Energy Conversion and Management 50 (2009) 3147–3157

Contents lists available at ScienceDirect

Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

Main routes for the thermo-conversion of biomass into fuels and chemicals.
Part 1: Pyrolysis systems
Mustafa Balat *, Mehmet Balat, Elif Kırtay, Havva Balat
Sila Science and Energy Company, University Mah, Trabzon, Turkey

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

Article history: Since the energy crises of the 1970s, many countries have become interest in biomass as a fuel source to
Received 16 January 2009 expand the development of domestic and renewable energy sources and reduce the environmental
Accepted 21 August 2009 impacts of energy production. Biomass is used to meet a variety of energy needs, including generating
Available online 11 September 2009
electricity, heating homes, fueling vehicles and providing process heat for industrial facilities. The meth-
ods available for energy production from biomass can be divided into two main categories: thermo-
Keywords: chemical and biological conversion routes. There are several thermo-chemical routes for biomass-based
Biomass
energy production, such as direct combustion, liquefaction, pyrolysis, supercritical water extraction, gas-
Pyrolysis
Thermal degradation
ification, air–steam gasification and so on. The pyrolysis is thermal degradation of biomass by heat in the
Pyrolysis liquids absence of oxygen, which results in the production of charcoal (solid), bio-oil (liquid), and fuel gas prod-
Applications ucts. Pyrolysis liquid is referred to in the literature by terms such as pyrolysis oil, bio-oil, bio-crude oil,
Upgrading bio-fuel oil, wood liquid, wood oil, liquid smoke, wood distillates, pyroligneous tar, and pyroligneous
acid. Bio-oil can be used as a fuel in boilers, diesel engines or gas turbines for heat and electricity
generation.
Crown Copyright Ó 2009 Published by Elsevier Ltd. All rights reserved.

1. Introduction
Growing worldwide concerns regarding environmental conse-
quences of heavy dependence on fossil fuels, particularly climate
change, are likely to constrain excessive use of fossil fuels in the
near future [1]. About 98% of carbon emissions result from fossil
fuel combustion [2]. Biomass is a renewable resource, whose utili-
zation has received great attention due to environmental consider-
ations and the increasing demands of energy worldwide [3].
Biomass is clean for it has negligible content of sulfur, nitrogen
and ash, which give lower emissions of sulfur dioxide (SO2), nitro-
gen oxides (NOx) and soot than conventional fossil fuels. Zero net
emission of carbon dioxide (CO2) can be achieved because CO2 re-
leased from biomass will be recycled into the plants by photosyn-
thesis quantitatively [4].
Since the energy crises of the 1970s, many countries have be-
come interest in biomass as a fuel source to expand the develop-
ment of domestic and renewable energy sources and reduce the
environmental impacts of energy production. Biomass has great
potential as a renewable energy source, both for the richer coun-
tries and for the developing world [5]. Various studies on global
bioenergy potential use a margin spanning from a few hundred
to more than 1000 EJ (exajoule) – depending on the assumptions
* Corresponding author. Tel.: +90 462 871 3025; fax: +90 462 871 3110.
E-mail address: mustafabalat@hotmail.com (M. Balat).
they make on agriculture, yields, population, etc. [6]. Biomass ac-
counts for 35% of primary energy consumption in developing coun-
tries, raising the world total to 14% of primary energy consumption
[7,8].
Biomass resources include wood and wood wastes, agricultural
crops and their waste byproducts, municipal solid waste, animal
wastes, waste from food processing, and aquatic plants and algae.
The average majority of biomass energy is produced from wood
and wood wastes (64%), followed by municipal solid waste (24%),
agricultural waste (5%) and landfill gases (5%) [9–11]. Many differ-
ent types of biomass can be grown for the express purpose of en-
ergy production. Crops that have been used for energy include:
sugar cane, corn, sugar beets, grains, elephant grass, kelp (sea-
weed) and many others [12]. There are two main factors which
determine whether a crop is suitable for energy use. Good energy
crops have a very high yield of dry material per unit of land (dry
tons/ha) [13,14]. A high yield reduces land requirements and low-
ers the cost of producing energy from biomass [14].
The remainder of this paper is organized as follows. Section 2
provides detailed information on the chemical structure and basic
components of biomass. Main routes for thermo-chemical conver-
sion of biomass are summarized in Section 3. Section 4 presents a
detailed review of biomass pyrolysis and pyrolysis technologies.
Section 5 discusses general characteristics of pyrolysis liquid prod-
ucts and their primary applications. Finally, Section 6 draws the
main conclusions of this paper.

0196-8904/$ - see front matter Crown Copyright Ó 2009 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2009.08.014
3148 M. Balat et al. / Energy Conversion and Management 50 (2009) 3147–3157

2. Chemical structure and basic components of biomass

The chemical structure and basic organic components in bio-

mass are extremely important in the development of processes
for producing derived fuels and chemicals. Biomass can generally
be defined as any hydrocarbon material which mainly consists of
carbon, hydrogen, oxygen and nitrogen [15]. A typical analysis of
dry wood yields carbon (52%), hydrogen (6.3%), oxygen (40.5%)
and nitrogen (0.4%). The proximate analysis of wood and bark
shows components as follow: volatile matter (80.0%, 74.7%), fixed
carbon (19.4%, 24.0%) and ash (0.65%, 1.3%), respectively [16,17].
The components of biomass include cellulose, hemicelluloses,
lignin, extractives, lipids, proteins, simple sugars, starches, water,
hydrocarbons, ash, and other compounds. The basic structure of all
woody biomass consists of three basic polymers: cellulose
(C6H10O5)x, hemicelluloses such as xylan (C5H8O4)m, and lignin
[C9H10O3 (OCH3)0.9–1.7]n in trunk, foliage, and bark. The proportion
of these wood constituents varies between species, and there are
distinct differences between hardwoods and softwoods. Hardwoods
or deciduous woods have a higher proportion of cellulose, hemicel-
luloses, and extractives than softwoods, but softwoods have a higher
proportion of lignin. In general, hardwoods contain about 43–47%
cellulose, 16–24% lignin, 25–35% hemicelluloses, and 2–8% extrac-
tives while softwoods contain about 40–44% cellulose, 25–31% lig- Fig. 2. Schematic illustration of sugar units of hemicelluloses.

