International Journal of Hydrogen Energy 31 (2006) 613 – 620

www.elsevier.com/locate/ijhydene

Potential evolution of Turkish agricultural residues as bio-gas,

bio-char and bio-oil sources
Ayhan Demirbas∗ , Erol Pehlivan, Turkan Altun
Department of Chemical Engineering, Selcuk University, 42031 Konya, Turkey

Received 21 June 2004; received in revised form 17 May 2005

Available online 19 July 2005

Abstract
A study has been conducted to evaluate the potential power production from the pyrolysis for bio-oil and bio-char, and
anaerobic digestion (for bio-gas), of agricultural residues in Turkey. Agricultural residues are potential renewable energy
resources such as bio-gas from anaerobic digestion, bio-oil from pyrolysis, and bio-char from carbonization and slow pyrolysis
processes. Anaerobic bio-gas production is an effective process for conversion of a broad variety of agricultural biomass to
methane to substitute natural gas and medium calorific value gases. When the pyrolysis temperature increased the bio-char yield
decreased. The bio-char yield increased with increasing particle size of the sample. Thermochemical conversion processes of
biomass are the most common and convenient methods for conversion into energy. Among the processes of energy production
from biomass, pyrolysis is the most popular thermal conversion process.
䉷 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Agricultural residue utilization; Bio-oil; Bio-gas; Bio-char; Turkey

1. Introduction
Since the 1970s oil price crisis, increased attention has
been focused on the development of technologies using new
and renewable sources of energy like biomass, geothermal,
solar power, wind, and hydropower. Biomass fuels (fuel-
wood, animal wastes, cereal residues, etc.) are used daily
in about half the world’s households as energy for cook-
ing and/or heating. Biomass sources, such as agricultural
residues, fruit stones and nut shells, are very good precur-
sors for the production of bio-oil, bio-char and bio-gas fuels
[1,2]. In the developing countries, these sources are more
important because many of these nations don’t have the
scarce fossil energy sources such as crude oil, natural gas,
∗ Corresponding author. Tel.: +90 462 230 7831;
fax: +90 462 248 8508.
E-mail address: ayhandemirbas@hotmail.com (A. Demirbas).
and coal. The new and renewable energy resource systems
offer attractive prospects because they are pollution free,
unlimited, and cheap [3].
Direct combustion is the old way of using biomass.
Biomass thermo—chemical conversion technologies such
as pyrolysis and gasification are certainly not the most
important options at present; combustion is responsible for
over 97% of the world’s bio-energy production. Use for
energy recovery is mainly by combustion, while pyrolysis
and gasification are being investigated at laboratory and
plot scales [4].
Biomass offers important advantages as a combustion
feedstock due to the high volatility of the fuel and the high
reactivity of both the fuel and the resulting char. Biomass
is in part due to the generally higher moisture content and
in part due to the high oxygen content. It is only organic
petroleum substitute which is renewable. However, it should
be noticed that in comparison with solid fossil fuels, biomass
contains much less carbon and more oxygen and has a

