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Fuel and Combustion Properties of Bio-wastes

Ayhan Demrbaşa
a
Department of Chemical Engineering Selcuk University Konya, Turkey

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Recovery, Utilization, and Environmental Effects, 27: 5, 451 — 462
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 Energy Sources, 27:451–462, 2005
Copyright © Taylor & Francis Inc.
ISSN: 0090-8312 print/1521-0510 online
DOI: 10.1080/00908310490441863

Fuel and Combustion Properties of Bio-wastes

AYHAN DEMİRBAŞ
Department of Chemical Engineering
Selcuk University
Konya, Turkey

All human and industrial processes produce wastes, that is, normally unused and
undesirable products of a specific process. Biomass absorbs carbon dioxide during
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growth, and emits it during combustion. Utilization of biomass as fuel for power
production offers the advantage of a renewable and CO2 -neutral fuel. Although the
structural, proximate and ultimate analyses results of bio-wastes differ considerably,
some properties of the biomass samples such as the hydrogen content, the sulfur
content and the ignition temperatures changed in a narrow interval. The burning
velocity of pulverized biomass fuels is considerably higher than that of coals. The use
of biomass fuels provides substantial benefits as far as the environment is concerned.

Keywords bio-waste, cofiring, combustion, fuel analysis, fuel properties

Bio-waste fuels potential include wood, short-rotation woody crops, agricultural wastes,
short-rotation herbaceous crops, animal wastes, and a host of other materials. Animal
wastes are another significant potential biomass resource for electricity generation, and,
like crop residues, have many applications, especially in developing countries. Biomass
is the only organic petroleum substitute that is renewable.
Biomass can be converted into liquid, solid and gaseous fuels with the help of
some physical, chemical and biological conversion processes. The conversion of biomass
materials has a precise objective to transform a carbonaceous solid material, which is
originally difficult to handle, bulky and of low energy concentration, into fuels having
physico-chemical characteristics that permit economic storage and transferability through
pumping systems.
The use of bio-waste fuels provides substantial benefits as far as the environment is
concerned. Biomass absorbs carbon dioxide during growth, and emits it during combus-
tion. Therefore, biomass helps the atmospheric carbon dioxide recycling and does not
contribute to the greenhouse effect. Biomass consumes the same amount of CO2 from
the atmosphere during growth as is released during combustion. In addition, overall CO2
emissions can be reduced because biomass is a CO2 -neutral fuel.
Some processes such as pyrolysis, gasification, anaerobic digestion and alcohol pro-
duction have widely been applied to biomass in order to obtain its energy content. Bio-
waste can be directly fired in dedicated boilers. However, cofiring bio-waste and coal
has technical, economical, and environmental advantages over the other options. Cofir-
ing bio-waste with coal, in comparison with single coal firing, helps reduce the total
emissions per unit energy produced.

Received 12 June 2003; accepted 21 July 2003.

Address correspondence to Professor Ayhan Demirbaş, Department of Chemical Engineering,
Selcuk University, Campus, 42031, Konya, Turkey. E-mail: ayhandemirbas@hotmail.com

451
 452 A. Demirbaş

Fuel Properties of Bio-wastes

The limitations were primarily due to relying on bio-waste as the sole source of fuel,
despite the highly variable properties of bio-waste. The high moisture and ash contents
in bio-wste fuels can cause ignition and combustion problems. The melting point of
the dissolved ash is also low, which causes fouling and slagging problems, because of
the lower heating values of bio-waste accompanied by flame stability problems. It is
anticipated that blending biomass with higher quality coal will reduce flame stability
problems, as well as minimize corrosion effects.
Bio-waste 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. How-
ever, it should be noticed that in comparison with solid fossil fuels, bio-waste contains
much less carbon and more oxygen and has a low heating value. Also, chlorine con-
tents of certain bio-wastes, like straw, can exceed the level of coal. In the combustion
applications, bio-waste has been fired directly either alone or along with a primary fuel.
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Chlorine, which is found in certain bio-waste types, such as straw, may affect operation
by corrosion. The high chlorine and alkali content of some bio-waste fuels raise con-
cerns regarding corrosion. The greatest concern focuses on high-temperature corrosion
of super-heater tubes induced by chlorine on the surface.
Bio-waste differs from coal in many important ways, including the organic, inorganic,
energy content, and physical properties. Table 1 shows the physical, chemical and fuel
properties of bio-waste and coal fuels. Relative to coal, bio-waste generally has less
carbon, more oxygen, more silica and potassium, less aluminum and iron, lower heating
value, higher moisture content, and lower density and friability (Table 1). The point on
the burning profile at which the rate of weight loss due to combustion is maximum
called as “peak temperature.” The burning profile peak temperature is usually taken as
a measure of the reactivity of the sample. The peak temperatures for biomass samples
generally vary from 560 K to 575 K.