nin, 25–29% hemicelluloses, and 1–5% extractives [18].
Cellulose, which is an abundant component in plants and wood,
comes in various forms and a large fraction comes from domestic
and industrial wastes [19]. Cellulose fibers provide wood’s strength
and comprise 40–50 wt.% of dry wood [20]. Some lignocellulosic
materials can have more cellulose than wood. Cellulose is a
remarkable pure organic polymer, consisting solely of units of
anhydroglocose held together in a giant straight chain molecule
[21]. Cellulose is a homopolysaccharide composed of b-D-glucopyr-
anose units linked together by (1?4)–glycosidic bonds (Fig 1). The
basic repeating unit of the cellulose polymer consists of two glu-
cose anhydride units, called a cellobiose unit [20]. Cellulose must
be hydrolyzed to glucose before fermentation to bio-ethanol. By
forming intramolecular and intermolecular hydrogen bonds be-
tween OH groups within the same cellulose chain and the sur-
rounding cellulose chains, the chains tend to be arranged parallel
and form a crystalline supermolecular structure. Then, bundles of
linear cellulose chains (in the longitudinal direction) form a micro-
fibril which is oriented in the cell wall structure [21,22]. Cellulose
is insoluble in most solvents and has a low accessibility to acid and
enzymatic hydrolysis [22–24].
A second major wood chemical constituent is hemicellulose,
which is also known as polyose. A variety of hemicelluloses usually
account for 25–35% of the mass of dry wood, 28% in softwoods, and
35% in hardwoods [25]. Hemicellulose is a mixture of various poly-
merized monosaccharides such as glucose, mannose, galactose, xy-
lose, arabinose, 4-O-methyl glucuronic acid and galacturonic acid
residues [20]. Hemicelluloses (arabinoglycuronoxylan and galac-
toglucomammans) are related to plant gums in composition, and
occur in much shorter molecule chains than cellulose [26]. The
hemicelluloses, which are present in deciduous woods chiefly as
pentosans and in coniferous woods almost entirely as hexosanes,
undergo thermal decomposition very readily [27]. Hemicelluloses
are derived mainly from chains of pentose sugars, and act as the
cement material holding together the cellulose micells and fiber
[26]. Formulas of the sugar component of hemicelluloses are listed
in Fig 2 [21]. Hemicelluloses exhibit lower molecular weights than
cellulose. The number of repeating saccharide monomers is only
150, compared to the number in cellulose (5000–10,000) [20].
Lignin is an aromatic polymer synthesised from phenylpropa-
noid precursors [28]. The basic chemical phenylpropane units of
lignin (primarily syringyl, guaiacyl and p-hydroxy phenol) as
shown in Fig 3 are bonded together by a set of linkages to form a
very complex matrix [22]. This matrix comprises a variety of func-
tional groups, such as hydroxyl, methoxyl and carbonyl, which im-
part a high polarity to the lignin macromolecule [29]. Softwood
and hardwood lignins belong to the first and second category,
respectively. Softwoods generally contain more lignin than hard-
woods [28]. Lignin contents on a dry basis in both softwoods and
hardwoods generally range from 20% to 40% by weight and from
10% to 40% by weight in various herbaceous species, such as ba-
gasse, corncobs, peanut shells, rice hulls and straws [15].
3. Thermo-chemical routes for biomass-based energy
production
Biomass is used to meet a variety of energy needs, including
generating electricity, heating homes, fueling vehicles and provid-
ing process heat for industrial facilities [17]. The methods available
for energy production from biomass can be divided into two main

Fig. 1. Chemical structure of cellulose.

