Energy Conversion and Management 50 (2009) 2239–2249

Contents lists available at ScienceDirect

Energy Conversion and Management

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

Biofuels securing the planet’s future energy needs

Ayhan Demirbas *
Sila Science, University Mah, Mekan Sok No: 24, Trabzon, Turkey

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

Article history: The biofuels include bioethanol, biobutanol, biodiesel, vegetable oils, biomethanol, pyrolysis oils, biogas,
Received 24 September 2008 and biohydrogen. There are two global biomass based liquid transportation fuels that might replace gas-
Accepted 16 May 2009 oline and diesel fuel. These are bioethanol and biodiesel. World production of biofuel was about 68 billion
Available online 16 June 2009
L in 2007. The primary feedstocks of bioethanol are sugarcane and corn. Bioethanol is a gasoline additive/
substitute. Bioethanol is by far the most widely used biofuel for transportation worldwide. About 60% of
Keywords: global bioethanol production comes from sugarcane and 40% from other crops. Biodiesel refers to a die-
Biofuel
sel-equivalent mono alkyl ester based oxygenated fuel. Biodiesel production using inedible vegetable oil,
Bioethanol
Biodiesel
waste oil and grease has become more attractive recently. The economic performance of a biodiesel plant
Economic and environmental impacts can be determined once certain factors are identified, such as plant capacity, process technology, raw
material cost and chemical costs. The central policy of biofuel concerns job creation, greater efficiency
in the general business environment, and protection of the environment.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction Today bioethanol is the most used non-fossil alternative engine

Liquid biofuels such as bioethanol and biodiesel may offer a
promising alternative [1–3]. Because of increase in petroleum
prices especially after petrol crisis in 1973 and then gulf war in
1991, geographically reduced availability of petroleum and more
stringent governmental regulations on exhaust emissions,
researchers have studied on alternative fuels and alternative solu-
tion methods [4–6]. The use of biofuels decreases the external en-
ergy dependence, promotion of regional engineering, increased
R&D, decrease in impact of electricity production and transforma-
tion; increases the level of services for the rural population, crea-
tion of employment, etc. [7–9].
The term biofuel or biorenewable fuel (refuel) is referred to as
solid, liquid or gaseous fuels that are predominantly produced
from biomass [10–17]. Liquid biofuels being considered world over
fall into the following categories: (a) bioalcohols [18–21], (b) veg-
etable oils [22–24] and biodiesels [25–27]; and (c) biocrude and
synthetic oils [28–37]. Biofuels are important because they replace
petroleum fuels. It is expected that the demand for biofuels will
rise in the future. Biofuels are substitute fuel sources to petroleum;
however, some still include a small amount of petroleum in the
mixture [38,39]. Biofuels are generally considered as offering many
priorities, including sustainability, reduction of greenhouse gas
emissions, regional development, social structure and agriculture,
security of supply [40–43].
* Tel.: +90 462 230 7831; fax: +90 462 248 8508.
E-mail address: ayhandemirbas@hotmail.com
fuel in the world. The choice of raw material depends on local con-
ditions. Bioethanol is good alternate fuel that is produced almost
entirely from food crops. The primary feedstock of this fuel is corn.
An important advantage of crop-based ethanol is its greenhouse
benefits [18,28]. Due to the increasing concern on environmental
protection, numerous researches on the usage of biodiesel are car-
ried out in recent years. Biodiesel has become more attractive re-
cently because of its environmental benefits [44–56].
The biggest difference between biofuels and petroleum feed-
stocks is oxygen content [57]. Biofuels are non-polluting, locally
available, accessible, sustainable and reliable fuel obtained from
renewable sources [58]. Sustainability of renewable energy sys-
tems must support both human and ecosystem health over the
long term, goals on tolerable emissions should look well into the
future [54,59,60]. Electricity generation from biofuels has been
found to be a promising method in the nearest future [29,61].
The future of biomass electricity generation lies in biomass inte-
grated gasification/gas turbine technology, which offers high-en-
ergy conversion efficiencies [8].
Liquid biofuels for transportation have recently attracted huge
attention in different countries all over the world because of its
renewability, sustainability, common availability, regional devel-
opment, rural manufacturing jobs, reduction of greenhouse gas
emissions, and its biodegradability [39,54]. Biofuels offer signifi-
cant benefits for energy security. Table 1 shows the availability
of modern transportation fuels. Policy drivers for biorenewable li-
quid biofuels have attracted in rural development and economic
opportunities for developing countries [62]. The European Union
is on the third rank of biofuel production world wide, behind Brazil

