 O 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.
Conclusion
The biomass samples were subjected to pyrolize for obtaining bio-chars at high tempera-
ture (950–1250◦ K) in a cylindrical reactor batch reactor. The aim of the work was to study
the effect of the treatment conditions such as temperature, particle size, and lignin and
inorganic matter contents on bio-char yield. 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 hazelnut shell results in a higher bio-char yield in
comparison with oak wood and wheat straw. Bio-chars from hazelnut shell and wheat
straw are more reactive in gasification than bio-chars from oak wood 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 (Zanzi, 2001).
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