 M. Balat et al. / Energy Conversion and Management 50 (2009) 3147–3157
Fig. 3. Schematic illustration of building units of lignin.
categories: thermo-chemical and biological conversion routes.
There are several thermo-chemical conversion routes of biomass,
such as pyrolysis, gasification, and combustion. Fig. 4 shows the
biomass thermo-chemical conversion processes. The products of
the thermo-chemical processes are divided into a volatile fraction
consisting of gases, vapors and tar components and a carbon rich
solid residue [15]. These different processing techniques tend to
emphasize different mechanism subsets within the large group of
potential chemical mechanisms by which biomass is converted to
primary products and thereafter further converted by varying de-
grees to final products [30].
4. Pyrolysis of biomass
Pyrolysis dates back to at least ancient Egyptian times, when tar
for caulking boats and certain embalming agents were made by
pyrolysis. In the 1980s, researchers found that the pyrolysis liquid
yield could be increased using fast pyrolysis where a biomass feed-
stock is heated at a rapid rate and the vapors produced are also
condensed rapidly [20]. Although pyrolysis is still under develop-
ing stage but during current energy scenario, pyrolysis has re-
Fig. 4. Biomass thermo-chemical conversion processes.
3149
ceived special attention as it can convert biomass directly into
solid, liquid and gaseous products by thermal decomposition of
biomass in absence of oxygen [31]. The liquid and gas products
can be used in engine and turbine for power generation.
4.1. Principles of biomass pyrolysis
Pyrolysis is the thermal decomposition of materials in the ab-
sence of oxygen or when significantly less oxygen is present than
required for complete combustion. Pyrolysis of biomass is a prom-
ising route for the production of solid (char), liquid (tar), and gas-
eous products as possible alternate sources of energy. The main
pyrolysis reaction is:
Biomass ! Charcoal þ Volatile matter ð1Þ
The goal of pyrolysis is the optimization of high-value fuel prod-
ucts from biomass by thermal and catalytic means [32]. Pyrolysis
produces energy fuels with high fuel-to-feed ratios, making it the
most efficient process for biomass conversion and the method
most capable of competing with and eventually replacing nonre-
newable fossil fuel resources [33]. The process can be adjusted to
favor charcoal, pyrolytic oil, gas, or methanol production with a
95.5% fuel-to-feed efficiency [34]. These products are of interest
as they are possible alternate sources of energy. Fig. 5 shows the
fractionation of biomass pyrolysis products.
The most interesting temperature range for the production of
the pyrolysis products is between 625 and 775 K. The charcoal
yield decreases as the temperature increases. Production of liquid
products is maximum at temperatures between 625 and 725 K
[9,35–37]. Temperature is the most important factor for the prod-
uct distribution of pyrolysis. Table 1 shows pyrolysis reactions at
different temperatures. At higher temperatures, the rather large
molecules present in the liquid and residual solid are broken down
to produce smaller molecules which enrich the gaseous fraction
[38]. Low temperatures and high residence times favor the produc-
tion of char, while the higher temperatures and short residence
times lead to high liquid production. Table 2 shows the results of
pyrolysis of solid waste and analysis of the gas content [39]. Yield
of products resulting from biomass pyrolysis can be maximized as
follows: (1) charcoal—a low temperature, low heating rate process,
3150 M. Balat et al. / Energy Conversion and Management 50 (2009) 3147–3157

Fig. 5. Fractionation of biomass pyrolysis products.

Table 1 The production of bio-liquids and other products (char and gas)
Pyrolysis reactions at different temperatures. by pyrolysis of biomass species has been extensively investigated
Condition Processes Products in the past. Some of these biomass species include beech wood
[44], bagasse [45,46], woody biomass [47,48], straws [49,50], seed-
Below 575 K Free radical Formation of carbonyl and
formation, carboxyl, evolution of CO and cakes [51,52], and municipal solid waste (MSW) [53,54].
elimination of water CO2 and mainly a charred
and residue 4.2. Pyrolysis processes for fuels and chemicals
depolymerization
Between 575 and Breaking of Mixture of levoglucosan,
725 K glycosidic linkages of anhydrides and
Pyrolysis process has been used for commercial production of a
polysaccharide by oligosaccharides in the form wide range of fuels and chemicals from biomass feedstocks.
substitution of a tar fraction Depending on the operating conditions, the pyrolysis process can
Above 725 K Dehydration, Formation of carbonyl be divided into three subclasses: conventional pyrolysis, fast pyro-
rearrangement and compounds such as
lysis and flash pyrolysis.
fission of sugar units acetaldehyde, glyoxal and
acrolein
Above 775 K A mixture of all A mixture of all above 4.2.1. Conventional pyrolysis
above processes products Conventional pyrolysis is defined as the pyrolysis, which occurs
Condensation Unsaturated A highly reactive char residue
under a slow heating rate. This condition permits the production of
products condense containing trapped free
and cleave to the radicals
solid, liquid, and gaseous pyrolysis products in significant portions
char [55–57]. Slow pyrolysis of biomass is associated with high charcoal
continent, but the fast pyrolysis is associated with tar, at low tem-
(2) liquid products—a low temperature, high heating rate, short gas perature (675–775 K) [58], and/or gas, at high temperature [35]. At
residence time process, and (3) fuel gas—a high temperature, low present, the preferred technology is fast or flash pyrolysis at high
heating rate, long gas residence time process. temperatures with very short residence times [59]. The ranges of
Catalytic pyrolysis is considered to be the most attractive way of the main operating parameters for pyrolysis processes are given
reducing the problems of the liquid pyrolysis products (polymeriza- in Table 3 [60].
tion, high viscosity, corrosivity) and in order to help in their handling
and treatment. It takes place in the absence of air in moderate tem- 4.2.2. Fast pyrolysis
peratures (775 K) and leads mainly to pyrolysis liquids, which can be Fast pyrolysis (more accurately defined as thermolysis) is a pro-
used as fuels or as a source of valuable chemicals. For the maximiza- cess in which a material, such as biomass, is rapidly heated to high
tion of the yield of the process (60–80 wt.% liquid yield) high heating temperatures in the absence of air (specifically oxygen) [61]. Fig. 6
rates and short residence times are required [40]. shows biomass fast pyrolysis system [62]. If the aim is the produc-
Pyrolysis lies at the heart of all thermo-chemical fuel conver- tion of mainly liquid and/or gaseous products a fast pyrolysis is
sion processes and is assumed to become an avenue to petro- recommended. In recent years fast pyrolysis process for biomass
leum-type products from biomass resources. Pyrolytic oil may has attracted a great deal of attention for maximizing liquid yields
be used directly as a liquid fuel, added to petroleum refinery [63]. Fast pyrolysis processes produce 60–75 wt.% of liquid bio-oil,
feedstocks, or catalytically upgraded to transport grade fuels 15–25 wt.% of solid char, and 10–20 wt.% of noncondensable gases,
[41,42]. In all thermo-chemical conversion processes, pyrolysis depending on the feedstock used [20]. Table 4 indicates the prod-
plays a key role in the reaction kinetics and hence in reactor de- uct distribution obtained from different processes of pyrolysis pro-
sign and determining product distribution, composition, and cess [64]. If the purpose were to maximize the yield of liquid
properties [43]. products resulting from biomass pyrolysis, a low temperature, high
heating rate, short gas residence time process would be required. If

Table 2
Results of pyrolysis of solid waste and analysis of the gas content.

