ARTICLE IN PRESS

Progress in Energy and Combustion Science 33 (2007) 1–18

www.elsevier.com/locate/pecs

Progress and recent trends in biofuels

Ayhan Demirbas
Department of Chemical Engineering, Selcuk University, Campus, 42031 Konya, Turkey
Received 28 March 2006; accepted 28 June 2006
Available online 22 August 2006

Abstract

In this paper, the modern biomass-based transportation fuels such as fuels from Fischer–Tropsch synthesis, bioethanol,
fatty acid (m)ethylester, biomethanol, and biohydrogen are briefly reviewed. Here, the term biofuel is referred to as liquid
or gaseous fuels for the transport sector that are predominantly produced from biomass. 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 socioeconomic issues related to the rural sector.
The term modern biomass is generally used to describe the traditional biomass use through the efficient and clean
combustion technologies and sustained supply of biomass resources, environmentally sound and competitive fuels, heat
and electricity using modern conversion technologies. Modern biomass can be used for the generation of electricity and
heat. Bioethanol and biodiesel as well as diesel produced from biomass by Fischer–Tropsch synthesis are the most modern
biomass-based transportation fuels. Bio-ethanol is a petrol additive/substitute. It is possible that wood, straw and even
household wastes may be economically converted to bio-ethanol. Bio-ethanol is derived from alcoholic fermentation 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
biodiesel due to its less polluting and renewable nature as against the conventional petroleum diesel fuel. Biodiesel is a
renewable replacement to petroleum-based diesel. Biomass energy conversion facilities are important for obtaining bio-oil.
Pyrolysis is the most important process among the thermal conversion processes of biomass. Brief summaries of the basic
concepts involved in the thermochemical conversions of biomass fuels are presented. The percentage share of biomass was
62.1% of the total renewable energy sources in 1995. The reduction of greenhouse gases pollution is the main advantage of
utilizing biomass energy.
r 2006 Elsevier Ltd. All rights reserved.

Keywords: Fischer–Tropsch synthesis; Steam reforming; Biohydrogen; Bio(m)ethanol; Biodiesel; Bio-oil

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Global biofuel scenarios . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Biohydrogen from biomass by steam reforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. Steam-reforming process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

Tel.: +90 462 230 7831; fax: +90 462 248 8508.
E-mail address: ayhandemirbas@hotmail.com.

0360-1285/$ - see front matter r 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.pecs.2006.06.001

2 A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18
3.2. Fuels from bio-syngas via
4. Bioethanol . . . . . . . . . . . . . . .
5. Biodiesel . . . . . . . . . . . . . . . . .
6. Biomethanol . . . . . . . . . . . . . .
7. Bio-oil . . . . . . . . . . . . . . . . . .
8. Conclusion . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . .
1. Introduction
The term bio-fuel is referred to as liquid or
gaseous fuels for the transport sector that are
predominantly produced from biomass. Bio-fuels
are generally considered as offering many priorities,
including sustainability, reduction of greenhouse
gas emissions, regional development, social struc-
ture and agriculture, security of supply [1]. World-
wide energy consumption has increased 17 fold in
the last century and emissions of CO2, SO2 and NOx
from fossil-fuel combustion are primary causes of
atmospheric pollution [2]. Known petroleum re-
serves are estimated to be depleted in less than 50
years at the present rate of consumption [3]. In
developed countries there is a growing trend
towards employing modern technologies and effi-
cient bio-energy conversion using a range of bio-
fuels, which are becoming cost-wise competitive
with fossil fuels [4].
Biomass has been recognized as a major world
renewable energy source to supplement declining
fossil fuel resources [5,6]. Biomass appears to be an
attractive feedstock for three main reasons. First, it
is a renewable resource that could be sustainably
developed in the future. Second, it appears to have
formidably positive environmental properties re-
sulting in no net releases of carbon dioxide (CO2)
and very low sulfur content. Third, it appears to
have significant economic potential provided that
fossil fuel prices increase in the future [7]. Ligno-
cellulosic bio-methanol have such low emissions
because the carbon content of the alcohol is
primarily derived from carbon that was sequestered
in the growing of the bio-feedstock and is only being
re-released into the atmosphere [8].
Transport sector is major consumer of petroleum
fuels such as diesel, gasoline, liquefied petroleum gas
(LPG) and compressed natural gas (CNG). This
sector is likely to suffer badly because of following
reasons: (a) Prices of petroleum in global market are
raising trend; (b) Petroleum reserves are limited and
it is monopoly of some oil-importing countries and
ARTICLE IN PRESS
Fisher–Tropsch synthesis (FTS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
......................................................... 9
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
rest of the world depends on them; (c) Number of
vehicles based on petroleum fuels is on increase
worldwide. Many research programs recently focus
on the development of concepts such as renewable
resources, sustainable development, green energy,
eco-friendly process, etc. in the transportation
sector. In developed countries there is a growing
trend towards employing modern technologies and
efficient bio-energy conversion using a range of
biofuels, which are becoming cost-wise competitive
with fossil fuels [9]. Advantages of bio-fuels are the
following: (a) Bio-fuels are easily available from
common biomass sources; (b) They are represent a
CO2 cycle in combustion; (c) Bio-fuels have a
considerable environmentally friendly potential;
(d) There are many benefits the environment,
economy and consumers in using bio-fuels; and (e)
They are biodegradable and contribute to sustain-
ability [10].
Currently, biomass converts to bio-oil by fast
pyrolysis and then the bio-oil converts to hydrogen
(H2) by catalytic steam reforming [11–13]. The yield
of H2 that can be produced from biomass is
relatively low, 16–18% based on dry biomass weight
[14]. Only the carbohydrate-derived bio-oil fraction
produced from biomass undergoes reforming. At
present, the amount of biomass-derived bio-oil
available for reforming is rather limited, but a
viable way to increase the production of H2 in a
biomass-based plant could be co-reforming of bio-
oil with natural gas [15]. If the purpose were to
maximize the yield of liquid products resulting from
biomass pyrolysis, a low temperature, high heating
rate, short gas residence time process would be
required. If 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 [16].
The Fischer–Tropsch Synthesis (FTS) produces
hydrocarbons of different length from a gas mixture
of H2 and CO (syngas) from biomass gasification
called as bio-syngas. The fundamental reactions of
synthesis gas chemistry are methanol synthesis,
 ARTICLE IN PRESS
A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18
FTS, oxo synthesis (hydroformylation), and
methane (CH4) synthesis [17]. The FTS process is
a process capable of producing liquid hydrocarbon
fuels from bio-syngas. The large hydrocarbons can
be hydrocracked to form mainly diesel of excellent
quality. The process for producing liquid fuels from
biomass, which integrates biomass gasification with
FTS, converts a renewable feedstock into a clean
fuel.
The products from FTS are mainly aliphatic
straight-chain hydrocarbons (CxHy). Besides the
CxHy also branched hydrocarbons, unsaturated
hydrocarbons, and primary alcohols are formed in
minor quantities. The product distribution obtained
from FTS includes the light hydrocarbons CH4,
ethene (C2H4) and ethane (C2H6), LPG (C3–C4,
propane and butane), gasoline (C5–C12), diesel fuel
(C13–C22), and light and waxes (C23–C33). The
distribution of the products depends on the catalyst
and the process parameters such as temperature,
pressure, and residence time. The FTS was exten-
sively investigated by many researchers [17–22].
Vegetable oils from renewable oil seeds can be use
when mixed with diesel fuels. Pure vegetable oil,
however, cannot be used in direct-injection diesel
engines, such as those regularly used in standard
tractors, since the vegetable oil cooking occurs after
several hours of use. Conversion of the vegetable
oils and animal fats into biodiesel has been under-
going further development over the past several
years [23–28]. Biodiesel represents an alternative to
petroleum-based diesel fuel. Chemically speaking,
biodiesel is a mixture of mono-alkyl esters of fatty
acids, most often obtained from extracted plant oils
and/or collected animal fats. Commonly accepted
biodiesel raw materials include the oils from soy,
canola, corn, rapeseed, and palm. New plant oils
that are under consideration include mustard seed,
peanut, sunflower, and cottonseed. The most
commonly considered animal fats include those
derived from poultry, beef, and pork [29].
Ethanol is the most widely used liquid biofuel. It
is an alcohol and is fermented from sugars, starches
or from cellulosic biomass. Most commercial
production of ethanol is from sugar cane or sugar
beet, as starches and cellulosic biomass usually
require expensive pretreatment. It is used as a
renewable energy fuel source as well as being used
for manufacture of cosmetics, pharmaceuticals and
also for the production of alcoholic beverages. Ethyl
alcohol is not only the oldest synthetic organic
chemical used by man, but it is also one of the most
3
important. In an earlier study [30], physiological
effects of inhibitors on ethanol from lignocellulosic
materials and fermentation strategies were compre-
hensively investigated.
2. Global biofuel scenarios
Renewable resources are more evenly distributed
than fossil and nuclear resources, and energy flows
from renewable resources are more than three
orders of magnitude higher than current global
energy use. Today’s energy system is unsustainable
because of equity issues as well as environmental,
economic, and geopolitical concerns that have
implications far into the future [31].
According to International Energy Agency (IEA),
scenarios developed for the USA and the EU
indicate that near-term targets of up to 6%
displacement of petroleum fuels with biofuels
appear feasible using conventional biofuels, given
available cropland. A 5% displacement of gasoline
in the EU requires about 5% of available cropland
to produce ethanol while in the USA 8% is
required. A 5% displacement of diesel requires
13% of USA cropland, 15% in the EU [32].
The dwindling fossil fuel sources and the increas-
ing dependency of the USA on imported crude oil
have led to a major interest in expanding the use of
bio-energy. The recent commitment by the USA
government to increase bio-energy three-fold in 10
years has added impetus to the search for viable
biofuels. The EU have also adopted a proposal for a
directive on the promotion of the use of bio-fuels
with measures ensuring that bio-fuels account for at
least 2% of the market for gasoline and diesel sold
as transport fuel by the end of 2005, increasing in
stages to a minimum of 5.75% by the end of 2010
[33]. Fig. 1 shows main biomass conversion
processes. Fig. 2 shows resources of main liquid
biofuels for automotives. Fig. 3 shows the shares of
alternative fuels compared to the total automotive
fuel consumption in the world as a futuristic view.
3. Biohydrogen from biomass by steam reforming
Biomass is a mixture of structural constituents
(hemicelluloses, cellulose and lignin) and minor
amounts of extractives which each pyrolyze at
different rates and by different mechanisms and
pathways. All biomass materials can be converted
to energy via thermochemical and biological pro-
cesses. Biomass gasification has attracted the
 ARTICLE IN PRESS
4 A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18