0196-8904/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2009.05.010
2240 A. Demirbas / Energy Conversion and Management 50 (2009) 2239–2249
Table 1
Availability of modern transportation fuels.
Fuel type Availability
Current Future
Gasoline Excellent Moderate–poor
Bioethanol Moderate Excellent
Biodiesel Moderate Excellent
Compressed natural gas (CNG) Excellent Moderate
Hydrogen for fuel cells Poor Excellent
and the United States. In Europe, Germany is the largest, and
France the second largest producer of biofuels [63].
2. Bioenergy from biomass
Modern bioenergy is commercial energy production from bio-
mass for industry, power generation, or transport fuels. Biomass
is the most common form of carbonaceous materials, widely used
in the third world. Bioenergy is an inclusive term for all forms of
biomass and biofuels. Green energy is an alternate term for renew-
able energy that the energy generated from sources which are con-
sidered environmentally friendly [39]. Green power refers to
electricity supplied from more readily renewable energy sources
than traditional electrical power sources. Green power products
have become widespread in many electricity markets worldwide
which can be derived from renewable energy sources [64]. Using
of green energy sources like hydro, biomass, geothermal, and wind
energy in electricity production reduces CO2, SO2 and NOx emis-
sions. Market research indicates that there is a large potential mar-
ket for green energy in Europe in general. Green power marketing
has emerged in more than a dozen countries around the world
[65].
Biomass gasification technologies provide the opportunity to
convert renewable biomass materials into clean fuel gases or syn-
thesis gases. These gaseous products can be burned to generate
heat or electricity, or they can potentially be used in the synthesis
of liquid transportation fuels, hydrogen, or chemicals. Gasification
offers a combination of flexibility, efficiency, and environmental
acceptability that is essential in meeting future energy require-
ments. Biomass fuelled renewable distributed generation technol-
ogies in rural electrification provide no-regret options with
significant CO2 emission mitigation potential when operated under
net-metering scheme [61]. The future of biomass electricity gener-
ation lies in biomass integrated gasification/gas turbine technol-
ogy, which offers high-energy conversion efficiencies [66].
Cogeneration, in and of itself, is an example of pollution preven-
tion. Cogenerators, by using excess heat, may enhance the effi-
ciency of total energy use by up to 80% or more from the typical
33–38% efficiency of electricity-only generation. A typical cogene-
ration system consists of an engine, steam turbine, or combustion
turbine that drives an electrical generator. Fig. 1 shows a gas tur-
bine topping cycle cogeneration system. Fig. 1 is a diagram of a
Exhaust
STEAM
EXHAUST
GAS
BOILER Condensate
Return PLANT
BIOFUEL
GAS GENERATOR ELECTRICITY
AIR TURBINE
Fig. 1. A representative cogeneration: a gas turbine topping cycle.
gas turbine of the type used for cogeneration power plants with
sizes about 500 kW to 50 MW. These turbines are similar to jet en-
gines used in aircraft. In this size range, gas turbines are more effi-
cient than any other type of fossil fuel fired power plants, reaching
electrical efficiencies of up to 45% and with the addition of waste
heat recovery (cogeneration), efficiencies of over 80%. When used
for cogeneration, the hot exhaust gases from the gas turbine are
passed through a heat exchanger where the heat is transferred to
water in pipes producing steam. A waste heat exchanger recovers
waste heat from the engine and/or exhaust gas to produce hot
water or steam. Cogeneration produces a given amount of electric
power and process heat with 15–35% less fuel than it takes to pro-
duce the electricity and process heat separately [67].
Fig. 2 illustrates comparison between energy inputs to separate
and cogenerative generation systems. Traditional coal, oil or natu-
ral gas fired thermal generating stations convert only about one-
third of the initial energy contained within the fuel into useful
electricity. The remainder of the energy is discarded as heat with-
out serving any useful purpose. From 10% to 35% of primary energy
use is wasted as conversion losses in power plants. Cogeneration
can increase the efficiency of a fossil fuel from an average of 40%
to over 80%. Fig. 2 illustrates the increase in efficiency. This in-
crease in efficiency can translate into lower costs and fewer emis-
sions of pollutants than the conventional alternative of generating
electricity and heat separately [67].
2.1. Biomass conversion processes
Biomass, mainly in the form of wood, is the oldest form of en-
ergy used by humans. Wood has been used in direct combustions
as an important energy source in developing countries [68]. Bio-
mass is used to meet a variety of energy needs, including generat-
ing electricity, heating homes, fueling vehicles, and providing
process heat for industrial facilities [69]. If briquettes from ligno-
cellulosic materials are to be used efficiently and rationally as fuel,
they must be characterized to determine such technological
parameters as their reactivity, moisture content, density, ashes,
volatile matter, and heat value, along with their major component
elements [70].
Biomass can be used as a solid fuel, or converted into liquid or
gaseous forms for the production of electric power, heat, chemi-
cals, or gaseous and liquid fuels. Thermochemical conversion pro-
cesses include three sub-categories: pyrolysis, gasification, and
liquefaction. Fig. 3 shows the biomass thermal conversion pro-
cesses. A variety of biomass resources can be used to convert to li-
quid, solid and gaseous fuels with the help of some physical,
thermochemical, biochemical and biological conversion processes.
Main biomass conversion processes are direct liquefaction, indirect
liquefaction, physical extraction, thermochemical conversion, bio-
chemical conversion, and electrochemical conversion. In liquefac-
tion, pyrolysis and gasification processes, high temperatures are
used to break down the wastes containing mostly hydrocarbons
with no (in liquefaction and pyrolysis) or less oxygen than inciner-
ation (in gasification).
2.1.1. Mechanisms of thermochemical biomass conversion processes
Thermal degradation of cellulose proceeds through two types of
reaction: a gradual degradation, decomposition, and charring on
heating at lower temperatures; and a rapid volatilization accompa-
nied by the formation of levoglucosan on pyrolysis at higher tem-
peratures. The hemicelluloses reacted more readily than cellulose
during heating. Dehydration reactions around 473 K are primarily
responsible for thermal degradation of lignin. Between 423 K and
573 K, cleavage of a- and b-aryl–alkyl-ether linkages occurs.
Around 573 K, aliphatic side chains start splitting off from the aro-
matic ring [71,72].
 A. Demirbas / Energy Conversion and Management 50 (2009) 2239–2249 2241

I. SEPARATE HEAT AND POWER SYSTEM

Output (15 units

Fuel Input Electricity Generator electricity)
(50 units) (efficiency 30%)

Fuel Input Overall usable energy: 55 units

(100 units)
Fuel Input Boiler
(50 units) (efficiency 80%) Output (40
units heat)

II. COGENERATION SYSTEM

Fuel Input Heat Transmission Output (56 units heat)

(100 units) (efficiency 80%)

Electricity Generator Output (30 units Overall cogeneration

(efficiency 30%) electricity) energy: 86 units

Fig. 2. Comparison between energy inputs to separate heat and power system and cogeneration system.