Temperature (K) Char (wt.%) Liquid (wt.%) Gas (wt.%) CO2 (vol.%) O2 (vol.%) HC (vol.%) CO (vol.%) Others (vol.%)
507 97.0 0.0 3.0 22.1 0.6 32.5 13.8 31.0
584 76.2 15.9 7.9 18.9 3.9 32.9 18.2 26.1
655 62.9 25.4 11.7 34.5 0.4 21.4 10.6 33.1
683 49.0 35.0 16.0 45.1 4.6 20.9 9.4 19.7
 M. Balat et al. / Energy Conversion and Management 50 (2009) 3147–3157 3151

Table 3 fuels [67]. The liquid bio-oil produced by fast pyrolysis has the con-
Range of the main operating parameters for pyrolysis processes. siderable advantage of being storable and transportable, as well as
Pyrolysis Solid residence Heating Particle Temperature the potential to supply a number of valuable chemicals that offer
technology time (s) rate (K/s) size (mm) (K) the attraction of much higher added value than fuels. Advantages
Conventional 450–550 0.1–1 5–50 550–950 of using fast pyrolysis liquids as fuel are listed in Table 5 [68]. Fast
Fast 0.5–10 10–200 <1 850–1250 pyrolysis technology can have relatively low investment costs and
Flash <0.5 >1000 <0.2 1050–1300 high energy efficiencies compared to other processes, especially on
a small scale. Fast pyrolysis in combination with an engine pro-
duces up to 15 MWe, in the highest efficiency, lowest capital and
electricity costs as compared to other thermal conversion pro-
cesses [69].

4.2.3. Flash pyrolysis

Fig. 6. Biomass fast pyrolysis system.
the purpose were to maximize the yield of fuel gas resulting from
biomass pyrolysis, a high temperature, low heating rate, long gas
residence time process would be preferred [17,23,60,65].
Rapid heating and rapid quenching produced the intermediate
pyrolysis liquid products, which condense before further reactions
break down higher-molecular-weight species into gaseous prod-
ucts. High reaction rates minimize char formation. Under some
conditions, no char is formed [12]. At higher fast pyrolysis temper-
atures, the major product is gas. Many researchers have attempted
to exploit the complex degradation mechanisms by conducting
pyrolysis in unusual environments [20].
There are four essential features of a fast pyrolysis process
[20,58]: (1) very high heating and heat transfer rates are used,
which usually requires a finely ground biomass feed, (2) a carefully
controlled pyrolysis reaction temperature is used, often in the 700–
775 K range, (3) short vapor residence times are used (typically
<2 s), and (4) pyrolysis vapors and aerosols are rapidly cooled to
give bio-oil. Commercial operation is currently only been achieved
from a transport or circulating fluid-bed system, and only for food
and flavouring products. Fluid-beds have also been studied exten-
sively, are an ideal R&D tool and have been scaled up to a plot plant
size with plans in hand for demonstration processes in several
locations within the European Union [66].
Fast pyrolysis is now commercially successful for production of
chemicals and is being actively developed for producing liquid
The flash pyrolysis of biomass is a promising route with regard
to the production of solid, liquid (bio-oil or bio-crude-oil) and gas-
eous products as possible alternate energy sources. Pyrolysis can
be used for the production of bio-oil if flash pyrolysis processes
are used and are currently at pilot stage [70]. The conversion of
biomass to crude oil can be having an efficiency of up to 70% for
flash pyrolysis processes [17,60,71]. So-called bio-crude can be
used in engines and turbines. Its use as feedstock for refineries is
also being considered. Some problems in the conversion process
and use of oil need to be overcome; these include poor thermal sta-
bility and corrosivity of the oil. Upgrading by lowering the oxygen
content and removing alkalis by means of hydrogenation and cat-
alytic cracking of the oil may be required for certain applications
[17,59].
Major problem of the present reactors for flash pyrolysis are the
quality and the stability of the produced oil, strongly affected by
char/ash content of bio-oil. Besides the known problems concern-
ing solid particles in the bio-oil, char fines will catalyze repolymer-
ization reactions inside the oil resulting in a higher viscosity. Char
can be removed after treatment of condensed products like filter-
ing the oil, which is disadvantageous because alkali, concentrated
in the char, will dissolve in the bio-oil due to because high acidity
of oil (pH = 2–3). Another option to remove the char is hot gas
cleaning of the oil vapor [69]. The flash pyrolysis of biomass inher-
ently results in the production of pyrolytic water, which is one of
the major drawbacks of the bio-oil produced. Nevertheless, the
Table 5
Advantages of using fast pyrolysis liquids as fuel. Source: Ref. [68].
– Pyrolysis liquid is the lowest cost liquid bio-fuel, and its CO2-balance is
clearly positive
– Possibility of utilization in small-scale power generation systems as well
as use in large power stations (co-firing)
– Possibility to decouple solid bio-fuel handling from utilization (reduced
capital and operation costs in utilization)
– Storability and transportability of liquid fuels
– High-energy density compared to atmospheric biomass gasification fuel
gases
– Intermittent operation feasible
– If light fuel oil is replaced, middle distillates are released to be used for
transportation
– Potential of using pyrolysis liquid in existing power plants

Table 4
Typical product yields (dry wood basis) obtained by different processes of pyrolysis of wood. Source: Ref. [64].