Table 1
Physical, chemical and fuel properties of
bio-waste and coal fuels

Property Biomass Coal

Fuel density (kg/m3 ) ∼500 ∼1300

Particle size ∼3 mm ∼100 µm
C content (wt% of dry fuel) 42–54 65–85
O content (wt% of dry fuel) 35–45 2–15
S content (wt% of dry fuel) max 0.5 0.5–7.5
SiO2 content (wt% of dry ash) 23–49 40–60
K2 O content (wt% of dry ash) 4–48 2–6
Al2 O3 content (wt% of dry ash) 2.4–9.5 15–25
Fe2 O3 content (wt% of dry ash) 1.5–8.5 8–18
Ignation temperature (K) 418–426 490–595
Peak temperature (K) 560–575 —
Friability Low High
Dry heating value (MJ/kg) 14–21 23–28
Source: Demirbaş (2003).
 Properties of Bio-wastes 453

Table 2
Ultimate analyses of typical fuel samples given in the literature
(wt% of dry fuel with ash)

Fuel sample C H N S O Reference

Hazelnut shell 52.8 5.6 1.4 0.04 42.6 Demirbaş (1997)

Sawdust 46.9 5.2 0.1 0.04 37.8 Abbas et al. (1994)
Corn stover 42.5 5.0 0.8 0.20 42.6 Paul and Buchele (1980)
Poplar 48.4 5.9 0.4 0.01 39.6 Ebeling and Jenkins (1985)
Rice husk 47.8 5.1 0.1 — 38.9 Hartiniati and Youvial (1989)
Cotton gin 42.8 5.4 1.4 0.50 35.0 LePori (1980)
Sugarcane bagasse 44.8 5.4 0.4 0.01 39.6 Ebeling and Jenkins (1985)
Peach pit 53.0 5.9 0.3 0.05 39.1 Ebeling and Jenkins (1985)
Alfafa stalk 45.4 5.8 2.1 0.09 36.5 Tillman (2000)
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Switchgrass 46.7 5.9 0.8 0.19 37.4 Tillman (2000)

Table 3
Ultimate analyses of typical fuel samples (wt% of dry fuel with ash)

Fuel sample C H N S Cl O (diff.)

Coal type 1 81.5 4.0 1.2 3.00 — 3.3

Red oak wood 50.0 6.0 0.3 — — 42.4
Wheat straw 41.8 5.5 0.7 — 1.5 35.5
Olive husk 49.9 6.2 1.6 0.05 0.2 42.0
Beech wood 49.5 6.2 0.4 — — 41.2
Spruce wood 51.9 6.1 0.3 — — 40.9
Corncob 49.0 5.4 0.5 0.20 — 44.5
Tea waste 48.0 5.5 0.5 0.06 0.1 44.0
Walnut shell 53.5 6.6 1.5 0.1 0.1 45.4
Almond shell 47.8 6.0 1.1 0.06 0.1 41.5
Sunflower shell 47.4 5.8 1.4 0.05 0.1 41.3
Sources: Demirbaş (1997); Demirbaş (1998b).