Biomass

Feedstock Processing

Thermochemical Conversion Biochemical Conversion

Pyrolysis Gasification Liquefaction Bioethanol Biodiesel

Syn-oil Syn-gas Bio-chemicals

Fig. 1. Main biomass conversion processes.

BIOFUELS

BIOETHANOL

BIODIESEL Wheat Maize Sugar beet Potatoes

Rapeseed Soybean Palm Sunflower

Fig. 2. Resources of main liquid biofuels for automotives.

Biofuels Natural gas Hydrogen reactive and forms stable chemical structures, and
20 consequently the activation energy increases as the
18 conversion level of biomass increases [35].
Alternative fuel consumption, %

16 Biomass gasification can be considered as a form

14 of pyrolysis, which takes place in higher tempera-
12 tures and produces a mixture of gases with H2
10
content ranging 6–6.5% [36,37]. H2 can be produced
from biomass via two thermochemical processes: (1)
8
gasification followed by reforming of the syngas,
6
and (2) fast pyrolysis followed by reforming of the
4 carbohydrate fraction of the bio-oil. In each
2 process, water–gas shift (WGS) is used to convert
0 the reformed gas into H2, and pressure swing
2000 2010 2020 2030 2040 2050 adsorption is used to purify the product.
Years Power generation from gaseous products from
Fig. 3. Shares of alternative fuels compared to the total biomass gasification is found to be the most
automotive fuel consumption in the world. Source: Ref. [70]. promising biomass gasification technology. Gasifi-
cation technologies provide the opportunity to
convert renewable biomass feedstocks into clean
highest interest among the thermochemical conver- fuel gases or synthesis gases. The synthesis gas
sion technologies as it offers higher efficiencies in includes mainly H2 and carbon monoxide (CO)
relation to combustion, whereas flash pyrolysis is which is also called as syngas. Bio-syngas is a gas
still in the development stage [34]. It is believed that rich in CO and H2 obtained by gasification of
as the reaction progresses the carbon becomes less biomass [38].
 ARTICLE IN PRESS
A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18
Currently, H2 is most economically produced
from natural gas. The most studied technology for
H2 production is steam-CH4 reforming, in which
CH4 reacts with steam to produce a mixture of H2,
CO2 and CO.
3.1. Steam-reforming process
In the steam-reforming reaction, steam reacts
with hydrocarbons in the feed to predominantly
produce CO and H2, commonly called synthesis gas.
Steam reforming can be applied various solid waste
materials including, municipal organic waste, waste
oil, sewage sludge, paper mill sludge, black liquor,
refuse-derived fuel, and agricultural waste. Steam
reforming of natural gas, sometimes referred to as
steam CH4 reforming is the most common method
of producing commercial bulk H2. Steam reforming
of natural gas is currently the least expensive
method of producing H2, and used for about half
of the world’s production of H2.
H2 production from carbonaceous solid wastes
requires multiple catalytic reaction steps: For the
production of high purity H2, the reforming of fuels
is followed by two water gas-shift reaction steps, a
final CO purification and CO2 removal. Steam
reforming, partial oxidation and autothermal re-
forming of CH4 are well-developed processes for the
production of H2. Stepwise steam reforming of CH4
for production of CO-free H2 has been investigated
at various process conditions by Choudhary and
Goodman [39]. The process consists of two steps
involving the decomposition of CH4 to CO-free H2
and surface carbon in the first step followed by
steam gasification of this surface carbon in the
second step. The amount of CO-free H2 formed in
the first step. The mixture of gases can be separated
and CH4-rich gas mixture returned to the first step
[39]. Steam, at high temperatures (975–1375 K) is
mixed with CH4 gas in a reactor with a Ni-based
catalyst at 3–25 bar pressure to yield CO and H2.
Steam reforming is the process by which CH4 and
other hydrocarbons in natural gas are converted into
H2 and CO by reaction with steam over a nickel
catalyst on a ceramic support. The H2 and CO are
used as initial material for other industrial processes.
CH4 þ H2 O Ð CO þ 3H2 DH ¼ þ251 kJ=mol:
(1)
It is usually followed by the shift reaction:
CO þ H2 O Ð CO2 þ H2 DH ¼ 42 kJ=mol: (2)
5
The theoretical percentage of H2 to water is 50%.
The further chemical reactions for most hydrocar-
bons that take place are
Cn Hm þ nH2 O Ð nCO þ ðm=2 þ nÞH2 : (3)
It is possible to increase the efficiency to over 85%
with an economic profit at higher thermal integra-
tion. There are two types of steam reformers for
small-scale H2 production: conventional reduced-
scale reformers and specially designed reformers for
fuel cells.
Commercial catalysts consist essentially of Ni
supported on a-alumina. Mg-promoted catalysts
showed a greater difficulty for Ni precursor’s
reduction besides different probe molecules (H2
and CO) adsorbed states. In the conversion of
cyclohexane, Mg inhibited the formation of hydro-
genolysis products. Nonetheless, the presence of Ca
did not influence the metallic phase. The impreg-
nated Ni/MgO-catalyst performed better than the
other types [40].
Comparison with other biomass thermochemical
gasification such as air gasification or steam
gasification, the supercritical water gasification can
directly deal with the wet biomass without drying,
and have high gasification efficiency in lower
temperature. The cost of H2 production from
supercritical water gasification of wet biomass was
several times higher than the current price of H2
from steam CH4 reforming. Biomass was gasified in
supercritical water at a series of temperature and
pressure during different resident times to form a
product gas composed of H2, CO2, CO, CH4, and a
small amount of C2H4 and C2H6 [41].
The yield of H2 from conventional pyrolysis of
corncob increases from 33% to 40% with increasing
of temperature from 775 to 1025 K. The yields of H2
from steam gasification increase from 29% to 45%
for (water/solid) ¼ 1 and from 29% to 47% for
(water/solid) ¼ 2 with increasing of temperature
from 975 to 1225 K. Fig. 4 shows comparisons
for the yield of H2 from supercritical fluid extrac-
tion (SFE), pyrolysis and steam gasification [(water/
solid) ¼ 2] of beech wood at different tempera-
tures. Distilled water was used in the SFE (the
critical temperature of pure water is 647.7 K). From
Fig. 4, the yield of H2 from SFE was considerably
high (49%) at lower temperatures. The pyro-
lysis was carried out at the moderate temperatures
and steam gasification at the highest temperatures
[42].