Biomass Thermal Conversion Processes
Excess air Partial air No air
Combustion Gasification Pyrolysis and
Hydrothermal liquefaction
Heat Fuel gases and syngas Liquids
Fig. 3. Biomass thermal conversion processes.
The gasification of biomass is a thermal treatment which results
in a high proportion of gaseous products and small quantities of
char (solid product) and ash. Complete gasification of biomass in-
volves several sequential and parallel reactions. Most of these reac-
tions are endothermic and must be balanced by partial combustion
of gas or an external heat source [73].
Liquefaction is a low-temperature, high-pressure thermochem-
ical process using a catalyst. In the liquefaction process, the micel-
lar-like broken-down fragments produced by hydrolysis are
degraded to smaller compounds by dehydration, dehydrogenation,
deoxygenation, and decarboxylation. These compounds once pro-
duced, rearrange through condensation, cyclization, and polymer-
ization, leading to new compounds. Thermal depolymerization
and decomposition of biomass, cellulose, hemicelluloses, and prod-
ucts were formed as well as a solid residue of charcoal [74].
Hydrogen liquefaction of sawdust in tetralin was performed in
an autoclave at below conditions: temperature range from 473 K
to 623 K; initial cool hydrogen pressure range from 4 to 10 MPa;
reaction time range from 10 to 100 min. The effect of variables
on the process of sawdust liquefaction was examined. The exis-
tence of H2 or tetralin improves both the conversion of sawdust
and the oil yield. The maximum oil yield from the liquefaction
was 67.1%. Temperature has a remarkable effect than initial cool
hydrogen pressure and reaction time on the process of sawdust liq-
uefaction [75].
The thermal liquefaction process by using glycerol occurs in
two steps, the faster first step in which the lignin is made available
by breaking of the lignin–carbohydrate bonds. The released lignin
is then dissolved in the organic phase. The slower second step
may be indicative of a much more complex process. Glycerol re-
duces the surface tension of the solvent at high temperature, thus
promoting the penetration of the alkali into the particles and the
diffusion of the breakdown products of lignin from the wood into
the solvent, assuring a uniform distribution of the reagents within
the wood [31].
2.2. Pyrolysis of biomass
Pyrolysis is the thermal decomposition of organic matter occur-
ring in the absence of oxygen or when significantly less oxygen is
present than required for complete combustion. Pyrolysis is the ba-
sic thermochemical process for converting biomass to a more use-
ful fuel. A study of pyrolysis of olive cake at the temperature range
from 673 K to 973 K has been carried out for production of bio-oil.
As the pyrolysis temperature was increased, the percentage mass
of char decreased whilst gas product increased [33].
Apricot stone (Prunus armeniaca L.) was pyrolyzed in a directly
heated fixed-bed reactor under nitrogen atmosphere. Pyrolysis
runs were performed using reactor temperatures between 673 K
and 973 K with heating rate of about 300 K/min. As the pyrolysis
temperature was increased, the percentage mass of char decreased
while gas product increased. The bio-oil obtained at 825 K, at
which the liquid product yield was maximum, was analyzed.
Chemical fractionation of bio-oil showed that only low quantities
of hydrocarbons were present, while oxygenated and polar frac-
tions dominated [76].
A comparative study of the thermochemical behavior of cotton-
seed cake in static, nitrogen and steam atmospheres has been car-
ried out. Pyrolysis under water vapor gave a rise in the yield as
opposed to pyrolysis under static and nitrogen atmospheres [77].
Oxidative pyrolysis of Cuban pine sawdust was investigated
using an autothermal fluidized bed reactor. The results indicated
that the liquid and char products obtained may be a potentially
valuable source of chemical feedstocks [78]. A continuous bench
2242 A. Demirbas / Energy Conversion and Management 50 (2009) 2239–2249
fluidized bed pyrolysis has been designed and is currently under
testing. The model and experimental results indicated that two
zones exist inside of the fluidization column. The dense bed where
the exothermic and endothermic reactions are active, and the free-
board zone where the temperature of the pyrolysis product de-
creases continuously; the bed temperature increases with an
increase in the air factor [79].
Bio-oils derived from biomass have been increasingly attracting
attention as alternative sources of fuels and chemicals. Fixed-bed
slow pyrolysis experiments have been conducted on a sample of
hazelnut bagasse to determine particularly the effects of pyrolysis
temperature, heating rate, particle size and sweep gas flow rate on
the pyrolysis product yields. Under the various pyrolysis condi-
tions applied in the experimental studies, the obtained char, liquid,
and gas yields ranged between 26 and 35 wt.%, 23 and 34.40 wt.%,
and 25 and 32 wt.%, respectively. The maximum bio-oil yield of
34.40% was obtained at the final pyrolysis temperature of 773 K,
with a heating rate of 10 K/min, particle size range of 0.425–
0.600 mm and a 150 cm3/min of sweep gas flow rate [80]. The
empirical formula of bio-oil that has a heating value of 34.57 MJ/
kg was established as CH1.45O0.33N0.127 [81]. The bio-oils were com-
posed of a range of cyclopentanone, methoxyphenol, acetic acid,
methanol, acetone, furfural, phenol, formic acid, levoglucosan, gua-
iocol and their alkylated phenol derivatives. The structural compo-
nents of the biomass samples mainly affect pyrolytic degradation
products [82].
3. Chemicals and fuels from biomass
Biomass provides a potential source of added value chemicals,
such as reducing sugars, furfural, ethanol and other products, by
using biochemical or chemical and thermochemical processes.
The gas phase of pyrolitic degradation products contains mostly
carbon monoxide and carbon dioxide, and minor proportions of
hydrogen, methane, ethane, and propane. The liquid fraction con-
sists mainly of water, with small proportions of acetaldehyde, pro-
pion aldehyde, butyraldehyde, acrolein, croton-aldehyde, furan,
acetone, butanedione, and methanol. The sugars from the hemicel-
luloses are also fermented to bioethanol [32].
More recently, many attempts have been made to utilize bio-
mass, such as wood, hazelnut shell, agricultural waste residues,