The ultimate analyses of typical fuel samples given in the literature and determined
are shown in Tables 2 and 3, respectively. It is difficult to establish a representative bio-
waste due to large property variations, but two examples are included here for comparison.
The composition variations among bio-waste fuels are larger than among coals, but as a
class, bio-waste has substantially more oxygen and less carbon than coal. Less obviously,
nitrogen, chlorine, and ash vary significantly among bio-waste fuels. These components
are directly related to NOx emissions, corrosion, and ash deposition. Bio-waste generally
has relatively low sulfur compared to coal.
The proximate analyses of selected bio-waste samples given in the literature and
determined as defined by ASTM are shown in Tables 4 and 5, respectively. The inorganic
properties of selected fuel samples are given in Table 10. Inorganic components in coal
vary by rank and geographic region. As a class, coal has more aluminum, iron, and
 454 A. Demirbaş

Table 4
Proximate analyses of selected bio-waste samples given in the literature
(wt% of dry fuel)

Volatile Fixed
Fuel sample Ash matter carbon Reference

Hazelnut shell 1.5 76.3 21.2 Demirbaş (1997)

Sawdust 2.8 82.2 15.0 Abbas et al. (1994)
Corn stover 5.1 84.0 10.9 Paul and Buchele (1980)
Poplar 1.3 — 16.4 Ebeling and Jenkins (1985)
Sugarcane bagasse 11.3 — 15.0 Ebeling and Jenkins (1985)
Peach pit 1.0 — 19.9 Ebeling and Jenkins (1985)
Rice husk 22.6 61.0 16.7 Hartiniati and Youvial (1989)
Alfafa stalk 6.5 76.1 17.4 Tillman (2000)
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Switchgrass 8.9 76.7 14.4 Tillman (2000)

Table 5
Proximate analyses of selected bio-waste samples
(wt% of dry fuel)

Fuel sample Ash Volatile matter Fixed carbon

Beech wood bark 5.7 65.0 29.3

Oak wood 0.5 77.6 21.9
Wheat straw 13.7 66.3 21.4
Olive husk 4.1 77.5 18.4
Beech wood 0.5 82.5 17.0
Spruce wood 1.7 80.2 18.1
Corncob 1.1 87.4 11.5
Tea waste 1.5 85.5 13.0
Walnut shell 2.8 59.3 37.9
Almond shell 3.3 74.0 22.7
Sunflower shell 4.0 76.2 19.8
Colza seed 6.5 78.1 15.4
Pine one 1.0 77.3 21.7
Cotton refuse 6.6 81.0 12.4
Olive refuse 9.2 66.1 24.7
Sources: Demirbaş (1997); Demirbaş (1998b); Haykırı-Açma (2003).

titanium than biomass. Bio-waste has more silica, potassium, and some times calcium
than coal. The wood and woody materials tend to be low in nitrogen and ash content,
while the agricultural materials can have high nitrogen (Tables 2 and 3) and ash contents
(Tables 4 and 5).
Straw may have a high content of chlorine and potassium, elements which are very
undesirable in power plant fuels. Levels of K2 O and Cl were found as 20.0% and 3.6% in
ash, respectively, in wheat straws (Table 6). A pretreatment process to remove potassium
 Properties of Bio-wastes 455

Table 6
Inorganic properties of typical fuel samples (wt% of ash)

Fuel sample Si2 O Al2 O2 TiO2 Fe2 O3 CaO MgO Na2 O K2 O SO3 P2 O5 Cl

Coal type 1 42.0 20.0 1.2 17.0 5.5 2.1 1.4 5.8 5.0 — —
Coal type 2 59.7 19.8 2.1 8.3 2.1 1.8 0.8 2.1 2.0 0.2 —
Coal type 3 51.5 22.6 2.0 14.9 3.3 0.9 1.0 2.0 3.5 0.2 —
Red oak wood 49.0 9.5 — 8.5 17.5 1.1 0.5 9.5 2.6 1.8 0.8
Wheat straw 48.0 3.5 — 0.5 3.7 1.8 14.5 20.0 1.9 3.5 3.6
Walnut shell 23.1 2.4 0.1 1.5 16.6 13.4 1.0 32.8 2.2 6.2 0.1
Almond shell 23.5 2.7 0.1 2.8 10.5 5.2 1.6 48.5 0.8 4.5 0.2
Sunflower shell 29.3 2.9 0.1 2.1 15.8 6.1 1.5 35.6 1.3 4.8 0.2
Olive husk 32.7 8.4 0.3 6.3 14.5 4.2 26.2 4.3 0.6 2.5 0.2
Hazelnut shell 33.7 3.1 0.1 3.8 15.4 7.9 1.3 30.4 1.1 3.2 0.1