6 A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18
50
45
Yield of hydrogen, vol.%
40
35
30
25
20
15
10
600 700 800 900 1000
Temperature, K
Fig. 4. Plots for yield of hydrogen from supercritical fluid (water)
extraction, pyrolysis and steam gasification [(water/solid) ¼ 2] of
beech wood at different temperatures. Source: Ref. [42].
3.2. Fuels from bio-syngas via Fisher– Tropsch
synthesis (FTS)
The FTS for the production of liquid hydro-
carbons from coal-based synthesis gas has been the
subject of renewed interest for conversion of coal
and natural gas to liquid fuels [43]. The use of iron-
based catalysts is attractive due to their high FTS
activity as well as their WGS reactivity, which helps
make up the deficit of H2 in the syngas from modern
energy-efficient coal gasifiers [44]. The FTS for the
production of transportation fuels and other che-
micals from synthesis has attracted much attention
due to the pressure from oil supply [45]. The interest
in use of iron-based catalysts stems from its
relatively low cost and excellent WGS reaction
activity, which helps to make up the deficit of H2 in
the syngas from coal gasification [46–48]. Hydro-
carbon synthesis from biomass-derived syngas (bio-
syngas) has been investigated as a potential way to
use biomass [49]. Only biomass offers the possibility
to produce liquid, carbon neutral, transportation
fuels [50]. The FTS is used to produce chemicals,
gasoline and diesel fuel. The FT products are
predominantly linear hence the quality of the diesel
fuel is very high. Since purified synthesis gas is used
in the FTS all the products are S- and N-free [51].
Suitable economic conditions given, the FTS is an
alternative route to liquid fuels and chemicals.
Being S- and N-free and low in aromatics, the fuels
are more environment friendly than those produced
from crude oil. In particular, the production of
environment friendly high-quality diesel fuel is an
attractive application of the FTS [52].
The FTS-based gas to liquids (GTL) technology
includes the three processing steps namely syngas
ARTICLE IN PRESS
generation, syngas conversion and hydroprocessing.
In order to make the GTL technology more cost-
effective, the focus must be on reducing both the
capital and the operating costs of such a plant [53].
For some time now the price has been up to $60 per
barrel. It has been estimated that the FT process
Supercritical fluid
extraction should be viable at crude oil prices of about
Conventional pyrolysis $20 per barrel [54,55]. The current commercial
Steam gasification applications of the FT process are geared at the
production of the valuable linear a olefins and of
1100 1200 fuels such as LPG, gasoline, kerosene and diesel.
Since the FT process produces predominantly
linear hydrocarbons the production of high-quality
diesel fuel is currently of considerable interest
[56]. The most expensive section of an FT complex
is the production of purified syngas and so its
composition should match the overall usage ratio of
the FT reactions, which in turn depends on the
product selectivity [57]. The industrial application
of the FT process started in Germany and by 1938
there were nine plants in operation having a
combined capacity of about 660  103 t per year
[58].
According to operating conditions the FTS
always produces a wide range of olefins, paraffins
and oxygenated products (alcohols, aldehydes, acids
and ketones). The variables that influence the
spread of the products are temperature, feed gas
composition, pressure, catalyst type and promoters
[57].
The high-temperature fluidized bed FT reactors
with iron catalyst are ideal for the production of
large amounts of linear-olefins. As petrochemicals
they sell at much higher prices than fuels. The olefin
content of the C3, C5–C12 and C13–C18 cuts are
typically 85%, 70% and 60%, respectively [57].
The Al2O3/SiO2 ratio has significant influences on
iron-based catalyst activity and selectivity in the
process of FTS. Product selectivities also change
significantly with different Al2O3/SiO2 ratios. The
selectivity of low molecular weight hydrocarbons
increases and the olefin to paraffin ratio in the
products shows a monotonic decrease with increas-
ing Al2O3/SiO2 ratio. Table 1 shows the effects of
Al2O3/SiO2 ratio on hydrocarbon selectivity [47].
Recently, Jun et al. [48] studied FTS over Al2O3 and
SiO2 supported iron-based catalysts from biomass-
derived syngas. They found that Al2O3 as a
structural promoter facilitated the better dispersion
of copper and potassium and gave much higher FTS
activity. The reaction results from FTS with
balanced syngas are given in Table 2 [48].
 ARTICLE IN PRESS
A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18 7

Table 1
Effects of Al2O3/SiO2 ratio on hydrocarbon selectivity

Hydrocarbon 100Fe/6Cu/5K/ 100Fe/6Cu/5K/ 100Fe/6Cu/5K/ 100Fe/6Cu/5K/ 100Fe/6Cu/5K/ 100Fe/6Cu/5K/

selectivities 25SiO2 3Al2O3/22SiO2 5Al2O3/20SiO2 7Al2O3/18SiO2 10Al2O3/15SiO2 25Al2O3
(wt%)

CH4 6.3 8.7 10.4 10.7 14.3 17.3

C2–4 24.5 27.8 30.8 29.9 33.4 46.5
C5–11 26.8 27.6 32.2 33.9 40.0 31.0
C12–18 21.9 21.2 15.8 15.0 6.0 4.9
C19+ 20.5 14.4 11.0 10.6 6.1 0.4

Reaction condition: 523 K, 2.0 MPa, H2/CO ¼ 2.0, and gas stream velocity: 2000 h1.
Source: Ref. [47].