waste paper and wheat straw, tea waste, and olive husk
[5,19,40,83–85]. The main biomass sources in use for energy pro-
duction range from forest residues, agricultural residues, pulp
and paper operation residues, animal waste, and landfill gas to en-
ergy crops [14,86–90].
Olive cake is a very promising material for the production of
bio-oil. The highest bio-oil yields from the olive cakes were 31.0%
at 700 K, 36.0% at 700 K and 41.0% at 700 K obtained from 10 K/s,
20 K/s and 40 K/s heating rate runs, respectively [34,22]. Olive cake
is a by-product of olive oil production and is a solid material consist-
ing of seed particles and the fleshy parts of olive. The Mediterranean
region represents 98% of the world’s olive tree population [91].
Various types of agricultural residues such as straw, plant
stems, leaves, pruning residues of fruit trees, oil seeds, stover, stalk,
stone, peel, seed, kernel shell, and husk were can be used as bio-
mass energy sources [40,92–95]. Ethanol from agricultural and for-
estry residues, energy crops, and other forms of lignocellulosic
biomass could address these issues and result in net CO2 reduc-
tions [19]. Hazelnut shell was subjected to thermogravimetric
analysis to establish burning profiles in a dynamic dry air atmo-
sphere. A strong relation was determined between the heating rate
and the intensity of the peaks on the burning profiles [96].
The fuel properties of mosses and algae, and the effect of pyro-
lysis temperature on the yield of bio-oil from moss and alga sam-
ples were investigated. The yield of bio-oil from pyrolysis of the
samples increased with temperature [93,97]. Pyrolysis process of
agricultural residues are the most common and convenient meth-
ods for conversion into bio-oil and bio-char [5].
Charcoal yield ranged from 24.23% to 37.89 wt.% and calorific
value varied from 17.29 to 33.47 MJ/kg. Conversion of charcoal
fines to solid fuel improved combustion quality [98]. Seven indig-
enous tree species of northeast India were pyrolyzed at tempera-
tures ranging from 573 K to 1073 K with two different heating
rates, 3 K/min and 20 K/min, and the effect of heating temperature
and heating rate on the products yield and char quality were ana-
lyzed and discussed [13]. The bagasse char samples were prepared
by carbonizing bagasse in a fixed-bed reactor at temperatures be-
tween 773 K and 1073 K. It was observed that raising the carbon-
ization temperature resulted in a significant decrease in
reactivity of bagasse char [99]. The chars from pyrolysis of the
demineralized biomasses can be used in adsorption applications
as activated carbons [35]. The properties of the char arising from
pyrolysis of sugarcane bagasse at 873 K and 1073 K were deter-
mined to evaluate potentialities for specific end uses. The chars
were found fairly adequate as solid biofuels [83].
The integrated organic waste-anaerobic digester-energy crop
production system as a eco-agricultural system and to use anaero-
bically digested cattle slurry as fertilizer for safflower production
was investigated [100]. Recycling of organic wastes by this system
can decrease input of chemical fertilizer and use of fossil fuels
[100]. Municipal wastewater treatment plants generate sludge as
a by-product of the physical, chemical and biological processes
used in the treatment of wastewater. Biogas can be produced from
wastewater sludge by using anaerobic digestion [11]. Most of the
total waste is organic, which could be utilized through a process
of anaerobic digestion and already has been in use for decades in
industrialized nations to produce clean burning methane gas, elec-
tricity, fuel, and fertilizers [101].
Reduction in the particle size of coir pith improved methane
yield about 1.5 times compared to natural sample. Whereas acid
treatment suppressed methane formation, alkali treatment has re-
sulted in a slight improvement [102]. Greenhouse gases emissions
from the widely accepted conventional biogas plants were investi-
gated [103]. Biogas can be used instead of compressed natural gas
to power gas vehicles, offering excellent air quality benefits as well
as carbon savings.
Bioethanol is a gasoline additive/substitute. Sugar cane, molas-
ses and corn are good sources of bioethanol. Bioethanol is derived
from alcoholic fermentation of sucrose or simple sugars, which are
produced from biomass by hydrolysis process [12]. It is possible
that corn stover may be economically converted to bioethanol
[28]. Future technologies may allow bioethanol to be produced
from a variety of source materials including wood, grass, straw
and green waste.
Methanol can be produced from hydrogen–carbon oxide mix-
tures by means of the catalytic reaction of carbon monoxide and
some carbon dioxide with hydrogen. Biosynthesis gas (bio-syngas)
is a gas rich in CO and H2 obtained by gasification of biomass.
Mixture of gases from organic waste materials is converted to
methanol in a conventional steam-reforming/water–gas shift
reaction followed by high-pressure catalytic methanol synthesis
[20].
Biodiesel is known as monoalkyl, such as methyl and ethyl, es-
ters of fatty acids. Biodiesel is produced from triglycerides by
transesterification process [45]. Biodiesel is the best candidate for
diesel fuels in diesel engines. Green biodiesel can be produced by
using natural biomethanol obtained from biosyngas [10]. Biodiesel
can be produced from a number of sources, including recycled
waste vegetable oil, oil crops and algae oil. Biodiesels play an
important role in meeting future fuel requirements in view of their
 A. Demirbas / Energy Conversion and Management 50 (2009) 2239–2249
nature (less toxic), and have an edge over conventional diesel as
they are obtained from renewable sources [104].
In general, the physical and chemical properties and the perfor-
mance of the cotton seed oil methyl ester were comparable to die-
sel fuel [42]. The effects of cotton seed oil methyl ester and diesel
fuel on a direct-injected, four-stroke, single-cylinder, air-cooled
diesel engine performance and exhaust emissions were investi-
gated. The results show that engine performance using cottonseed
oil methyl ester fuel differed little from engine performance and
torque with diesel fuel. As to the emissions, there was an approx-
imate 30% reduction in CO and approximate 25% reduction in NOx
[42]. The emission-forming gasses, such as carbon dioxide and car-