Process Conditions Product yield (%)

Liquid Char Gas
Fast Moderate temperature, around 775 K, short hot vapor residence time 1 s 75 12 13
Intermediate Moderate temperature, around 775 K, moderate hot vapor residence time 10–20 s 50 20 30
Slow (carbonization) Low temperature, around 675 K, very long solids residence time 30 35 35
Gasification High temperature, around 1075 K, long vapor residence time 5 10 85
3152 M. Balat et al. / Energy Conversion and Management 50 (2009) 3147–3157
presence of water has both positive and negative effects on the bio-
oil properties [72].
5. Biomass-based pyrolysis liquids
Pyrolysis liquid is referred to in the literature by terms such as
pyrolysis oil, bio-oil, bio-crude oil, bio-fuel oil, wood liquid, wood
oil, liquid smoke, wood distillates, pyroligneous tar, pyroligneous
acid [58]. The liquid products from biomass pyrolysis are dark
brown viscous oils. Combustion tests [68,73–75] have demon-
strated that these liquid products could be burnt efficiently in stan-
dard or in slightly modified burners. The chemistry of pyrolysis oils
is qualitatively well known, although detailed quantitative compo-
sitions are usually not available. The main components are organic
acids, aldehydes, ketones, phenols, anhydrosugars such as levoglu-
cosan, pyrolytic lignin (comprising guaiacyl- and syringylbased
fragments of the original lignin polymer) and substantial quanti-
ties of water, typically 25% [76]. Chemical composition of fast pyro-
lysis liquid is given in Table 6 [77]. The flexibility of the biomass
pyrolysis unit allows experimentation with various feedstocks
and catalyst types. In Fig. 7 the product results using three differ-
ent reactor types are compared with the ones from a fixed bed
reactor [78].
Liquid fraction of pyrolysis products consists of two phases: an
aqueous phase containing a wide variety of organo–oxygen com-
pounds of low molecular weight and a non-aqueous phase contain-
ing insoluble organics (mainly aromatics) of high molecular
weight. This phase is called as bio-oil or tar. Ratios of acetic acid,
Table 6
Chemical composition of fast pyrolysis liquid. Source: Ref. [77].
Major components Mass %
Water 20–30
Lignin fragments: insoluble pyrolytic lignin 15–30
Aldehydes: formaldehyde, acetaldehyde, 10–20
hydroxacetaldehyde, glyoxal, methylglyoxal
Carboxylic acids: formic acid, propionic, butyric, 10–15
pentanoic, hexanoic, glycolic (hydroxyacetic)
Carbohydrates: cellobiosan, a-D-levoglucosan, 5–10
oligosaccharides, 1.6-anhydroglucofuranose
Phenols: phenol, cresols, guaiacols, syringols 2–5
Furfurals 1–4
Alcohols: methanol, ethanol 2–5
Ketones: acetol (1-hydroxy-2-propanone), cyclo 1–5
pentanone
Fig. 7. Components of bio-oil produced from biomass fast pyrolysis.
methanol, and acetone of aqueous phase were higher than those
of non-aqueous phase [27].
5.1. Bio-oil
Bio-oil is a liquid mixture of oxygenated compounds containing
carbonyl, carboxyl and phenolic functional groups. One of the main
drawbacks of the bio-oil is that the composition of the pyrolytic
oils is very similar to that of the original biomass and is very differ-
ent from petroleum-derived fuels and chemicals [79]. Bio-oil con-
sists of [61]: water, 20–25%; water insoluble pyrolytic lignin, 25–
30%; organic acids, 5–12%; non-polar hydrocarbons, 5–10%; anhyd-
rosugars, 5–10%; and other oxygenated compounds, 10–25%. The
water content of bio-oils contributes to their low energy density,
lowers the flame temperature of the oils, leads to ignition difficul-
ties, and, when preheating the oil, can lead to premature evapora-
tion of the oil and resultant injection difficulties. In contrast to
petroleum oils, which are non-polar and in which water is insolu-
ble, bio-oils are highly polar and can readily absorb over 35% water
[32].
Bio-oil is a renewable liquid fuel produced by the fast pyrolysis
of biomass, with a lower heating value of about 16 MJ/kg compared
with 43 MJ/kg for diesel [80]. Typical properties of wood pyrolysis
bio-oil and of No 2 Diesel fuel are shown in Table 7 [81]. Bio-oil is
expensive as a transport fuel, but it presents the advantage of easy
handling, transport, storage, combustion, retrofitting and flexibility
in production and marketing [82].
The kinematic viscosity of bio-oil varies from as low as 11 mm2/
s to as high as 115 mm2/s at 313 K depending on nature of the
feedstock, temperature of pyrolysis process, thermal degradation
degree and catalytic cracking, the water content of the bio-oil,
the amount of light ends that have collected, and the pyrolysis pro-
cess used [83]. The density of the oxygenated bio-oils is much
higher i.e. 1150–1300 kg/m3, than petroleum derived hydrocarbon
oils. The bio-oils having relatively higher densities typically have
lower water contents. Wood derived pyrolysis liquid has density
of typically 1200 kg/m3 for a water content of 25 wt.% at 293 K
[84]. Bio-oil is moderately acidic, having a pH in the range of
2.5–3.0 (similar to the acidity of vinegar) [85]. For this reason the
oils are corrosive to common construction materials such as carbon
steel and aluminum and can affect some sealing materials [86].
5.2. Bio-oil applications
The main applications of bio-oil have been reviewed by Bridg-
water [86]. The main bio-oil applications are summarized in
Fig. 8. Chemical groups can be obtained from biomass bio-oil by
fast pyrolysis are acids, aldehydes, alcohols, sugars, esters, ketones,
phenolics, oxygenates, hydrocarbons, and steroids. Chemicals from
biomass bio-oil by fast pyrolysis are given in Table 8 [87]. The bio-
Table 7
Typical properties of wood pyrolysis bio-oil and of No 2. Diesel fuel.
Bio-oil No 2. Diesel fuel
Moisture content 15–30 n.a.
pH 2.5 1
Specific gravity 1.20 0.847
Elemental analysis C 55–58 86
(wt.%)
H 5.5–7.0 11.1
O 35–40 0
N 0–0.2 1
S n.d. 0.8
HHV (MJ/kg) as produces 16–19 44.7
Viscosity 40–100 cp (315 K, 25% <2.39 (325 K)
water)
 M. Balat et al. / Energy Conversion and Management 50 (2009) 3147–3157 3153