Source: Demirbaş (1998b); Demirbaş (2003).

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from straw fuel may be based on pyrolysis followed by char wash. The straw is pyrolyzed
at moderate temperatures at which the potassium is retained in the char. Potassium and
residual chlorine is extracted from the residual char by water (Jensen et al., 2001). Char
and pyrolysis gases may then be used in a conventional boiler without problems due to
the high straw potassium content. To evaluate this pretreatment process, knowledge about
the char wash process is needed. Alkalis, when reacted with sulfates and chlorine, may
harm thermochemical conversion systems, fouling heat exchange surfaces, gas-turbine
blades, and other power system components (Richard et al., 1998).

Combustion Properties of Bio-wastes

In general, combustion models of bio-waste can be classified as macroscopic or micro-
scopic. The macroscopic properties of bio-wastes are given for macroscopic analysis,
such as ultimate analysis, heating value, moisture content, particle size, bulk density, and
ash fusion temperature. Properties for microscopic analysis include thermal, chemical
kinetic, and mineral data. Fuel characteristics such as ultimate analysis, heating value,
moisture content, particle size, bulk density, and ash fusion temperature of bio-wastes
have been reviewed (Bushnell et al., 1989). Fuel properties for the combustion analysis
of bio-wastes can be conveniently grouped into physical, chemical, thermal, and mineral
properties.
Physical property values vary greatly and properties such as density, porosity, and
internal surface area are related to bio-waste fuels, whereas bulk density, particle size,
and shape distribution are related to fuel preparation methods.
Important chemical properties for combustion are the ultimate analysis, proximate
analysis, analysis of pyrolysis products, higher heating value, heat of pyrolysis, heating
value of the volatiles, and heating value of the char.
Thermal property values such as specific heat, thermal conductivity, and emissivity
vary with moisture content, temperature, and degree of thermal degradation by one order
of magnitude. Thermal degradation products of biomass consist of moisture, volatiles,
char and ash. Volatiles are further subdivided into gases such as light hydrocarbons,
carbon monoxide, carbon dioxide, hydrogen and moisture, and tars. The yields depend
on the temperature and heating rate of pyrolysis. Some properties vary with species,
location within the bio-waste, and growth conditions. Other properties depend on the
 456 A. Demirbaş
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Figure 1. Burning profile of sunflower shell. Source: Haykırı-Açma (2003).

combustion environment. Where the properties are highly variable, the likely range of
the property is given (Ragland et al., 1991).

Some Combustion Properties of Selected Biomass Samples

Non-isothermal and isothermal thermogravimetric techniques have commonly been used
to investigate the reactivities of carbonaceous materials (Küçükbayrak, 1993; Şentorun
and Küçükbayrak, 1996; Yaman and Küçükbayrak, 1997). A plot of the rate of weight
loss against temperature while burning a sample under oxidizing atmosphere is referred
to as burning profile (Wagoner and Duzy, 1967). The burning profiles of sunflower shell
and pine cone samples are shown in Figures 1 and 2. The first peak, observed on the
burning profiles of the biomass samples, corresponds to their moisture release. After

Figure 2. Burning profile of pine cone. Source: Haykırı-Açma (2003).