bon monoxide from combustion of biodiesel, generally are less
than diesel fuel. Sulfur emissions are essentially eliminated with
pure biodiesel [4].
Physical and chemical properties of methyl ester of waste cook-
ing oil were determined in the laboratory. Obtained results were
compared with No. 2 diesel fuel [56]. The specific fuel consumption
for biodiesel fuels tended to be higher than that for normal diesel
fuel, the exhaust smokiness values of biodiesels were considerably
lower than that for petroleum diesel. On the other hand, there
were no significant differences observed for torque, power and ex-
haust smokiness [105].
A new lipase immobilization method, textile cloth immobiliza-
tion, was developed for conversion of soybean oil to biodiesel. The
test results indicate that the maximum yield of biodiesel of 92%
was obtained at the conditions of hexane being the solvent, water
content being 20 wt.%, and reaction time being 24 h [51].
The dynamic transesterification reaction of peanut oil in super-
critical methanol media was investigated. The reaction tempera-
ture and pressure were in the range of 523–583 K and 10.0–
16.0 MPa, respectively. The molar ratio of peanut oil to methanol
was 1:30. It was found that the yield of methyl esters was higher
than 90% under the supercritical methanol [14].
Problems to be studied include fuel storage stability, fuel sol-
ubility, and oxidative stability of recycled soybean-derived bio-
diesel were investigated. Unlike newly manufactured soy oils, it
was found that this recycled soy oil was not stable in fuels
[53]. The oxidative and thermal degradation occurs on the double
bonds of unsaturated aliphatic carbons chains in biolipids.
Oxidation of biodiesel results in the formation of hydroperoxides
[49].
Biohydrogen is gaining increasing attention as an encouraging
future energy. Biomass can be thermally processed through gasifi-
cation or pyrolysis to produce hydrogen. The combustion of hydro-
gen does not produce CO2, CO, SO2, VOC and particles, but entails
emission of vapor and NOx [106].
The yields of hydrogen from the pyrolysis and the steam gasifi-
cation increase with increasing of temperature. The highest yields
were obtained from the pyrolysis (46%) and steam gasification
(55%) of wheat straw while the lowest yields from olive waste
[107]. Hydrothermal gasification of biomass wastes has been iden-
tified as a possible system for producing hydrogen. Supercritical
and subcritical water has attracted much attention as an environ-
mentally benign reaction medium and reactant [108]. Biohydrogen
has the potential to solve two major energy problems: reducing
dependence on petroleum and reducing pollution and greenhouse
gas emissions [109]. Future technologies may allow biohydrogen
to be produced economically from biorenewable feedstocks. Biohy-
drogen as the most promising candidates for tomorrow’s non-car-
bon transport fuels.
The liquefaction of hydrogen gas on platinum (Pt)-supported
carbon nano-layers was investigated. In the experiments, H2PtCl6
was used as Pt precursor and to prepare the Pt catalytic reaction
nano-layer, the required amounts of H2PtCl6 were mixed with 5
wt.% carbon prepared by burning naphthalene in air. The yield of
2243
liquefied hydrogen was 7.4% weight of Pt-catalyzed carbon for
30 min [110].
The mixture of H2 + CO is called as synthesis gas or syngas. Bio-
syngas is a gas rich in CO and H2 obtained by gasification of bio-
mass. The aim of Fischer–Tropsch Synthesis (FTS) is synthesis of
long-chain hydrocarbons from CO and H2 gas mixture. The prod-
ucts from FTS are mainly aliphatic straight-chain hydrocarbons
(CxHy). Steam reforming of hydrocarbons, partial oxidation of hea-
vy oil residues, selected steam reforming of aromatic compounds,
and gasification of coals and solid wastes to yield a syngas, fol-
lowed by water–gas shift conversion to produce H2 and CO2, are
well-established processes [107,111].
4. Economic and environmental impacts of biofuels
Biofuels offer a number of technical and environmental benefits
over conventional fossil fuels, which make them attractive as alter-
natives for the transport sector. The benefits include greenhouse
gas reductions including reduced carbon dioxide emissions, which
will contribute to domestic and international targets, the diversifi-
cation of the fuel sector, biodegradability, sustainability, and an
additional market for agricultural products. Biofuels help to protect
and create jobs. Table 2 shows the major benefits of biofuels. Major
benefits of biodiesel are given in Table 3.
According to a study by the European Commission, European
production of biofuels equivalent to 1% of EU automotive fuel con-
sumption would help to protect and/or create between 45,000 and
75,000 jobs. Biofuels can be used as an alternative fuel for trans-
port, as can other alternatives such as liquid natural gas (LNG),
compressed natural gas (CNG) and liquefied petroleum gas (LPG).
In the longer term, significant use of biofuels could offer large car-
bon savings. Policy drivers for renewable liquid biofuels have at-
tracted particularly high levels of assistance in some countries
given their promise of benefits in several areas of interest to gov-
ernments, including agricultural production, greenhouse gas emis-
sions, energy security, trade balances, rural development and
economic opportunities for developing countries [1].
Bioethanol can be used directly in cars designed to run on pure
ethanol or blended with gasoline to make ‘‘gasohol”. Anhydrous
ethanol is required for blending with gasoline. No engine modifica-
tion is typically needed to use the blend. Ethanol can be used as an
octane-boosting, pollution-reducing additive in unleaded gasoline.
World production of ethanol from sugar cane, maize and sugar
Table 2
Major benefits of biofuels.
Economic impacts Sustainability
Fuel diversity
Increased number of rural manufacturing jobs
Increased income taxes
Increased investments in plant and equipment
Agricultural development
International competitiveness
Reducing the dependency on imported petroleum
Environmental impacts Greenhouse gas reductions
Reducing of air pollution
Biodegradability
Higher combustion efficiency
Improved land and water use
Carbon sequestration
Energy security Domestic targets
Supply reliability
Reducing use of fossil fuels
Ready availability
Domestic distribution
Renewability
2244 A. Demirbas / Energy Conversion and Management 50 (2009) 2239–2249