high viscosity, coking, and corrosive ness are probably the most
challenging and have so far limited the range of bio-oil applications
[86]. Some problems related to using pyrolysis liquids as a fuel in
boilers, engines and turbines are summarized in Table 9, adapted
from Oasmaa et al. [89].
The heating value of bio-oil is much lower than that for fossil
fuel, because of the large number of oxygenated compounds and
a significant portion of water. Nevertheless, flame combustion tests
showed that fast pyrolysis oils could replace heavy and light fuel
oils in industrial boiler applications [20,58,90–92]. The bio-oil
composition depends on the feedstock as well as on the process
type and conditions. Zheng and co-workers [93] studied fast pyro-
lysis of cotton stalk at temperatures between 755 K and 805 K in a
fluidized bed and obtained the maximum yield of bio-oil (55%) at
temperature 785 K. The results of the study showed that the bio-
oil obtained under these conditions can be directly used as a fuel
Fig. 8. Applications for bio-oil. Source: Ref. [86].
oil for combustion in a boiler or a furnace without any upgrading.
For pyrolysis liquids to be used or to be acceptable for boiler appli-
cations, the following minimum requirements must be achieved
[89]: (1) preheating to 345–355 K immediately prior to combus-
Table 8
tion, to reduce the viscosity to 2–4 cSt, and no recirculation of
Chemicals from biomass bio-oil by fast pyrolysis.
heated product back to the storage tank (because this can cause
Chemical Minimum, wt.% Maximum, wt.% polymerization), (2) startup and shutdown on conventional fuel,
Levoglucosan 2.9 30.5 to avoid deposition and coking of nozzles, and (3) ensuring a suffi-
Hydroxyacetaldehyde 2.5 17.5 ciently low concentration of solids (<0.1 wt.%).
Acetic acid 6.5 17.0
Bio-oil has been successfully fired in a diesel test engine, where
Formic acid 1.0 9.0
Acetaldehyde 0.5 8.5 it behaves very similar to diesel in terms of engine parameters and
Furfuryl alcohol 0.7 5.5 emissions [94]. The most important changes involve the fuel pump,
1-hydroxy-2-propanone 1.5 5.3 the linings, and the injection system. Slight modifications of both
Catechol 0.5 5.0
the bio-oil and the diesel engine can render bio-oils an acceptable
Methanol 1.2 4.5
Methyl glyoxal 0.6 4.0
substitute for diesel fuel in stationary engines [20]. At least 400 h
Ethanol 0.5 3.5 operation has been achieved on a 250 kWe specially modified
Cellobiosan 0.4 3.3 dual-fuel engine and limited experience has been gained on a mod-
1,6-anhydroglucofuranose 0.7 3.2 ified 2.5 MWe industrial gas turbine [58]. Long term demonstra-
Furfural 1.5 3.0
tion of bio-oil in diesel engines and gas turbine has not been
Fructose 0.7 2.9
Glyoxal 0.6 2.8 possible due to lack of large quantities bio-oil [95]. For engine
Formaldehyde 0.4 2.4 applications, the minimum property specifications required are
4-methyl-2,6-dimetoxyphenol 0.5 2.3 as follows [89]: (1) solids content of <0.1 wt.%, (2) viscosity in
Phenol 0.2 2.1 the range of 10–20 cSt, (3) maximum physical and chemical prop-
Propionic acid 0.3 2.0
Acetone 0.4 2.0
erty variation. For turbine applications, the minimum requirement
Methylcyclopentene-ol-one 0.3 1.9 is that the particle size must be <10 lm. For turbine applications,
Methyl formate 0.2 1.9 the minimum property specifications required is a solids content
Hydroquinone 0.3 1.9 of <0.1 wt.% [89]. It is necessary to conduct large-scale and long-
Acetol 0.2 1.7
duration tests on boilers, engines and gas turbines before accepting
2-cyclopenten-1-one 0.3 1.5
Syringaldehyde 0.1 1.5 pyrolysis liquids as commercial fuels. These tests will require a
1-hydroxy-2-butanone 0.3 1.3 substantial supply of liquids with specified properties established
3-ethylphenol 0.2 1.3 by the producers and users [66].
Guaiacol 0.2 1.1