0360-3199/$30.00 䉷 2005 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2005.06.003
614 A. Demirbas et al. / International Journal of Hydrogen Energy 31 (2006) 613 – 620
low-heating value. Biomass firing, in comparison with coal
firing, helps reduce the total emissions per unit energy pro-
duced. A renewable fuel such as waste product or energy
crop-derived biomass fuels is a lowest-cost option for re-
ducing greenhouse gas emissions.
Agricultural residues such as straws, nut shells, fruit
shells, fruit seeds, plant stalks, stovers, green leaves, and
molasses are potential renewable energy resources. Current
disposal methods for these agricultural residues have caused
widespread environmental concerns. For example, disposal
of rice and wheat straw by open-field burning causes air
pollution [5].
Agricultural “green energy” production is the principal
contributor in economic development of a developing coun-
try. Its economy development is based on agricultural pro-
duction and most people live in the rural areas. Implemen-
tation of integrated community development programs is
therefore very necessary. It is believed that integrated com-
munity development contributes to push up socio-economic
development of the country.
Anaerobic biological treatment of the agricultural solid
waste is a process which has received increased attention
during the last few years. Conversion of these wastes to
methane provides some energy and can have a beneficial
effect on the environment, and during the digestion process
bacteria in the manure are killed, which is a great benefit
to environmental health. The production of methane during
the anaerobic digestion of biologically degradable organic
matter depends on the amount and kind of material added
to the system.
2. Turkey’s bio-gas potential
2.1. Anaerobic digesters and methane production
The first methane digester plant was built at a leper colony
in Bombay, India, in 1859 [6]. A methane digester system,
commonly referred to as an anaerobic digester (AD) is a
device that promotes the decomposition of manure or di-
gestion of the organics in manure to simple organics and
gaseous bio-gas products. There are three types of continu-
ous digesters: vertical tank systems, horizontal tank or plug-
flow systems, and multiple tank systems. Proper design, op-
eration, and maintenance of continuous digesters produce a
steady and predictable supply of usable bio-gas.
Several types of bio-digesters have been developed in-
cluding the floating drum, the fixed dome, the bag, the plas-
tic tube [7], the plug flow and the up-flow anaerobic sludge
blanket digesters. Fig. 1 shows an on-farm bio-gas system.
Anaerobic decomposition is a complex process. Methane
is produced in environments where organic matter accumu-
lates, and oxygen is absent [8]. The process by which anaer-
obic bacteria decompose organic matter into methane, car-
bon dioxide, and a nutrient-rich sludge involves a step-wise
series of reactions requiring the cooperative action of sev-
MANURE FEEDING
ANAEROBIC DIGESTER SLUDGE STORAGE
BIOGAS STORAGE NITROGEN-RICH MANURE
COOKING HEATING FIELD APPLICATION
Fig. 1. An on-farm bio-gas system.
eral organisms. It occurs in three basic stages as the result of
the activity of a variety of microorganisms. Initially, a group
of microorganisms converts organic material to a form that
a second group of organisms utilizes to form organic acids.
Methane-generating (methanogenic) anaerobic bacteria uti-
lize these acids and complete the decomposition process. In
the first stage, a variety of primary producers (acidogens)
break down the raw wastes into simpler fatty acids. In the
second stage, a different group of organisms (methanogens)
consume the organic acids produced by the acidogens, gen-
erating bio-gas as a metabolic byproduct. On average, aci-
dogens grow much more quickly than methanogens. Finally,
the organic acids are converted to bio-gas.
A variety of factors affect the rate of digestion and bio-
gas production. The most important is temperature. Anaer-
obic bacteria communities can endure temperatures ranging
from below freezing to above 330.4 K, but they thrive best
at temperatures of about 309.9 (mesophilic) and 327.6 K
(thermophilic). Bacteria activity, and thus bio-gas produc-
tion, falls off significantly between about 312.6 and 324.9 K
and gradually from 308.2 to 273.2 K.
Average 68% of the cultivated land produces grains, wheat
ranking first, barley second, and corn third in developing
countries. Agricultural solid residues are potential renew-
able energy resources [9]. Contents of carbon (C), hydrogen
(H) and oxygen (O), fixed carbon (FC) and volatile mate-
rial (VM), and higher heating value (HHV) of agricultural
solid residues are given in Table 1. Wheat straw wastes rep-
resent a potential energy resource if they can be properly
and biologically converted to methane. They are renewable
and their net CO2 contribution to the atmosphere is zero.
Manures and manure/straw mixtures have been extensively
investigated as sources of bio-gas [10–16].
In a process of manure and straw mixture digestion, for
first 3 days, methane yield was almost 0% and carbon diox-
ide generation was almost 100%. In this period, digestion
occurred as aerobic fermentation to carbon dioxide. The
yields of methane and carbon dioxide gases were fifty–fifty
at 11th day. At the end of the 20th day, the digestion reached
the stationary phase. The methane content of the bio-gas
was in the range of 73–79% for the runs, the remainder
 A. Demirbas et al. / International Journal of Hydrogen Energy 31 (2006) 613 – 620 615