Table 3 Table 5
Major benefits of biodiesel. Fuel economy impacts of biodiesel use.

Economic impacts Sustainability Percent of biodiesel in diesel fuel % Reduction in miles/gallon

Environmental impacts
Fuel diversity
20 0.9–2.1
Increased number of rural manufacturing jobs
100 4.6–10.6
Increased income taxes
Increased investments in plant and equipment
Agricultural development
International competitiveness
Reducing the dependency on imported petroleum
5
Inherent lubricity
Higher cetan number 4.5
Greenhouse gas reductions
4
Reducing of air pollution
Biodegradability 3.5
Higher combustion efficiency

Billion gallo n
Improved land and water use 3
Carbon sequestration
Lower sulfur content 2.5
Lower aromatic content 2
Less toxicity
Energy security Domestic targets 1.5
Supply reliability 1
Higher flash point
Reducing use of fossil fuels 0.5
Ready availability
Domestic distribution 0
Renewability USA Brazil China India France

Fig. 4. The top five bioethanol producers (billion gallons) in 2006.

Table 4
Biodiesel production capacity of European Union in 2003.
60
Country (1000 metric tons)
Germany 1025
France 500 50
Total world production, billion liters

Italy 420
Austria 50
Denmark 40 Ethanol
40
United Kingdom 5
Sweden 8 Biodiesel
Total 2048
30

beet increased from less than 20 billion L in 2000 to over 40 billion 20

L in 2005. This represents around 3% of global gasoline use. Produc-
tion is forecasted to almost double again by 2010 [112].
Biodiesel is a synthetic diesel-like fuel produced from vegetable
oils, animal fats or waste cooking oil. It can be used directly as fuel,
which requires some engine modifications, or blended with petro-
leum diesel and used in diesel engines with few or no modifica-
tions. At present, biodiesel accounts for less than 0.2% of the
diesel consumed for transport [112]. Biodiesel has become more
attractive recently because of its environmental benefits. The cost
of biodiesel, however, is the main obstacle to commercialization
of the product. With cooking oils used as raw material, the viability
of a continuous transesterification process and recovery of high
quality glycerol as a biodiesel by-product are primary options to
be considered to lower the cost of biodiesel [113,114]. Table 4
shows biodiesel production capacity of European Union in 2003.
The possible impact of biodiesel on fuel economy is positive as gi-
ven in Table 5 [115].
Renewable alcohols are at present more expensive of synthesis-
ethanol from ethylene and of methanol from natural gas. The simul-
taneous production of biomethanol (from sugar juice) in parallel to
the production of bioethanol appears economically attractive in
locations where hydro-electricity is available at very low cost.
The EU production of biofuels amounted to around 2.9 billion L
in 2004, with bioethanol totalling 620 million liters and biodiesel
the remaining 2.3 billion L. The feed stocks used for ethanol pro-
10
0
1979 1984 1989 1994 1999 2004
Years
Fig. 5. World production of ethanol and biodiesel, 1980–2007.
duction are cereals and sugar beet, while biodiesel is manufactured
mainly from rapeseeds. In 2004, EU biodiesel production used 27%
of EU rapeseed crop. In the same year, bioethanol production used
0.4% of EU cereals production and 0.8% of EU sugar beet produc-
tion. The EU is by far the world’s biggest producer of biodiesel with
Germany producing over half of the EU’s biodiesel. France and Italy
are also important biodiesel producers, while Spain is the EU’s
leading bioethanol producer [112].
Between 1991 and 2001, world ethanol production rose from
around 16 billion L a year to 18.5 billion L. Brazil was the world’s
leading ethanol producer until 2005 when US production roughly
equalled Brazil’s. The United States become the world’s leading
ethanol producer in 2006. China holds a distant but important
third place in world rankings, followed by India, France, Germany
 A. Demirbas / Energy Conversion and Management 50 (2009) 2239–2249
Table 6
Average international prices for common biocrude, fat, crops and oils used as
feedstock for biofuel production in 2007 (US$/ton).
Biocrude
Crude palm oil
Maize
Rapeseed oil
Soybean oil
Sugar
Wheat
Yellow grease
and Spain. Fig. 4 shows the top five bioethanol producers in 2006
[116]. Fig. 5 shows world production of ethanol and biodiesel,
1980–2007.
4.1. Current costs, prices and economic impact of the biofuels
Biofuels production costs can vary widely by feedstock, conver-
sion process, scale of production and region. On an energy basis,
ethanol is currently more expensive to produce than gasoline in
all regions considered. Only ethanol produced in Brazil comes close
to competing with gasoline. Ethanol produced from corn in the US
is considerably more expensive than from sugar cane in Brazil, and
ethanol from grain and sugar beet in Europe is even more expen-
sive. These differences reflect many factors, such as scale, process
efficiency, feedstock costs, capital and labor costs, co-product
accounting, and the nature of the estimates.
The cost of large-scale production of bio-based products is cur-
rently high in developed countries. For example, the production
cost of biofuels may be three times higher than that of petroleum
fuels, without, however, considering the non-market benefits. Con-
versely, in developing countries, the costs of producing biofuels are
much lower than in the OECD countries and very near to the world
market price of petroleum fuel [112]. Average international prices
for common biocrude, fat, crops and oils used as feedstock for bio-
fuel production in 2007 are given in Table 6 [1].
Agriculture ethanol is at present more expensive of synthesis-
ethanol from ethylene. The simultaneous production of biometha-
nol (from sugar juice) in parallel to the production of bioethanol,
appears economically attractive in locations where hydro-electric-
ity is available at very low cost (0.01 $ Kwh) [117].
Currently there is no global market for ethanol. The crop types,
agricultural practices, land and labor costs, plant sizes, processing
technologies and government policies in different regions consid-
erably vary ethanol production costs and prices by region. Ethanol
from sugar cane, produced mainly in developing countries with
warm climates, is generally much cheaper to produce than ethanol
from grain or sugar beet in IEA countries. For this reason, in coun-
tries like Brazil and India, where sugar cane is produced in substan-
tial volumes, sugar cane-based ethanol is becoming an increasingly
cost-effective alternative to petroleum fuels. Estimates show that
bioethanol in the EU becomes competitive when the oil price
reaches US$70 a barrel while in the United States it becomes com-
petitive at US$50–60 a barrel. For Brazil the threshold is much low-
er – between US$25 and US$30 a barrel. Other efficient sugar
producing countries such as Pakistan, Swaziland and Zimbabwe
have production costs similar to Brazil’s [118]. Anhydrous ethanol,
blendable with gasoline, is still somewhat more expensive. Prices
in India have declined and are approaching the price of gasoline.
For biofuels, the cost of feedstock (crops) is a major component
of overall costs. In particular, the cost of producing oil-seed-de-
rived biodiesel is dominated by the cost of the oil and by competi-
tion from high-value uses like cooking. The largest ethanol cost
component is the plant feedstock. Operating costs, such as feed-
stock cost, co-product credit, chemicals, labor, maintenance, insur-
2245
ance and taxes, represent about one-third of total cost per liter, of
which the energy needed to run the conversion facility is an impor-
tant (and in some cases quite variable) component. Capital cost
167 recovery represents about one-sixth of total cost per liter. It has
703 been showed that plant size has a major effect on cost [119]. The
179
824
plant size can reduce operating costs by 15–20%, saving another
771 $0.02–$0.03 per liter. Thus, a large plant with production costs of
223 $0.29 per liter may be saving $0.05–$0.06 per liter over a smaller
215 plant [119].
412
4.2. Environmental impact of biofuels
Subsidies and incentives are provided independently from the
environmental impact that ethanol may have during its entire life
cycle, therefore, supporting biofuel production in the United States.
In 2001, the European Commission launched a policy to promote
the use of biofuels for transport in order to reduce greenhouse
gas emissions and the environmental impact of transport, as well
as to increase security of supply, technological innovation and agri-
cultural diversification [112].
Biodiesel has become more attractive recently because of its
environmental benefits. Biodiesel is superior to conventional diesel
in terms of its sulfur content, aromatic content and flash point. It is
essentially sulfur free and non-aromatic while conventional diesel
can contain up to 500 ppm SO2 and 20–40 wt.% aromatic com-
pounds. These advantages could be a key solution to reducing
the problem of urban pollution since gas emissions from the trans-
portation sector contribute a significant amount to the total gas
emissions. Diesel, in particular, is dominant for black smoke partic-
ulate together with SO2 emissions and contributes to a one-third of
the total transport generated greenhouse gas emissions [55]. There
was an average of decreasing of 14% for CO2, 17.1% for CO and
22.5% for smoke density when using biodiesel [56].
The biofuels include bioethanol, biobutanol, biodiesel, vegetable
oils, biomethanol, pyrolysis oils, fuels from Fischer–Tropsch syn-
thesis, biogas, and biohydrogen. There are several reasons for bio-
fuels to be considered as relevant technologies by both developing
and industrialized countries. They include energy security reasons,
environmental concerns, foreign exchange savings, and socioeco-
nomic issues related to the rural sector. Due to its environmental
merits, the share of biofuel in the automotive fuel market will grow
fast in the next decade [41,120].
4.2.1. Reduction of exhaust emissions by using biodiesel in CIEs
Biofuels such as bioethanol, biomethanol, biohydrogen and bio-
diesel generally results lower emissions than those of fossil based
engine fuels. Many studies on the performances and emissions of
compression ignition engines, fuelled with pure biodiesel and
blends with diesel oil, have been performed and are reported in
the literature [121,122].
Vegetable oils have become more attractive recently because of
their environmental benefits and the fact that it is made from
renewable resources. Dorado et al. [123] describe experiments on
the exhaust emissions of biodiesel from olive oil methyl ester as
alternative Diesel fuel fueled in a Diesel direct injection Perkins
engine.
The methyl ester of vegetable oil was evaluated as a fuel in CIE
by researchers [124]. They concluded that the performance of the
esters of vegetable oil did not differ greatly from that of Diesel fuel.
The brake power was nearly the same as with Diesel fuel, while the
specific fuel consumption was higher than that of Diesel fuel. Based
on crankcase oil analysis, engine wear rates were low but some oil
dilution did occur. Carbon deposits inside the engine were normal,
with the exception of intake valve deposits. The results showed the
transesterification treatment decreased the injector coking to a
level significantly lower than that observed with D2 [125].
2246 A. Demirbas / Energy Conversion and Management 50 (2009) 2239–2249