 Properties of Bio-wastes 457

releasing the moisture, some small losses in the mass of the sample occurred due to
desorption of the adsorbed gases. A sudden loss in the mass of the samples started at the
temperatures between 450–500 K, representing the release of some volatiles and their
ignition. In the rapid burning region, the rate of mass loss proceeded so rapidly that
it reached to its maximum value. Rapid loss of mass immediately slowed down at the
temperatures between 600 K and 700 K. After then, burning rate apparently decreased
and consequently some small losses in the mass of the sample continuously went on as
long as temperature was increased up to 1273 K, indicating the slow burning of the partly
carbonized residue. At the end of hold time at 1273 K, samples reached to the constant
weight after given periods (Haykırı-Açma, 2003).
The most important characteristic temperatures of a burning profile are ignition
temperature and peak temperature (Haykırı-Açma et al., 2001). The ignition temperature
corresponds to the point at which the burning profile underwent a sudden rise. The
ignition temperatures of samples were determined from their burning profiles. Table 7
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shows some combustion properties of selected bio-waste samples. As seen in Table 7, the
temperatures were determined as 475 K for sunflower shell, 463 K for colza seed, 475 K
for pine cone, 467 K for cotton refuse and 473 K for olive refuses (Haykırı-Açma, 2003).
In combustion, the point on the burning profile at which the rate of weight loss due to is
maximum known as peak temperature. The burning profile peak temperature is usually
taken as a measure of the reactivity of the sample. These temperatures were found as
573 K for sunflower shell, as 535 K for colza seed, as 565 K for pine cone, as 598 K
for cotton refuses and as 537 K for olive refuse (Table 7). The rate of weight loss at the
burning profile peak temperature is called the maximum combustion rate. The maximum
combustion rates of the sunflower shell, colza seed, pinecone, cotton refuse and olive
refuse was calculated as 5.5, 2.8, 5.2, 3.7, and 3.4 mg/min, respectively (Haykırı-Açma,
2003).
The weight loss percentages of five different biomass samples versus temperature
are illustrated in Figure 3. From Figure 3, the weight losses of the samples increased
sharply above 500 K. The weight loss differences between olive refuse and other samples
started to increase above 620 K. Olive refuse has the lowest volatile matter content and
the highest ash content; in other words, olive refuse has the lowest combustible part.
The weight loss percentages of the sunflower shell, colza seed, pinecone, cotton refuse
and olive refuse at 1273 K were % 95.07, 91.05, 84.80, 86.74, and 78.69, respectively
(Haykırı-Açma, 2003).

Table 7
Some combustion properties of selected bio-waste samples

Ignition Maximum Peak

temperature combustion rate temperature
Sample (K) (mg/min) (K)

Sunflower shell 417 5.50 573

Colza seed 423 2.80 535
Pine cone 463 5.20 565
Cotton refuse 423 3.70 598
Olive refuse 438 3.40 537
Source: Haykırı-Açma (2003).
 458 A. Demirbaş
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Figure 3. Weight loss percentages of different biomass samples versus temperature. Symbols for
the biomass samples: 䊏: Sunflower shell, 䉭: Colza seed, 䊉: Pine cone, 䊊: Cotton refuse, 䉫: Olive
refuse. Source: Haykırı-Açma (2003).