Table 1 Table 2
Contents of C, H and O, fixed carbon (FC) and volatile mate- Turkey’s total and recoverable bioenergy potential of animal wastes
rial (VM), and higher heating value (HHV) of agricultural solid in 1997
residues (wt.% of moisture, nitrogen, ash and extractive free basis)
Kind of animal Total Coefficient Total Recoverable
Sample C H O FC VM HHV number of energy energy
of animalsa conversion potential potential
Walnut shell 50.5 5.8 43.7 21.3 78.7 20.3 (thousand (ktoe per (ktoe) (ktoe)
Hazelnut shell 49.8 5.9 44.3 20.6 79.4 19.8 head) thousand
Tea waste 48.4 5.6 44.2 86.0 14.0 17.4 animals)
Almond shell 49.9 6.4 43.7 76.6 23.4 19.1
Corncob 47.5 6.0 46.5 18.8 81.2 19.1 Sheep and goats 75,095 0048 3604 1081
Corn stover 46.5 5.9 46.2 20.4 79.6 18.8 Donkey, horse, 1370 0235 322 97
Cotton stalk 46.8 6.2 47.0 24.0 76.0 19.6 mule & camel
Wheat straw 49.3 5.7 45.0 21.6 78.4 19.3 Poultry 311,500 0003 935 281
Olive husk 50.9 6.3 42.8 19.5 80.5 19.5 Cattle and buffalo 12,121 0245 2970 891
Rice straw 48.8 5.6 45.2 19.9 80.1 19.0 a Source: [42].
Sunflower shell 48.7 6.0 45.3 20.1 79.9 19.5
Sugarcane bagasse 47.3 6.3 46.4 16.9 75.2 18.3
Rapeseed cake 52.9 8.7 38.4 19.1 80.9 24.1
Table 3
Source: [2,9,41]. Trends in agricultural production of Turkey

Type of 1995 1997 1999 2001

agricultural product
being principally carbon dioxide. During a 30-day digestion
period, ∼ 80–85% of the bio-gas was produced in the first Sunflower 900,000 900,000 950,000 930,000
15–18 days. This implies that the digester retention time can Sesame 30,000 28,000 28,100 30,000
be designed to 15–18 days instead of 30 days. Peanut 70,000 82,000 75,000 80,000
Soybean 75,000 40,000 66,000 60,000
Agricultural residues are difficult to degrade bio-
Pistachio 36,000 70,000 40,000 30,000
chemically. Pretreatment of straw by mechanical size reduc-
Almond 37,000 33,000 43,000 42,000
tion, heat treatment and/or chemical treatment with strong Walnut 110,000 115,000 120,000 116,000
acids or bases usually improves the digestibility. Chemical Hazelnut 435,000 410,000 550,000 610,000
pretreatment methods are bicarbonate treatment, alkaline Wheat 18,000,000 18,650,000 18,000,000 18,800,000
peroxide treatment and ammonia treatment. Ammonia treat- Barley 7,700,000 8,200,000 7,700,000 8,100,000
ment has several advantages over the other treatments, such Corn 551,000 576,000 640,000 615,000
as being a source of nitrogen for biodegradation and the Olive 515,000 520,000 535,000 510,000
fact that no separate wastewater streams are generated from Tea (green leaves) 524,000 752,000 720,000 780,000
the pretreatment process. Tobacco 524,000 300,000 420,000 380,000
Sugar beet 11,171,000 18,553,000 17,840,000 18,200,000
Agricultural residues contain low nitrogen and have
Cotton lint 837,000 795,000 860,000 885,000
carbon-to-nitrogen ratios (C/N) around 60–90. The proper
C/N ratio for anaerobic digestion is 25–35 [17]; therefore, Source: [43].
nitrogen needs to be supplemented to enhance the anaer-
obic digestion of agricultural solid residues. Nitrogen can
be added in inorganic form such as ammonia or in organic gives the total and recoverable bio-energy potential of animal
form such as livestock manure, urea, or food wastes. Once wastes in Turkey. The recoverable bio-energy potential of
nitrogen is released from the organic matter, it becomes animal wastes in Turkey was 2.4 million tons oil equivalent
ammonium which is water soluble. Recycling nitrogen in (Mtoe) in 1998.
the digested liquid reduces the amount of nitrogen needed. Turkey, being an agricultural country, has abun-
dant sources of agricultural wastes and crop residues.
Table 3 shows the trends in agricultural production of
3. Turkey’s biomass, agricultural residue and animal Turkey. Among Organization for Economic Co-operation
waste potentials and Development (OECD) countries, Turkey takes the
fourth place from the top in the estimated total energy
Since animal husbandry is highly developed in Turkey, a potential from crop residues with 9.5 Mtoe. Biogas produc-
substantial amount of animal wastes are produced each year. tion potential in Turkey was estimated at 1.5–2 Mtoe [18].
In Turkey, much effort has been put into bio-gas research Not much progress has been made in using this resource,
and development projects since the 1960s. In addition to and there is one waste-to-energy power plant in operation
feasibility studies on bio-gas utilization, many digesters have in Izmit (Turkey) with an installed capacity of 5.4 MW.
been constructed at different places in the country. Table 2 Wet biomass materials can be converted effectively into
616 A. Demirbas et al. / International Journal of Hydrogen Energy 31 (2006) 613 – 620