Although most researchers agree that vegetable oil ester fuels are
suitable for use in CIE, a few contrary results have also been ob-
tained. The results of these studies point out that most vegetable
oil esters are suitable as Diesel substitutes but that more long term
studies are necessary for commercial utilization to become
practical.
Fuel characterization data show some similarities and differ-
ences between biodiesel fuels and Diesel [125]:
 Specific weight is higher for biodiesel, heat of combustion is
lower and viscosities are 1.3–1.6 times that of D2 fuel.
 Pour points for biodiesel fuels vary from 274 to 298 K higher for
biodiesel fuels depending on the feedstock.
 Sulfur content for biodiesel fuel is 20–50% that of D2 fuel.
 The esters all have higher levels of injector coking than D2 fuel.
Several municipalities are considering mandating the use of low
levels of biodiesel in diesel fuel on the basis of several studies
which have found hydrocarbon (HC) and particulate matter (PM)
benefits from the use of biodiesel.
The use of biodiesel to reduce N2O is attractive for several rea-
sons. First, biodiesel contains little nitrogen, as compared with Die-
sel fuel which is also used as a re-burning fuel. The N2O reduction
was strongly dependent on initial N2O concentration and only
slightly dependent upon temperature, where increased tempera-
ture increased N2O reduction. This results in lower N2O production
from fuel nitrogen species for biodiesel. In addition, biodiesel con-
tains virtually trace amount of sulfur, so SO2 emissions are reduced
in direct proportion to the Diesel fuel replacement.
Neat biodiesel and biodiesel blends reduce particulate matter
(PM), hydrocarbons (HC) and carbon monoxide (CO) emissions
and increase nitrogen oxides (NOx) emissions compared with die-
sel fuel used in an unmodified diesel engine [115]. The emission
impacts of 20 vol.% soybean-based biodiesel added to an average
base petrodiesel is given in Table 7 [115].
Table 7
Emission impacts of 20 vol.% soybean-based biodiesel added to an average base
petrodiesel.
Percent change in emissions
The total net emission of carbon dioxide (CO2) is considerably
less than that of diesel oil and the amount of energy required for
the production of biodiesel is less than that obtained with the final
product. In addition, the emission of pollutants is somewhat less.
CO2, one of the primary greenhouse gasses, is a trans-boundary
gas, which means that, after it is emitted by a source, it is quickly
dispersed in our atmosphere by natural processes. Biodiesel re-
duces CO2 emissions. Table 8 shows the average biodiesel emis-
sions compared to conventional diesel, according to EPA [115].
Table 9 shows the average changes in mass emissions from diesel
engines using the biodiesel mixtures relative to the standard diesel
fuel [126].
Results indicate that the transformities of biofuels are greater
than those of fossil fuels, thus showing that a larger amount of re-
sources is required to get the environmental friendly product. This
can be explained by the fact that natural processes are more effi-
cient than industrial ones. On the other hand, the time involved
in the formation of the fossil fuels is considerably different from
that required for the production of the biomass [127]. Coconut
BD can yield reductions of 80.8–109.3% in net CO2 emissions rela-
tive to PD [128].
Different scenarios for the use of agricultural residues as fuel for
heat or power generation are analyzed. Reductions in net CO2
emissions are estimated at 77–104 g/MJ of diesel displaced by bio-
diesel. The predicted reductions in CO2 emissions are much greater
than values reported in recent studies on biodiesel derived from
other vegetable oils, due both to the large amount of potential fuel
in the residual biomass and to the low-energy inputs in traditional
coconut farming techniques [128]. Unburned hydrocarbon emis-
sions from biodiesel fuel combustion decrease compared to regular
petroleum diesel. The use of blends of biodiesel and diesel oil are
preferred in engines, in order to avoid some problems related to
the decrease of power and torque and to the increase of NOx emis-
sions with increasing content of pure biodiesel in the blend [129].
Emissions of all pollutants except NOx appear to decrease when
biodiesel is used. The fact that NOx emissions increase with
20
Percentage change in exhaust emissions