Table 2
Reaction results from FTS with balanced syngas (H2-supplied bio-syngas)

Conversion (%) Hydrocarbon distribution (C mol %) Olefin selectivity (%) in C2–C4

CO CO2 CO+CO2 CH4 C2–C4 C5–C7 C8+

82.9 0.3 21.2 12.6 39.2 21.9 26.3 84.9

88.2 28.9 43.6 13.8 37.7 22.2 26.4 84.0

Reaction conditions: Fe/Cu/Al/K (100/6/16/4), CO/CO2/Ar/H2 (6.3/19.5/5.5/69.3), 1 MPa, 573 K and 1800 mL/(gcat h).
Source: Ref. [48].

More recently, there has been some interest in the
use of FTS for biomass conversion to synthetic
hydrocarbons. The bio-syngas consists mainly of
H2, CO, CO2 and CH4. Although the composition
of bio-syngas is not suitable for direct using in the
FTS, it can be tailored by CH4 reforming, WGS
reaction and CO2 removal. To maximize the
utilization of C sources, the steam reforming of
bio-syngas with additional natural gas feedstock can
be considered [58–62]. Hydrocarbon synthesis from
bio-syngas has been investigated as a potential way
to use biomass. The FTS has been carried out using
CO/CO2/H2/Ar (11/32/52/5 vol%) mixture as a
model for bio-syngas on co-precipitated Fe/Cu/K,
Fe/Cu/Si/K and Fe/Cu/Al/K catalysts in a fixed bed
reactor. Some performances of the catalysts that
depended on the syngas composition are also
presented [48].
To produce bio-syngas from a biomass fuel the
following procedures are necessary: (a) Gasification
of the fuel; (b) Cleaning of the product gas; (c)
Usage of the synthesis gas to produce chemicals;
and (d) Usage of the synthesis gas as energy carrier
in fuel cells. Fig. 5 shows the production of diesel
fuel from bio-syngas by FTS. Bio-syngas is a gas
rich in CO and H2 obtained by gasification of
biomass. Biomass can be converted to bio-syngas by
non-catalytic, catalytic and steam gasification pro-
cesses. The composition of bio-syngas from biomass
gasification is given in Table 3.
The FTS was established in 1923 by German
scientists Franz Fisher and Hans Tropsch. The main
aim of FTS is synthesis of long-chain hydrocarbons
from CO and H2 gas mixture. The FTS is described
by the set of equations [63,64]:
Basic FTS reactions:
nCO þ 2nH2 ! ð2CH2 2Þ þ nH2 O; (4)
nCO þ ð2n þ 1ÞH2 ! Cn H2nþ1 þ nH2 O; (5)
nCO þ ðn þ m=2ÞH2 ! Cn Hm þ nH2 O; (6)
where n is the average length of the hydrocarbon
chain and m is the number of H2 atoms per carbon.
All reactions are exothermic and the product is a
mixture of different hydrocarbons in that paraffin
and olefins are the main parts.
Cobalt (Co) catalysts have the advantage of a
higher conversion rate. The Co catalysts are in
general more reactive for hydrogenation and
produce therefore less unsaturated hydrocarbons
and alcohols compared to iron catalysts. In the FTS
 ARTICLE IN PRESS
8 A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18

BIOMASS STEAM GASIFICATION

AND REFORMING

BIO-SYNGAS

GAS CLEANING AND

CONDITIONING

FISHER-TROPSCH SYNTHESIS

GASOLINE LIKE FUELS

PRODUCT UPGRADE AND REFINING
(By products)

DIESEL FUEL
(Main product)

Fig. 5. Production of diesel fuel from bio-syngas by Fischer–Tropsh synthesis.