Table 4 Table 6
Turkey’s annual energy biomass potential in 2001 Turkey’s agricultural residue potential in 2001
Type of biomass Annual potential Energy potential Agricultural residue Annual production Energy potential
(million tons) (Mtoe)b (million tons) (Mtoe)c

Annual crops 55 14.9 Wheat straw 26.4 7.2

Perennial crops 16 4.1 Barley straw 13.5 3.9
Forest residues 18 5.4 Maize stalk 4.2 1.2
Residues from 10 3.0 Cotton hull 2.9 0.9
agro industry Sunflower head 2.7 0.8
Residues from 6 1.8 Sugar beet waste 2.3 0.7
wood industry Hazelnut shell 0.8 0.3
Animal wastes 7 1.5 Oat straw 0.5 0.2
Other 5 1.3 Rye straw 0.4 0.1
Total 117 32.0 Rice husk 0.4 0.1
Fruit peel 0.3 0.1
b Mtoe: million of oil equivalent. Total 54.4 15.5
c Mtoe: million of oil equivalent.
Table 5
Total recoverable bio-energy potential in Turkey
Type of biomass Energy potential trial products such as cotton, flax, sesame and poppy have
(Mtoe) been grown for a long time in Turkey. Soybean is grown in
Dry agricultural residue 4.5 the Mediterranean region. Many kinds of fruits are grown
Wet agricultural residue 0.3 in most parts of the country. Various agricultural residues
Animal waste 2.4 are available in Turkey as sources of biomass energy. The
Forestry and wood processing residue 4.3 disposal of the straw in the fields has been by burning or
Municipal wastes and human excreta 1.3 sometimes by ploughing it back into the soil. Because the
Fuel wood 4.2 higher heating value of straw is about 0.65 that of a high-
Total recoverable bio-energy 17.0 grade coal (its higher heating value is about 28 MJ/kg), the
surplus straw is equivalent to about 16.4 million tons of
coal. Important agricultural residues and their estimated en-
ergy values are given in Table 6. For agricultural residues
the total amount calculated on dry basis has been measured
usable energy with anaerobic microbes. Bacteria break
to be approximately 54.4 million tons. The annual energy
down volatile solids in the manure and convert them into
equivalent is about 15.5 Mtoe.
methane gas (65%) and carbon dioxide (35%). The bio-gas
may be used to heat the digester, to heat farm buildings, or
to produce electricity. The amount of bio-gas produced is
determined by the temperature of the system, the microbes 4. Bio-char from Agricultural Residues
present, the volatile solids content of the feedstock, and
the retention time. In developing countries such as Turkey, Many reports have appeared on the development of acti-
bio-gas digesters typically treat the dung from 15 to 30 vated carbon from cheaper and readily available materials.
cattle from a single family or a small village. The resulting Activated bio-chars are obtained through one of two gen-
energy produced for cooking saves forests and preserves eral methods: (a) either by partial gasification of the primary
the nutrients in the dung. char with steam or carbon dioxide or a mixture of both to
Turkey’s annual biomass potential is given in Table 4. The increase their porosity or (b) by chemical activation of the
amount is approximately 32 Mtoe. Table 5 shows the total precursor with a chemical like zinc chloride or phosphoric
recoverable bio-energy potential of Turkey. This is estimated acid [19].
to be about 17 Mtoe. Turkey for many years has used fuel Agricultural Residues, such as fruit stones, nutshells and
wood, animal wastes, agricultural crop residues, and logging corcobs, are very good precursors for the production of ac-
wastes for direct combustion. These sources are often called tivated carbons [20,21]. In the sense of environmental pro-
non-commercial energy sources, but in Turkey, fuel wood is tection, the utilization of these wastes has awakened the in-
a tradable commodity, since it is the primary fuel of rural terest for development of processes for production of carbon
and urban poor districts. adsorbents based on agricultural wastes. Both the nature of
Turkey is a developing country with rich agricultural po- the precursors and the production process has a strong in-
tential. About 70% of the cultivated land produces grains fluence on the porous structure and adsorption properties of
with wheat ranking first, barley second and corn third. Indus- the resulting activated carbons.
 A. Demirbas et al. / International Journal of Hydrogen Energy 31 (2006) 613 – 620 617