Cofiring of Bio-waste and Coal Blends

Cofiring refers to the combustion of bio-waste and coal for power production. Cofiring
bio-waste with coal, in comparison with single coal firing, helps reduce the total emissions
per unit energy produced. Coal and bio-waste fuels are quite different in composition.
Cofiring bio-waste with coal has the capability to reduce both NOx and SOx levels from
existing pulverized-coal fired power plants. Cofiring may also reduce fuel costs, minimize
waste and reduce soil and water pollution depending upon the chemical composition of
the biomass used. The oldest of all fuels, bio-wastes, and the old original fuel of the
industrial revolution, coal, are key to this move to a new mission. Technical issues that
can lead to doubt about of bio-waste cofiring with coal are being resolved through testing
and experience (Hughes, 2000).
As such, the air pollution emissions accompanying the coal combustion are signif-
icant. Among these pollutants are oxides of sulfur (SOx ) and nitrogen (NOx ), which
lead to acid rain and ozone depletion. In addition, greenhouse gas emissions (CO2 , CH4 ,
etc.) have become a global concern. Numerous methods have been proposed for reducing
gaseous emissions of SO2 , NOx and CO2 from fossil fuel combustion and for reducing
costs associated with these mitigation techniques.
Recent studies have shown that burning bio-waste with fossil fuels has a positive
impact both on the environment and the economics of power generation (Sami et al.,
2001; Hughes and Tillman, 1998; Harding and Adams, 2000). The emissions of SO2 and
NOx were reduced in most cofiring of bio-waste and coal techniques.
Table 8 shows the physical properties and dry heating values of bio-waste and coal
fuels. Bio-waste is much less dense and has significantly higher aspect ratios than coal.
It is also much more difficult to reduce to small sizes. Bio-waste that is cofired with
coal can be as much as 1/4 inch, sometimes more. These physical properties give rise to
several interesting combustion issues (Table 8).
 Properties of Bio-wastes 459

Table 8
Physical properties and dry heating values of
bio-waste and coal fuels

Property Biomass Coal

Fuel density (kg/m3 ) ∼500 ∼1300

Particle size ∼3 mm ∼100 µm
Dry heating value (MJ/kg) 16 25
Source: Demirbas (2003).

Table 9
Ultimate analyses of typical fuel samples
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C H N S Cl Ash O (diff.)

Coal 81.5 4.0 1.2 3.0 — 7.0 3.3

Red oak wood 50.0 6.0 0.3 — — 1.3 42.4
Wheat straw 41.8 5.5 0.7 — 1.5 15.0 35.5
Source: Demirbas (2003).

Table 10
Inorganic properties of typical fuel samples

Si2 O Al2 O2 TiO2 Fe2 O3 CaO MgO Na2 O K2 O SO3 P2 O5 Cl

Coal 42.0 20.0 1.2 17.0 5.5 2.1 1.4 5.8 5.0 — —
Red oak wood 49.0 9.5 — 8.5 17.5 1.1 0.5 9.5 2.6 1.8 0.8
Wheat straw 48.0 3.5 — 0.5 3.7 1.8 14.5 20.0 1.9 3.5 3.6

Source: Demirbaş (2003).

Table 9 shows the ultimate analysis results of typical fuel samples. The elemen-
tal composition differences between coal and bio-waste are indicated by the ultimate
analyses (Table 9). Coal compositions vary with coal rank and geographic region, with
two representative examples of a high-rank eastern coal and a low-rank western coal
indicated here. It is difficult to establish a representative biomass due to large property
variations, but two examples are included here for comparison. The composition vari-
ations among bio-waste fuels are larger than among coals, but as a class, biomass has
substantially more oxygen and less carbon than coal. Less obviously, nitrogen, chlorine,
and ash vary significantly among bio-waste fuels. These components are directly related
to NOx emissions, corrosion, and ash deposition.
Table 10 shows the inorganic properties of typical fuel samples. The inorganic prop-
erties of coal also differ significantly from bio-waste (Table 10). Inorganic components
in coal vary by rank and geographic region. As a class, coal has more aluminum, iron,
and titanium than bio-waste. Table 11 shows the proximate analysis results of typical
fuel samples. Bio-wastes have more silica, potassium, and some times calcium than coal.
A proximate analysis (Table 11), as defined by ASTM, is the determination by prescribed
methods of moisture, volatile matter, fixed carbon (by difference) and ash.
 460 A. Demirbaş

Table 11
Proximate analyses of typical fuel samples

Moisture Ash Volatile matter Fixed carbon

(% of fuel) (% of dry fuel) (% of dry fuel) (% of dry fuel)

Coal 4.8 ± 2.6 8.3 ± 1.5 2.4 ± 5.9 43.6 ± 3.8

Oak wood 6.5 ± 0.8 0.5 ± 0.1 78.6 ± 3.8 21.5 ± 2.1
Wheat straw 7.3 ± 1. 12.7 ± 3.6 64.0 ± 5.1 23.4 ± 2.5
Source: Demirbaş (2003).