Table 3 Typical operation conditions for the FTS are a

Composition of bio-syngas from biomass gasification temperature range of 475–625 K and pressures of
Constituents % by volume (dry and nitrogen free)
15–40 bar, depending on the process. The kind and
quantity of liquid product obtained is determined
Carbon monoxide (CO) 28–36 by the reaction temperature, pressure and residence
Hydrogen (H2) 22–32 time, the type of reactor, and the catalyst used.
Carbon dioxide (CO2) 21–30
Catalysts and reactors have been extensively in-
Methane (CH4) 8–11
Ethene (C2H4) 2–4 vestigated for liquid phase FTS [66–68]. Iron
catalysts have a higher tolerance for sulfur, are
cheaper, and produce more olefin products and
alcohols. However, the lifetime of the Fe catalysts is
short and in commercial installations generally
one mole of CO reacts with two moles of H2 in the limited to 8 weeks.
presence Co-based catalyst to afford a hydrocarbon The design of a biomass gasifier integrated with a
chain extension (–CH2–). The reaction of synthesis FTS reactor must be aimed at achieving a high yield
is exothermic (DH ¼ 165 kJ/mol): of liquid hydrocarbons. For the gasifier, it is
important to avoid CH4 formation as much as
CO þ 2H2 ! 2CH2 2 þ H2 O DH ¼ 165 kJ=mol:
possible, and convert all carbon in the biomass to
(7) mainly CO and CO2 [67]. The gas cleaning is an
The –CH2– is a building stone for longer hydro- important process before FTS. Gas cleaning is even
carbons. A main characteristic regarding the per- more important for the integration of a biomass
formance of the FTS is the liquid selectivity of the gasifier and a catalytic reactor. To avoid poisoning
process [65]. For this reaction given with Eq. (7) is of FTS catalyst, tar, hydrogen sulfide, carbonyl
necessary a H2/CO ratio of at least 2 for the sulfide, ammonia, hydrogen cyanide, alkali and dust
synthesis of the hydrocarbons. When iron (Fe)- particles must be removed thoroughly [65].
based catalysts are used with WGS reaction activity Synthetic FTS diesel fuels can have excellent
the water produced in the reaction (2) can react with autoignition characteristics. The FTS diesel is
CO to form additional H2. The reaction of synthesis composed of only straight chain hydrocarbons and
is exothermic (DH ¼ 204 kJ/mol). In this case a has no aromatics or sulfur. Reaction parameters are
minimal H2/CO ratio of 0.7 is required: temperature, pressure and H2/CO ratio. FTS
product composition strongly influenced by catalyst
2CO þ H2 ! 2CH2 2 þ CO2 DH ¼ 204 kJ=mol: composition: product from Co catalyst higher in
paraffins and product from Fe catalyst higher in
(8) olefins and oxygenates [69].
 ARTICLE IN PRESS
A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18
4. Bioethanol
Carbohydrates (hemicelluloses and cellulose) in
plant materials can be converted to sugars by
hydrolysis process. Fermentation is an anaerobic
biological process in which sugars are converted to
alcohol by the action of microorganisms, usually
yeast. The resulting alcohol is ethanol. The value of
any particular type of biomass as feedstock for
fermentation depends on the ease with which it can
be converted to sugars.
Anaerobic digestion of bio-wastes occurs in the
absence of air, the resulting gas called as biogas, is a
mixture consisting mainly of CH4 and CO2. Biogas
is a valuable fuel which is produced in digesters
filled with the feedstock like dung or sewage. The
digestion is allowed to continue for a period of from
10 days to a few weeks [69].
Cellulose is a remarkable pure organic polymer,
consisting solely of units of anhydro glocose held
together in a giant straight chain molecule. Cellu-
lose must be hydrolyzed to glucose before fermenta-
tion to ethanol. Conversion efficiencies of cellulose
to glucose may be dependent on the extent of
chemical and mechanical pretreatments to structu-
rally and chemically alter the pulp and paper mill
wastes. The method of pulping, the type of wood,
and the use of recycled pulp and paper products also
could influence the accessibility of cellulose to
cellulase enzymes [70]. Cellulose is insoluble in most
solvents and has a low accessibility to acid and
enzymatic hydrolysis. Hemicelluloses (arabinoglycur-
onoxylan and galactoglucomammans) are related to
plant gums in composition, and occur in much
shorter molecule chains than cellulose. The hemi-
celluloses, which are present in deciduous woods
chiefly as pentosans and in coniferous woods almost
entirely as hexosanes, undergo thermal decomposi-
tion very readily. Hemicelluloses are derived mainly
from chains of pentose sugars, and act as the cement
material holding together the cellulose micells and
fiber [71]. Hemicelluloses are largely soluble in alkali
and, as such, are more easily hydrolyzed.
Bioethanol is a fuel derived from renewable
sources of feedstock; typically plants such as wheat,
sugar beet, corn, straw, and wood. Bioethanol is a
petrol additive/substitute. It is possible that wood,
straw and even household wastes may be economic-
ally converted to bioethanol. Table 4 shows ethanol
production in different continents [72].
Bioethanol can be used as a 5% blend with petrol
under the EU quality standard EN 228. This blend
9
Table 4
Ethanol production in different continents (billion liters/year)
America Asia Europe Africa Oceania
22.3 5.7 4.6 0.5 0.2
Source: Ref. [74].
requires no engine modification and is covered by
vehicle warranties. With engine modification,
bioethanol can be used at higher levels, for example,
E85 (85% bioethanol).
Bioethanol can be produced from a large variety
of carbohydrates with a general formula of
(CH2O)n. Fermentation of sucrose is performed
using commercial yeast such as Saccharomyces
ceveresiae. Chemical reaction is composed of enzy-
matic hydrolysis of sucrose followed by fermenta-
tion of simple sugars [73]. First, invertase enzyme in
the yeast catalyzes the hydrolysis of sucrose to
convert it into glucose and fructose.
C12 H22 O11 ! C6 H12 O6 þ C6 H12 O6 . (9)
Sucrose Glucose Fructose
Second, zymase, another enzyme also present in the
yeast, converts the glucose and the fructose into
ethanol.
C6 H12 O6 ! 2C2 H5 OH þ 2CO2 : (10)
Gluco-amylase enzyme converts the starch into D-
glucose. The enzymatic hydrolysis is then followed
by fermentation, distillation and dehydration to
yield anhydrous bioethanol. Corn (60–70% starch)
is the dominant feedstock in starch-to-bioethanol
industry worldwide.
Carbohydrates (hemicelluloses and cellulose) in
lignocellulosic materials can be converted to
bioethanol. The lignocellulose is subjected to
delignification, steam explosion and dilute acid
pre-hydrolysis, which is followed by enzymatic
hydrolysis and fermentation into bioethanol
[74–77]. A major processing step in an ethanol
plant is enzymatic saccharification of cellulose to
sugars through treatment by enzymes; this step
requires lengthy processing and normally follows a
short-term pretreatment step [78]. Fig. 6 shows the
flow chart for the production of bioethanol from
cereal grain or straw.
Hydrolysis breaks down the H2 bonds in the
hemicellulose and cellulose fractions into their sugar
components: pentoses and hexoses. These sugars
can then be fermented into bioethanol. The most
commonly applied methods can be classified in two
 ARTICLE IN PRESS
10 A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18
CEREAL GRAIN OR STRAW
Course powder flour
Acid hydrolysis, fermentation and distillation
Crude alcohol Stillage
Dehydratio Drying
BIOETHANOL Animal feed
Fig. 6. Flow chart for the production bioethanol from cereal
grain or straw.
groups: chemical hydrolysis (dilute and concen-
trated acid hydrolysis) and enzymatic hydrolysis. In
the chemical hydrolysis, the pretreatment and the
hydrolysis may be carried out in a single step. There
are two basic types of acid hydrolysis processes
commonly used: dilute acid and concentrated acid.
The biggest advantage of dilute acid processes is
their fast rate of reaction, which facilitates contin-
uous processing. Since 5-carbon sugars degrade
more rapidly than 6-carbon sugars, one way to
degrade sugar degradation is to have a two-stage
process. The first stage is conducted under mild
process conditions to recover the 5-carbon sugars
while the second stage is conducted under harsher
conditions to recover the 6-carbon sugars.
Concentrated sulfuric or hydrochloric acids are
used for hydrolysis of lignocellulosic materials. The
concentrated acid process uses relatively mild
temperatures, and the only pressures involved are
those created by pumping materials from vessel to
vessel. Reaction times are typically much longer
than for dilute acid. This process provides a
complete and rapid conversion of cellulose to
glucose and hemicelluloses to 5-carbon sugars with
little degradation. The critical factors needed to
make this process economically viable are to
optimize sugar recovery and cost effectively re-
covers the acid for recycling. The solid residue from
the first stage is dewatered and soaked in a 30–40%
concentration of sulfuric acid for 1–4 h as pre-
cellulose hydrolysis step. The solution is again
dewatered and dried, increasing the acid concentra-
tion to about 70%. After reacting in another vessel
for 1–4 h at low temperatures, the contents are
separated to recover the sugar and acid. The sugar/
acid solution from the second stage is recycled to the
first stage to provide the acid for the first stage
hydrolysis [69].
The primary advantage of the concentrated acid
process is the potential for high sugar recovery
efficiency. The acid and sugar are separated via ion
exchange and then acid is re-concentrated via
multiple effect evaporators.
5. Biodiesel
Vegetable oil (m)ethyl esters, commonly referred
to as ‘‘biodiesel,’’ are prominent candidates as
alternative diesel fuels. The name biodiesel has been
given to transesterified vegetable oil to describe its
use as a diesel fuel [79]. There has been renewed
interest in the use of vegetable oils for making
biodiesel due to its less polluting and renewable
nature as against the conventional diesel, which is a
fossil fuel leading to a potential exhaustion [80].
Biodiesel is technically competitive with or offer
technical advantages compared to conventional
petroleum diesel fuel. The vegetable oils can be
converted to their (m)ethyl esters via transesterifica-
tion process in the presence of catalyst. Methyl,
ethyl, 2-propyl and butyl esters were prepared from
vegetable oils through transesterification using
potassium and/or sodium alkoxides as catalysts.
The purpose of the transesterification process is to
lower the viscosity of the oil. Ideally, transesterifica-
tion is potentially a less expensive way of transform-
ing the large, branched molecular structure of the
bio-oils into smaller, straight chain molecules of the
type required in regular diesel combustion engines.
Transesterifications of vegetable oils in super-
critical methanol are carried out without using any
catalyst. A few studies have been conducted via
non-catalytic transesterification with supercritical
methanol (SCM) [81–87]. Saka and Kusdiana [82]
and Demirbas [79] have firstly proposed that
biodiesel fuels may be from vegetable oil. A novel
process of biodiesel fuel production has been
developed by a non-catalytic supercritical methanol
method. Compared with the catalytic processes
under barometric pressure, the supercritical metha-
nol process is non-catalytic, purification of products
is much simpler, shorter reaction time, more
environmentally friendly and lower energy use.
However, the reaction requires temperatures of
 ARTICLE IN PRESS
A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18 11