Table 7 Carbon Oxygen

Characterization of pyrolysis products obtained at 723 K with heat-
ing rate of 40 K/s run 100

Element content in char, wt% daf

Property Method Bio-char 80
Carbon, wt% ASTM D 487 84.99
Hydrogen, wt% ASTM D 3177 2.82 60
Oxygen, wt% By difference 12.11
Nitrogen, wt% 0.08
40
Empirical formula From ultimate CH0.397 O0.107 N0.0009
(ash free basis) analysis
Higher heating ASTM D 3286 30.73 20
value, MJ/kg

Source: [23]. 0
450 650 850 1050
Temperature, K
The starting materials used in commercial production of
Fig. 2. Effect of temperature on carbon and oxygen contents in
activated carbons are those with high carbon contents such
bio-char from bio-waste. Particle size: 1.5–2.5 mm.
as wood, lignite, peat, and coal of different ranks or low-
cost and abundantly available agricultural byproducts. Ac-
tive carbons can be manufactured from virtually any car- Hydrogen content in char, wt% daf 6
bonaceous precursor, but the most commonly used materials
wood, coal and coconut shell [22]. 5
The char gasification forms an important part of biomass
gasification. The major thermochemical gasification reac- 4
tions include the following:
Carbon char to methane: 3

C + 2H2 ↔ CH4 (1) 2

Carbon char to oxides: 1

450 650 850 1050
C + O2 → CO2 , and C + CO2 ↔ 2CO. (2) Temperature, K

Carbon char to CO and H2 : Fig. 3. Effect of temperature on hydrogen content in bio-char from
bio-waste. Particle size: 1.5–2.5 mm.
C + CO2 + H2 O ↔ CO + H2 . (3)