Pyrolysis of Bio-wastes
Pyrolysis is defined as the thermal destruction of organic materials in the absence of
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oxygen. Pyrolysis is the basic thermochemical process for converting bio-waste into a
more useful fuel (Demirbaş, 1998a). Bio-waste is heated in the absence of oxygen,
or partially combusted in a limited oxygen supply, to produce a hydrocarbon rich gas
mixture, an oil-like liquid and a carbon rich solid residue.
In pyrolysis process, bio-waste is converted into liquid (bio-oil or bio-crude), charcoal
and non-condensable gasses, acetic acid, acetone, and methanol by heating the bio-waste
to about 750 K in the absence of air. The process can be adjusted to favor charcoal,
pyrolytic oil, gas, or methanol production with a 95.5% fuel-to-feed efficiency. Pyrolysis
can be used for the production of bio-oil if flash pyrolysis processes are used and are
currently at 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
(Demirbaş, 2000a).
As with coal, pyrolysis is a relatively slow chemical reaction occurring at low tem-
peratures. The reaction mechanisms of biomass pyrolysis are complex but can be defined
in five stages for wood (Demirbaş, 2000b):
1. Moisture and some volatile loss.
2. Breakdown of hemicellulose; emission of CO and CO2 .
3. Exothermic reaction causing the woody bio-waste temperature to rise from 525
to 625 K; emission of methane, hydrogen and ethane.
4. External energy is now required to continue the process.
5. Complete decomposition occurs.

Co-pyrolysis
Co-pyrolysis of carbonaceous material are complex functions of the experimental condi-
tions under which the pyrolysis process proceeds. The most important factors that affect
the yield and composition of the volatile fraction liberated are: coal rank or biomass type,
maceral composition, particle size, temperature (i.e., temperature-time history), heating
rate, atmosphere, pressure and reactor configuration. Co-pyrolysis of carbonaceous ma-
terial divided into a hydrogen-rich volatile fraction, consisting of gases, vapors, and
tar-components, and a carbon-rich solid residue. The pyrolysis process consists of a very
complex set of reactions involving the formation of radicals. The radicals are very reactive
 Properties of Bio-wastes 461

and can undergo secondary reactions like cracking and carbon deposition, both inside
and outside the particle. Stabilization of a radical, primarily via hydrogen addition, leads
to a volatile component. The evolution of tar is controlled by mass transport in which the
tar molecules evaporate into the light gas species and are carried out the particle at rates
proportional to their vapor pressure and the volume of light gas. High pressure reduces
the volume of light gases and hence reduces the yield of heavy molecules with low
vapor pressure. Polymerization and condensation reactions, occurring via recombination
of both volatile and non-volatile radical components, result in the formation of the solid
char particle. High pyrolysis heating rates produced chars with large macroporosites,
more open pore structures, and larger macropore surface areas. Tar formation increases
with increasing heating rate. The co-pyrolysis of the lignite sample and the bio-waste
sample that resulted was the addition of lignite gave a slight synergistic effect in terms of
increasing the oil yield from the hazelnut shell and also reduced the molecular weights
of the resultant oil considerably.
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Conclusion
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.
It was observed that the investigated bio-waste materials showed different combustion
characteristics. The structural, proximate and ultimate analyses results of bio-wastes differ
considerably.
Pyrolysis produces energy fuels with high fuel-to-feed ratios, making it the most
efficient process for bio-waste conversion, and the method most capable of competing
and eventually replacing non-renewable fossil fuel resources. The conversion of bio-waste
to crude oil can have an efficiency of up to 70% for flash pyrolysis processes. The so-
called biocrude can be used in engines and turbines. Its use as feedstock for refineries
is also being considered. Some interesting trends have been obtained, especially with
respect to the effect of net heating rate and temperature on the pyrolysis time. The
reported literature results indicate a decrease in final pyrolysis time as the net heating
rate or temperature is increased (Rezzoug and Caport, 2003).

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