Table 5
Comparisons between catalytic methanol (MeOH) process and supercritical methanol (SCM) method for biodiesel from vegetable oils by
transesterification

Catalytic MeOH process SCM method

Methylating agent Methanol Methanol

Catalyst Alkali (NaOH or KOH) None
Reaction temperature (K) 303–338 523–573
Reaction pressure (MPa) 0.1 10–25
Reaction time (min) 60–360 7–15
Methyl ester yield (wt%) 96 98
Removal for purification Methanol, catalyst, glycerol, soaps Methanol
Free fatty acids Saponified products Methyl esters, water
Smelling from exhaust Soap smelling Sweet smelling

525–675 K and pressures of 35–60 MPa [82,84].

Table 5 shows the comparisons between catalytic
methanol process and supercritical methanol meth-
od for biodiesel from vegetable oils by transester-
ification. Fig. 7 shows non-catalytic biodiesel
production in supercritical alcohol.
The most important variables affecting the
methyl ester yield during the transesterification
reaction are molar ratio of alcohol to vegetable oil
and reaction temperature. Biodiesel has become
more attractive recently because of its environmen-
tal benefits. The viscosity values of vegetable oils are
between 27.2 and 53.6 mm2/s whereas those of
vegetable oil methyl esters are between 3.59 and
4.63 mm2/s [86,87]. The flash point values of
vegetable oil methyl esters are highly lower than
those of vegetable oils. Biodiesel is an environmen-
tally friendly fuel that can be used in any diesel
engine without modification.
The bio-diesel esters were characterized for their
physical and fuel properties including density,
viscosity, iodine value, acid value, cloud point, pour
point, gross heat of combustion and volatility. The
biodiesel fuels produced slightly lower power and
torque, and higher fuel consumption than no. 2
diesel fuel. Biodiesel is better than diesel fuel in
terms of sulfur content, flash point, aromatic
content and biodegradability [88].
If the biodiesel valorized efficiently at energy
purpose, so would be benefit for the environment
and the local population, job creation, provision of
modern energy carriers to rural communities, avoid
urban migration and reduction of CO2 and sulfur
levels in the atmosphere.
The cost of biodiesels varies depending on the
base stock, geographic area, variability in crop
production from season to season, the price of the
Vegetable oil
Methanol High Pressure Reactor
Biodiesel
Fig. 7. Non-catalytic biodiesel production in supercritical
alcohol.
crude petroleum and other factors. Biodiesel has
over double the price of petroleum diesel. The high
price of biodiesel is in large part due to the high
price of the feedstock. However, biodiesel can be
made from other feedstocks, including beef tallow,
pork lard, and yellow grease [86].
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 [88,89]. The vegetable oil
fuels were not acceptable because they were more
expensive than petroleum fuels. With recent in-
creases in petroleum prices and uncertainties con-
cerning petroleum availability, there is renewed
interest in vegetable oil fuels for diesel engines.
Most of the biodiesel that is currently made uses
soybean oil, methanol, and an alkaline catalyst. The
high value of soybean oil as a food product makes
production of a cost-effective fuel very challenging.
However there are large amounts of low-cost oils
and fats such as restaurant waste and animal fats
that could be converted to biodiesel. The problem
with processing these low-cost oils and fats is that
they often contain large amounts of free fatty acids
 ARTICLE IN PRESS
12 A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18
(FFA) that cannot be converted to biodiesel using
an alkaline catalyst [84,90].
A review of 12 economic feasibility studies shows
that the projected costs for biodiesel from oilseed or
animal fats have a range US$0.30–0.69/l, including
meal and glycerin credits and the assumption of
reduced capital investment costs by having the
crushing and/or esterification facility added onto an
existing grain or tallow facility. Rough projections
of the cost of biodiesel from vegetable oil and waste
grease are, respectively, US$0.54–0.62/l and
US$0.34–0.42/l. With pre-tax diesel priced at
US$0.18/l in the US and US$0.20–0.24/l in some
European countries, biodiesel is thus currently not
economically feasible, and more research and
technological development will be needed [84,91].
6. Biomethanol
Methanol can be used as one possible replace-
ment for conventional motor fuels. It has been seen
as a possible large volume motor fuel substitute at
various times during gasoline shortages. It was often
used in the early part of the century to power
automobiles before inexpensive gasoline was widely
introduced. Synthetically produced methanol was
widely used as a motor fuel in Germany during the
World War. Methanol is commonly used in
biodiesel production for its reactivity. Methanol
can be used as one possible replacement for
conventional motor fuels. The use of methanol as
a motor fuel received attention during the oil crises
of the 1970s due to its availability and low cost.
Problems occurred early in the development of
gasoline–methanol blends. As a result of its low
price some gasoline marketers over blended. Many
tests have shown promising results using 85–100%
by volume methanol as a transportation fuel in
automobiles, trucks and buses (Table 6).
Methanol, also known as ‘‘wood alcohol.’’
Sustainable methods of methanol production are
currently not economically viable. Methanol is
Table 6
Main production facilities of methanol and biomethanol
Methanol
Catalytic synthesis from CO and H2
Natural gas
Petroleum gas
Distillation of liquid from coal pyrolysis
produced from synthetic gas or biogas and evalu-
ated as a fuel for internal combustion engines. The
production of methanol is a cost-intensive chemical
process. Therefore, in current conditions, only waste
biomass such as old wood or bio-waste is used to
produce methanol [92].
Methanol is poisonous and burns with an
invisible flame. Methanol has just like ethyl alcohol
a high octane rating and hence an Otto engine is
preferable. Most processes require supplemental
oxygen for the intermediate conversion of the
biomass into a synthesis gas (H2+CO). A readily
available supply of H2 and oxygen, therefore,
should improve the overall productivity of bio-
mass-derived methanol [93].
Before modern production technologies were
developed in the 1920s, methanol was obtained
from wood as a co-product of charcoal production
and, for this reason, was commonly known as wood
alcohol. Methanol is currently manufactured world-
wide by conversion or derived from syngas, natural
gas, refinery off-gas, coal or petroleum:
2H2 þ CO ! CH3 OH: (11)
The chemical composition of syngas from coal
and then from natural gas can be identical with the
same H2/CO ratio. A variety of catalysts are
capably of causing the conversion, including re-
duced NiO-based preparations, reduced Cu/ZnO
shift preparations, Cu/SiO2 and Pd/SiO2, and Pd/