5.3. Upgrading of bio-oil to transportation fuels

Bio-oil is known to be viscous, acidic, and thermally unstable

oils were composed of a range of cyclopentanone, methoxyphenol,
acetic acid, methanol, acetone, furfural, phenol, formic acid, levo-
glucosan, guaiocol and their alkylated phenol derivatives. Acetic
acid is formed in the thermal decomposition of all three main com-
ponents of biomass. In the pyrolysis reactions of biomass: water is
formed by dehydration; acetic acid comes from the elimination of
acetyl groups originally linked to the xylose unit; furfural is formed
by dehydration of the xylose unit; formic acid proceeds from car-
boxylic groups of uronic acid; and methanol arises from methoxyl
groups of uronic acid [11,32,88].
Bio-oil can be used as a fuel in boilers, diesel engines or gas tur-
bines for heat and electricity generation. The properties of bio-oil
result in several significant problems during its use as a fuel in
standard equipment such as boilers, engines, and gas turbines con-
structed for combustion petroleum-derived fuels. Poor volatility,
and contains high proportion of oxygenated compounds. The chal-
lenge is to produce bio-oil of high quality that can replace or sup-
plement the current fossil fuel usage. One way to ensure this is to
improve the quality of bio-oil produced either at source prior to
full production or by upgrading the product [96,97]. Bio-oils can
be upgraded into a liquid transportation fuel by three different
routes [98]: (1) hydrodeoxygenation with typical hydrotreating
catalysts (typically sulfided CoMo or NiMo supported on alumina),
(2) zeolite upgrading, or (3) forming emulsions with the diesel fuel.
Alternatively, bio-oils and chars can be converted into H2 or syn-
gas by steam-reforming. The intended purposes of using catalysts
are [96]: (1) enhance the cracking reactions of the heavy molecules
in pyrolysis products resulting in the production of lighter and less
viscous bio-oil, (2) reduce the formation of carboxylic acids making
bio-oil less corrosive, and (3) enhance the formation of more valu-
3154 M. Balat et al. / Energy Conversion and Management 50 (2009) 3147–3157

Table 9
Issues related to using pyrolysis liquids as a fuel in boilers, engines and turbines. Source: Ref. [89].

Property Specification to be met Current value Problem (s) Possible solution (s)
by present
technology
Variation Max. 10% >50% Changes in feed and process Quality control system
parameters
Water <27 wt.% 18–40 Inhomogeneity, phase Feedstock drying increase (<323 K) of condensation
separation (>30 wt.% water) temperature
Total solidsa <0.01 wt.% 60.5 wt.% Wear of injectors, increased Homogeneous particle size distribution of the feed, hot
liquids instability, high CO vapor filter, three cyclones on reactor exit, liquids
emissions filtration/centrifugation
Inorganicsb <0.01 wt.% <0.1 wt.% Feedstock choice, hot vapor filter, three cyclones on
reactor exit, liquids filtration/ centrifugation
Homogeneity Single-phase Variation Uneven liquid quality Feedstock moisture <12 wt.% liquid water content
<27 wt.%
Stability Max.100% increase in viscosity in aging 50–150% Changes in liquid properties Alcohol addition [methanol preferred, but ethanol/2-
test (24 h 353 K, viscosity during storage and use propanol safer to use]
measurement at 313 K)
Flash point Dependent on country >313 K Safety regulations for Adjusting the liquid condensation temperature
transportation
c
pH FDS 2–3 Corrosion of fuel lines All pipework, vessels, and gaskets must be acid resistant
LHV FDSc 16–19 MJ/kg 50% lower than fuel oil, does Increase pump pressure to injectors, increase diameter of
not auto-ignite at start-up fuel lines, dual fueling (%), combustion chamber
modification
Viscosity FDSc >50 cSt at 293 K Too high for most fuel Preheat liquids to reduce viscosity, add cosolvent
injectors (alcohol), use of emulsions
c
Lubricity FDS Not determined Buildup of lacquer on the Improvement in lubricity/flow properties, additives
injection needle and fuel
pump plunger
a
Includes char, ash, and sand.
b
Includes ash and sand.
c
FDS cannot be influenced or specified.