NOx (nitrogen oxides) +2.0

PM (particular matter) 10.1 0
HC (hydrocarbons) 21.1
CO (carbon monoxide) 11.0

-20

Table 8
Average biodiesel emissions (%) compared to conventional diesel, according to EPA -40
(2002). NOx
Emission type Pure biodiesel Biodiesel + 80% PM
20% petrodiesel -60 CO
B100 B20
HC
Total unburned hydrocarbons (HC) 67 20
Carbon monoxide 48 12
-80
0 20 40 60 80 100
Particulate matter 47 12
NOx +10 +2 Percent of biodiesel
Sulfates 100 20
Polycyclic aromatic hydrocarbons 80 13 Fig. 6. Curves for average emission impacts of vegetable oil-based biodiesel for CIE:
percent change in emissions vs. petroleum diesel fuel.

Table 9
Average changes in mass emissions from diesel engines using the biodiesel mixtures relative to the standard diesel fuel (%).

Mixture CO NOx SO2 Particular matter Volatile organic compounds

B20 13.1 +2.4 20 8.9 17.9
B100 42.7 +13.2 100 55.3 63.2
 A. Demirbas / Energy Conversion and Management 50 (2009) 2239–2249
10
Percent change in exhaust emissions
0 Technol 2008;22:69–95.
-10
-20
-30 NOx
PM
-40
CO
-50
-60
0 20 40 60
Percent of biodiesel
Fig. 7. Curves for average emission impacts of animal-based biodiesel for CIE:
percent change in emissions vs. petroleum diesel fuel.
increasing biodiesel concentration could be a detriment in areas
that are out of attainment for ozone. Fig. 6 shows the average emis-
sion impacts of vegetable oil-based biodiesel for Compression Igni-
tion Engine (CIE). Fig. 7 shows average emission impacts of animal-
based biodiesel for CIE [130]. One of the most impressive charac-
teristics of biodiesel is that when burned it has fewer particulates
than a petroleum-based diesel.
5. Conclusions
This paper examines the potential roles of biofuels in the 21st
century with a global energy model treating the entire fuel supply
chain in detail. The biofuels as gasoline additive/substitute (bioeth-
anol) and as diesel-equivalent (biodiesel) become major alterna-
tive of petroleum based transportation fuels.
There are several reasons for biofuels to be considered as rele-
vant technologies by both developing and industrialized countries.
They include energy security reasons, environmental concerns, for-
eign exchange savings, and socioeconomic issues related to the
rural sector. Biofuels are of rapidly growing interest for reasons
of energy security, diversity, and sustainability benefits. Biofuels
offer significant benefits for energy security. Biofuels also offer
the promise of numerous benefits related to energy security, eco-
nomics, and the environment.
Bioethanol is a petrol additive/substitute fuel. It is possible that
wood, straw and even household food wastes may be economically
converted to bioethanol. Bioethanol is derived from alcoholic fer-
mentation of sucrose or simple sugars, which are produced from
biomass by hydrolysis process. Currently crops generating starch,
sugar or oil are the basis for transport fuel production. There has
been renewed interest in the use of vegetable oils for making bio-
diesel due to its less polluting and renewable nature as against the
conventional petroleum diesel fuel.
Biodiesel is a renewable replacement to petroleum-based die-
sel. Brief summaries of the basic concepts involved in the thermo-
chemical conversions of biomass fuels are presented.
Biofuels such as bioethanol, biomethanol, biohydrogen and bio-
diesel generally results lower emissions than those of fossil based
engine fuels.
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