ZnO [94,95].
Methanol is currently made from natural gas but
can also be made using biomass via partial
oxidation reactions [96]. Biomass and coal can be
considered as a potential fuel for gasification and
further syngas production and methanol synthesis
[95]. Adding sufficient H2 to the synthesis gas to
convert all of the biomass into methanol carbon
than double the methanol produced from the same
biomass base [97]. Waste material can be partially
converted to methanol, which the product yield for
the conversion process is estimated to be 185 kg of
methanol per metric ton of solid waste [98,99].
Biomethanol
Catalytic synthesis from CO and H2
Distillation of liquid from wood pyrolysis
Gaseous products from biomass gasification
Synthetic gas from biomass and coal
 ARTICLE IN PRESS
A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18
Agriculture-(m)ethanol is at present more expensive
of synthesis ethanol from ethylene and of methanol
from natural gas [100].
Biomass resources can be used to produce
methanol. The pyroligneous acid obtained from
wood pyrolysis consists of about 50% methanol,
acetone, phenols and water [98,101]. As a renewable
resource, biomass represents a potentially inexhaus-
tible supply of feedstock for methanol production.
The composition of bio-syngas from biomass for
producing methanol is presented in Table 3. Current
natural gas feedstocks are so inexpensive that even
with tax incentives renewable methanol has not
been able to compete economically. Technologies
are being developed that may eventually result in
commercial viability of renewable methanol.
Methanol from coal could be a very important
source of liquid fuel in the future. The coal is first
pulverized and cleaned, then fed to a gasifier bed
where it is reacted with oxygen and steam to
produce the syngas. Once these steps have been
taken, the production process is much the same as
with the other feedstocks with some variations in
the catalyst used and the design of the converter
vessel in which the reaction is carried out. Methanol
made using synthesis gas (syngas) with H2 and CO
in a 2:1 ratio (Table 3). The syngas was transformed
to methanol in a fixed catalyst bed reactor. Coal-
derived methanol has many preferable properties as
free of sulfur and other impurities, could replace
petroleum in transportation, or be used as a peaking
fuel in combustion turbines, or supply a source of
H2 for fuel cells. The technology for making
methanol from natural gas is already in place and
requires only efficiency improvements and scale-up
to make methanol an economically viable alter-
native transportation fuel [102].
In recent years, a growing interest has been
observed in the application of methanol as an
alternative liquid fuel, which can be used directly for
powering Otto engines or fuel cells [103]. The
feasibility of achieving the conversion has been
demonstrated in a large-scale system in which a
product gas is initially produced by pyrolysis and
gasification of a carbonaceous matter. Syngas from
biomass is altered by catalyst under high pressure
and temperature to form methanol. This method
will produce 100 gallons of methanol per ton of feed
material [104].
The gases produced can be steam reformed to
produce H2 and followed by WGS reaction to
further enhance H2 production. When the moisture
13
content of biomass is higher than 35%, it can be
gasified in a supercritical water condition [105].
Supercritical water gasification is a promising
process to gasify biomass with high moisture
contents due to high gasification ratio (100%
achievable) and high H2 volumetric ratio (50%
achievable) [106–108]. H2 produced by biomass
gasification was reported to be comparable to that
by natural gas reforming [109]. The process is more
advantageous than fossil fuel reforming in consid-
eration of environmental benefits. It is expected that
biomass thermochemical conversion will be one of
the most economical large-scale renewable H2
technologies.
The strategy is based on producing H2 from
biomass pyrolysis using a co-product strategy to
reduce the cost of H2 and concluded that only this
strategy could compete with the cost of the
commercial hydrocarbon-based technologies [110].
This strategy will demonstrate how H2 and bio-fuel
are economically feasible and can foster the devel-
opment of rural areas when practiced on a larger
scale. The process of biomass to activated carbon is
an alternative route to H2 with a valuable co-
product that is practiced commercially [111].
The simultaneous production of bio-methanol
(obtained by the hydrogenation of CO2 developed
during the fermentation of sugar juice), in parallel
to the production of bio-ethanol, appears economic-
ally attractive in locations where hydro-electricity is
available at very low cost (0.01$ KWh) and where
lignocellulosic residues are available as surpluses.
The gas is converted to methanol in a conven-
tional steam-reforming/WGS reaction followed by
high-pressure catalytic methanol synthesis:
CH4 þ H2 O ! CO þ 3H2 : (12)
CO þ H2 O ! CO2 þ H2 : (13)
Eqs. (12) and (13) are called as gasification/shift
reactions.
CO þ 2H2 ! CH3 OH (14)
or
CO2 þ 3H2 ! CH3 OH þ H2 O: (15)
Eqs. (14) or (15) are methanol synthesis reactions.
Fig. 8 shows production of biomethanol from
carbohydrates by gasification and partial oxidation
with O2 and H2O.
The energy value of residues generated worldwide
in agriculture and the forest-products industry
 ARTICLE IN PRESS
14 A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18
CARBOHYDRATES
(CH2O)n
Drying and Crushing into Powder
Gasification and Partial Oxidation with O2 and H2O
Temperature: 1250 K
Mixture of Gases: H2, CO, CO2, H2O
Catalytic Synthesis: CO + 2H2 → CH3OH
Pressure: 4-8 MPa
BIOMETHANOL
Fig. 8. Biomethanol from carbohydrates by gasification and
partial oxidation with O2 and H2O.
amounts to more than one-third of the total
commercial primary energy use at present [112].
Bio-energy supplies can be divided into two broad
categories: (a) organic municipal waste and residues
from the food and materials sectors; and (b)
dedicated energy crops plantations. Bio-energy
from biomass, both residues and energy crops, can
be converted into modern energy carriers such as
H2, methanol, ethanol or electricity [113].
Methanol can be produced from biomass essen-
tially any primary energy source. Thus, the choice of
fuel in the transportation sector is to some extent
determined by the availability of biomass. As
regards the difference between H2 and methanol
production costs, conversion of natural gas, bio-
mass and coal into H2 is generally more energy
efficient and less expensive than conversion into
methanol [113].
7. Bio-oil
The term bio-oil is used mainly to refer to liquid
fuels. There are several reasons for bio-oils to be
considered as relevant technologies by both devel-
oping and industrialized countries. They include
energy security reasons, environmental concerns,
foreign exchange savings, and socioeconomic issues
related to the rural sector.