The hot combustion products (CO2 and H2 O) are further
reduced by the char. These endothermic reactions generate
synthetic gas (syngas): CO and H2 (Eq. 3), 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 particles are subjected to pyrolysis.
The reactions of CO2 and H2 O with the char to produce
CO and H2 are considerably slower than the drying, pyroly-
sis 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 utiliza-
tion of biomass as a raw material for gasification. The char-
acterization of pyrolysis products from pine bark obtained
at 723 K with heating rate of 40 K/s run (Table 7) was given
in the earlier study [23].
Fig. 2 shows the effect of temperature on carbon and
oxygen contents in bio-char from bio-waste. Fig. 3 shows the
effect of temperature on hydrogen content in the bio-char.
The results of the elemental analysis (Figs. 2 and 3) 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 [24].
Active carbons are carbonaceous materials with highly de-
veloped internal surface area and porosity. Activated carbon
is widely used as an effective adsorbent in many applica-
tions such as air separation and purification, vehicle exhaust
emission control, solvent recovery, and catalyst support be-
cause 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 [25].
The activated carbons were characterized by N2 gas
adsorption, phenol, iodine, and methylene blue adsorp-
tion from solution. These molecules are important for the
characterization of activated carbons.
618 A. Demirbas et al. / International Journal of Hydrogen Energy 31 (2006) 613 – 620
The bio-char can be used in the preparation of active car-
bon when its pore structure and surface area are appropriate.
Chemical additives (AlCl3 , FeCl3 , H3PO4 , NH4 Cl, KOH,
and ZnCl2 ) slightly affect the first step by inhibiting hemi-
celluloses decomposition and accelerating cellulose decom-
position through the dehydration reaction. Phosphoric acid
exhibited the largest influence on the pyrolysis process. At
concentrations higher than 30% H3 PO4 , the two weight loss
steps ascribed to hemicelluloses and cellulose decomposi-
tion overlapped. Bio-char with an alkaline character of the
surface, tar, and gas products are obtained by steam pyrol-
ysis of biomass (almond shells, nut shells, apricot stones,
cherry stones, and grape seeds). The chemical character of
the oxygen containing functional groups on the bio-char sur-
face revealed that they are polyfunctional cationities [26].
Thermal activation under the single-step steam pyrolysis
route, at 975 K, provides better adsorbing carbon with much
developed porosity and enhanced carbon product. Chemical
activation by H3 PO4 at 775 K proved very effective in pro-
ducing high quality activated carbon with well-developed
porosity and high-adsorption capacity for both organic and
inorganic substrates.
4.1. Mechanism of char formation
Lignin gives higher yields of charcoal and tar from wood
although lignin has threefold of methoxyl content than that
of wood [2,27,28]. The formation of char from lignin un-
der 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.
(1974) [29]. 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 pres-
ence of moisture increased the yield of char from the py-
rolysis of wood waste at temperatures between 660 and
730 K, while Stray et al. (1986) [30] found only a slight
effect for water added on the hydrogenolysis of both hard-
wood and softwood lignins at temperatures between 470
and 675 K. The thermolysis reactions of the kraft lignin is
compmainly of breaking the most reactive bonds like the
methyl C–O bond of the methoxyl group and the condensa-
tion reactions to high molecular weight products (char) that
follows.
The degradation of cellulose to a more stable anhydro-
cellulose, which gives higher bio-char yield, is the domi-
nant reaction at temperature < 575 K [31]. At temperatures
> 575 K, cellulose depolymerizes, producing volatiles.
The initial degradation reactions include depolymeriza-
tion, hydrolysis, oxidation, dehydration, and decarboxyla-
tion [32]. The isothermal pyrolysis of cellulose in air and
milder conditions, in the temperature range 623–643 K, was
investigated [33]. Under these conditions, the pyrolysis reac-
tions produced 62–72% aqueous distillate and left 10–18%
charred residue.
The hemicelluloses undergo thermal decomposition very
readily. The hemicelluloses reacted more readily than cel-
lulose during heating. The thermal degradation of hemicel-
luloses begins above 373 K during heating for 48 h; hemi-
celluloses and lignin are depolymerized by steaming at high
temperature for a short time. The metoxyl content of wet
meals decreased at 493 K [34].
The stronger effect of the heating rate on the formation of