able products like hydrocarbons that can increase the heating va- [98,99]. The zeolite ZSM-5 catalysts have a strong acidity, high
lue of the bio-oil. activities and shape selectivities which convert the oxygenated
Hydrodeoxygenation of bio-oils involves treating bio-oils at
moderate temperatures (575–875 K) with high-pressure H2 in
the presence of heterogeneous catalysts to remove the oxygen Table 10
Comparison of different catalysts for zeolite upgrading of wood-derived fast pyrolysis
and form saturated C–C bonds. The energy content of the fuel is
bio-oils. Source: Ref. [98].
significantly increased, and the stability of the fuel increases dur-
ing hydrodeoxygenation [98,99]. Most hydrodeoxygenation of Silica-alumina
bio-oils has focused on sulfided CoMo/Al2O3 and NiMo/Al2O3 cata- HZSM- (SiO2–Al2O3 ratio SAPO- SAPO- MgAPO-
lysts, which are used for hydrotreating industrial feedstocks. These 5 0.14) 5 11 36
catalysts have shown to be active in the upgrading of bio-oils. Gut- Catalyst properties
ierrez et al. [100] studied hydrodeoxygenation of guaiacol in a Pore size (nm) 0.54 3.15 0.80 0.56 0.75
BET surface area 329 321 330 205 196
batch system using commercial alumina supported CoMo and
(m2/g)
NiMo catalysts under a total pressure of 8.0 MPa in the tempera- Acid area (cm2/ 224.9 125.5 76.0 15.5
ture range from 475 to 625 K. The results of the study showed that g)a
the conversion of guaiacol and the amount of hydrodeoxygenation Product yields (wt.% of feed)
products were higher on the NiMo than on the CoMo catalyst at the Organic liquid 33.6 24.9 22.2 19.9 16.3
lowest temperatures tested (475–575 K). Thus, the NiMo catalyst product
was more active than the CoMo in this temperature range. Gas 6.1 10.3 12.2 10.1
Coke + charb 20.5– 40 30.0 25.5 38.7
Catalytic steam reforming of bio-oil at 1025–1125 K over a Ni-
30.2
based catalyst is a two-step process that includes the shift reaction Tarc 0–4.1 9.5 11.9 10.1
[101]: Aqueous fraction 25.0 24.2 26.3 23.1
Composition organic liquid product (wt.%)
Bio-oil þ H2 O ! CO þ H2 ð2Þ Total 86.7 45.6 51.0 56.8 51.6
CO þ H2 O ! CO2 þ H2 ð3Þ hydrocarbons
d
Aromatics 85.9 2.1 27.5 29.1 26.7
The overall stoichiometry gives a maximum yield of 0.172 g H2/ Aliphatics 18.6 43.5 23.5 24.4 23.4
g bio-oil (11.2% based on wood) [101].
Reaction temperature 643 K.
a
CH1:9 O0:7 þ 1:26H2 O ! CO2 þ 2:21H2 ð4Þ Acid area is measured by ammonia TPD and represents Bronsted plus Lewis acid
sites.
b
Bio-oils can also be upgraded using zeolite catalysts to reduce Coke is defined as organics that could only be removed from catalyst by cal-
cinations. Char is defined as organics deposited in the reactor due to thermal
the oxygen content and improve the thermal stability. Tempera-
decomposition, and these compounds were not on the catalyst.
tures of 625–775 K and atmospheric pressure are used for zeolite c
Tar are the heavy oils deposited on the catalysts that were only removed with a
upgrading. The advantages of using a zeolite catalyst are that no hexane/acetone wash.
d
H2 is required, atmospheric processing reduces operating cost, Toluenes and xylenes are the most common aromatics for HZSM-5, whereas
and the temperatures are similar to those for bio-oil production benzene is the most common aromatic for SAPO and MgAPO catalysts.
 M. Balat et al. / Energy Conversion and Management 50 (2009) 3147–3157
oil to a hydrocarbon mixture in the C1 to C10 range [102]. How-
ever, because the majority of research on the upgrading process
using zeolite catalysts has been performed in secondary upgrad-
ing units, the process has several disadvantages [103]. To over-
come these problems, catalysts with a larger pore size than
that of ZSM-5 have attracted much attention for their potential
for reducing the catalyst deactivation rate and giving a higher or-
ganic yield [97]. Table 10 shows the results for zeolite upgrading
of wood-derived fast-pyrolysis bio-oils with different catalysts. It
is expected that zeolite related materials with bigger pores
would allow larger pyrolysis products, particularly lignin-derived
compounds, to enter, reformulate and exit the catalyst matrix
with less chances of coke deposition and blocking of pores
[97]. Compared with catalytic hydrogenation, though catalytic
cracking proceeds at atmospheric pressure, disadvantages are,
however, low yield (14–22.5%), easy coking (26.1–38.5%) and
thus shorter life of catalyst [104].
The strategy is based on producing hydrogen from biomass
pyrolysis using a co-product strategy to reduce the cost of hydro-
gen and concluded that only this strategy could compete with
the cost of the commercial hydrocarbon-based technologies
[105]. This strategy will demonstrate how hydrogen and bio-fuel
are economically feasible and can foster the development of rural
areas when practiced on a larger scale. The process of biomass to
activated carbon is an alternative route to hydrogen with a valu-
able co-product that is practiced commercially [106].
6. Conclusions
Biomass is a source of gaseous, liquid, charcoal fuels and chem-
ical raw materials. The methods available for energy production
from biomass can be divided into two main categories: thermo-
chemical and biological conversion routes. The technology of ther-
mo-chemical conversion is one of them, which includes three sub-
categories: pyrolysis, gasification, and direct liquefaction. The
products of the thermo-chemical processes are divided into a vol-
atile fraction consisting of gases, vapors and tar components and a
carbon rich solid residue. These different processing techniques
tend to emphasize different mechanism subsets within the large
group of potential chemical mechanisms by which biomass is con-
verted to primary products and thereafter further converted by
varying degrees to final products.
In all thermo-chemical conversion processes, pyrolysis plays a
key role in the reaction kinetics, reactor design and determining
product distribution, composition, and properties. The biomass
pyrolysis is attractive because solid biomass and wastes can be
readily converted into liquid products. These liquids, as crude
bio-oil or slurry of charcoal of water or oil, have advantages in
transport, storage, combustion, retrofitting and flexibility in pro-
duction and marketing.
For maximization of the yield of liquid products resulting
from biomass pyrolysis, a low temperature, high heating rate,
and short gas residence time process would be required.
For a high char production, a low temperature, low heating rate
process would be chosen. For maximization of the yield of fuel
gas resulting from pyrolysis, a high temperature, low heating
rate, and long gas residence time process would be preferred.
Charcoal can be made from small, chipped pieces of wood to
large logs. It generally takes five tons of wood to produce one
ton of charcoal. Charcoal has many advantages in industrial use
over other heating agents due to a low sulfur content, a high car-
bon to ash ratio, relatively few and unreactive inorganic impuri-
ties, a specific pore structure with a large surface area, little
smoke discharge.
3155
Acknowledgements
The authors would like to thank Professor Ayhan Demirbasß for
his helpful comments on this paper.
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