bio-char from biomass than from coal may be attributed to
the cellulose content of the biomass [35]. 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 de-
volatilization of the biomass in rapid pyrolysis favors the
formation of char with high porosity and high reactivity
[36]. 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 [37].
5. Bio-oil from agricultural residues
Agricultural residues have been estimated to represent
significant potential for the development of the bio-energy
industry in numerous countries. Biomass is now well rec-
ognized as a potential renewable source of energy. Thermo-
chemical conversion of biomass is one of the most common
and convenient method for conversion into energy. This in-
cludes direct combustion, pyrolysis, gasification, liquefac-
tion, and carbonization. Among the processes of energy pro-
duction from biomass, pyrolysis is the most popular thermal
conversion process.
Pyrolysis can be used for the production of bio-oil if flash
pyrolysis processes are used and are currently at pilot stage
[38]. 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 [39].
Pyrolysis produces energy fuels with high fuel-to-feed ra-
tios, making it the most efficient process for biomass conver-
sion, and the method most capable of competing and even-
tually replacing non-renewable fossil fuel resources [40].
The conversion of biomass to bio-oil can be having an
efficiency of up to ∼ 70% for flash pyrolysis processes.
Table 8 shows the properties of bio-oil from rapeseed cake.
The HHV of rapeseed cake was found as 36.4 MJ/kg. This
bio-oil can be used in engines and turbines in practice. Its
use as feedstock for refineries is also being considered. Some
interesting trends have been obtained, especially with re-
spect to the effect of net heating rate and temperature on the
pyrolysis time.
 A. Demirbas et al. / International Journal of Hydrogen Energy 31 (2006) 613 – 620
Table 8
Properties of bio-oil from rapeseed cake
Property Bio-oil
Density, at 15 vC, kg/m3 993
Elemental composition, wt %
Carbon 73.74
Hydrogen 10.69
Oxygen 10.51
Sulphur 0.11
Nitrogen 4.65
Ash, wt% 0.30
Empirical formula C18.67 H32.48 NO2
(ash free basis)
Heating value, MJ/kg 36.4
Source: [40].
5.1. Energy value of agricultural residues
The energetic content of biomass is usually calculated by
means of empirical formulae for the higher heating value
(HHV) from using ultimate and proximate analyses data.
It is well known ∼ 3 different wood species present simi-
lar heating values as a consequence of comparable carbon
content. However, variations are observed for other types
of biomass and mainly for agricultural residues, given the
rather high ash content. HHVs for agricultural residues were
calculated using the equation given the earlier study [41].
HHV = 3.35(C) + 142.3(H) − 15.6(O), (4)
where C is carbon, H is hydrogen and O is oxygen contents
in agricultural residue fuels.
6. Conclusions
The aim of this study was to evaluate the potential power
production from the pyrolysis for bio-oil and bio-char and
anaerobic digestion for bio-gas of agricultural residues in
Turkey. Agricultural residues are potential renewable en-
ergy resources such as bio-gas from anaerobic digestion,
bio-oil from pyrolysis, and bio-char from carbonization and
slow pyrolysis processes. When the pyrolysis temperature
increased the bio-char yield decreased. The bio-char yield
increased with increasing particle size of the sample. Among
the thermochemical processes for conversion of agricultural
residues into energy, pyrolysis is the most popular thermal
conversion process.
Biomass has a significantly lower heating value than most
coal. This is in part due to the generally higher moisture
content and in part due to the high oxygen content. Biomass
firing, in comparison with coal firing, helps reduce the total
emissions per unit energy produced. A renewable fuel such
619
as waste product or energy crop-derived biomass fuels is a
lowest-cost option for reducing greenhouse gas emissions.
Agricultural residues were converted to methane-rich gas
mixture. Anaerobic biomethane production is an effective
process for conversion of a broad variety of agricultural
residues to methane to substitute natural gas and medium
calorific value gases. Methane generating bacteria and other
microbes help digest dying plants in anaerobic conditions.
Agricultural solid residues represent a potential energy re-
source if they can be properly and biologically converted to
methane.
The activated carbons produced from fruit shells and
stones have high surface areas and highly developed mi-
cropore structure. Adsorptive properties were measured by
using methylene blue, phenol and iodine as adsorbates.
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