Bio-oils are liquid or gaseous fuels made from
biomass materials, such as agricultural crops,
municipal wastes and agricultural and forestry by-
products via biochemical or thermochemical pro-
cesses. They can substitute conventional fuels in
vehicle engines—either totally or partially in a blend
[114]. The organic fraction of almost any form of
biomass, including sewage sludge, animal wastes
and industrial effluents, can be broken down
through anaerobic digestion into CH4 and CO2
mixture called as ‘‘biogas’’ [115]. Biogas is an
environment friendly, clean, cheap and versatile
fuel [116].
Pyrolysis/cracking, defined as the cleavage to
smaller molecules by thermal energy. H2 can be
produced economically from woody biomass [117].
Biomass can be thermally processed through
gasification or pyrolysis to produce H2. The main
gaseous products from biomass are the following
[118–122]:
Pyrolysis of biomass ! H2 þ CO2 þ CO
þ Gaseous and liquid hydrocarbons; (16)
Catalytic steam reforming of biomass
! H2 þ CO2 þ CO; (17)
FTS of ðH2 þ COÞ
! Gaseous and liquid hydrocarbons: (18)
The conventional pyrolysis of biomass is asso-
ciated with the product of interest that is the high
charcoal content, but the fast pyrolysis is associated
with the products of interest are tar, at low
temperature (675–775 K) [123–126], and/or gas, at
high temperature [127].
8. Conclusion
The term biofuel is referred to as liquid fuels for
the transport sector that are predominantly pro-
duced from biomass. Biofuels include energy
security reasons, environmental concerns, foreign
exchange savings, and socioeconomic issues related
to the rural sector. The Fischer–Tropsch synthesis
(FTS) uses various catalysts to produce linear
hydrocarbons and oxygenates, including unrefined
gasoline, diesel, and wax ranges. Co catalysts have
the advantage of a higher conversion rate and a
longer life. The Co catalysts are in general more
reactive for hydrogenation and produce therefore
less unsaturated hydrocarbons and alcohols com-
pared to iron catalysts.
 ARTICLE IN PRESS
A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18
Most traditional biofuels, such as ethanol from
corn, wheat, or sugar beets, and biodiesel from oil
seeds, are produced from classic agricultural food
crops that require high-quality agricultural land for
growth. Bioethanol is a petrol additive/substitute.
Bioethanol can be produced from plentiful, domes-
tic, cellulosic biomass resources such as herbaceous
and woody plants, agricultural and forestry resi-
dues, and a large portion of municipal solid waste
and industrial waste streams. Production of
bioethanol from biomass is one way to reduce both
the consumption of crude oil and environmental
pollution.
Biodiesel is an environmentally friendly alterna-
tive liquid fuel that can be used in any diesel engine
without modification. There has been renewed
interest in the use of vegetable oils for making
biodiesel due to its less polluting and renewable
nature as against the conventional petroleum diesel
fuel. Due to its environmental merits, the share of
biofuel in the automotive fuel market will grow fast
in the next decade. There are several reasons for
biofuels to be considered as relevant technologies by
both developing and industrialized countries.
References
[1] Reijnders L. Conditions for the sustainability of biomass
based fuel use. Energy Policy 2006;34:863–76.
[2] Türe S, Uzun D, Ture IE. The potential use of sweet
sorghum as a non-polluting source of energy. Energy
1997;22:17–9.
[3] Sheehan J, Cambreco V, Duffield J, Garboski M, Shapouri
H. An overview of biodiesel and petroleum diesel life
cycles. A report by US Department of Agriculture and
Energy, 1998. p. 1–35.
[4] Puhan S, Vedaraman N, Rambrahaman BV, Nagarajan G.
Mahua (Madhuca indica) seed oil: a source of renewable
energy in India. J Sci Ind Res 2005;64:890–6.
[5] Ozcimen D, Karaosmanoglu F. Production and character-
ization of bio-oil and biochar from rapeseed cake. Renew
Energy 2004;29:779–87.
[6] Jefferson M. Sustainable energy development: performance
and prospects. Renew Energy 2006;31:571–82.
[7] Cadenas A, Cabezudo S. Biofuels as sustainable technol-
ogies: perspectives for less developed countries. Technol
Forecast Social Change 1998;58:83–103.
[8] Difiglio C. Using advanced technologies to reduce motor
vehicle greenhouse gas emissions. Energy Policy 1997;25:
1173–8.
[9] Demirbas A. Biomass resources for energy and chemical
industry. Energy Edu Sci Technol 2000;5:21–45.
[10] Puppan D. Environmental evaluation of biofuels. Period
Polytech Ser Soc Man Sci 2002;10:95–116.
[11] Wang D, Czernik S, Montané D, Mann M, Chornet E.
Biomass to hydrogen via pyrolysis and catalytic steam
15
reforming of the pyrolysis oil and its fractions. IEC Res
1997;36:1507–18.
[12] Wang D, Czernik S, Chornet E. Production of hydrogen
from biomass by catalytic steam reforming of fast pyrolysis
oils. Energy Fuels 1998;12:19–24.
[13] Czernik S, French R, Feik C, Chornet E. Production of
hydrogen from biomass by pyrolysis/steam reforming. In:
Gregoire-Padró C, Lau F, editors. Advances in hydrogen
energy. New York: Kluwer Academic/Plenum Publishers;
2000. p. 87–91.
[14] Demirbas A. Yields of hydrogen-rich gaseous products via
pyrolysis from selected biomass samples. Fuel 2001;80:
1885–91.
[15] Demirbas A. Hydrogen production via pyrolytic degrada-
tion of agricultural residues. Energy Sources 2005;27:
769–75.
[16] Demirbas A. Hydrogen-rich gas from fruit shells via
supercritical water extraction. Int J Hydrogen Energy
2004;29:1237–43.
[17] Prins MJ, Ptasinski KJ, Janssen FJJG. Exergetic optimisa-
tion of a production process of Fischer–Tropsch fuels from
biomass. Fuel Proc Technol 2004;86:375–89.
[18] Demirbas A. Recent advances in biomass conversion
technologies. Energy Educ Sci Technol 2000;6:19–40.
[19] Mirzaei AA, Habibpour R, Faizi M, Kashi E. Character-
ization of iron-cobalt oxide catalysts: effect of different
supports and promoters upon the structure and morphol-
ogy of precursors and catalysts. Appl Catal A General
2006;301:272–83.
[20] Sie ST, Krishna R. Fundamentals and selection of
advanced FT-reactors. Appl Catal A: General 1999;186:
55–70.
[21] Ahón VR, Costa Jr EF, Monteagudo JEP, Fontes CE,
Biscaia Jr EC, Lage PLC. A comprehensive mathematical
model for the Fischer–Tropsch synthesis in well-mixed
slurry reactors. Chem Eng Sci 2005;60:677–94.
[22] Rapagna S, Jand N, Foscolo PU. Catalytic gasification of
biomass to produce hydrogen rich gas. Int J Hydrogen
Energy 1998;23:551–7.
[23] Haas MJ, McAloon AJ, Yee WC, Foglia TA. A process
model to estimate biodiesel production costs. Biores
Technol 2006;97:671–8.
[24] Prakash CB. A critical review of biodiesel as a transporta-
tıon fuel in Canada. A technical report. Canada: GCSI—
Global Change Strategies International Inc.; 1998.
[25] Demirbas A. Diesel fuel from vegetable oil via transester-
ification and soap pyrolysis. Energy Sources 2002;24:
835–41.
[26] Meher LC, Sagar DV, Naik SN. Technical aspects of
biodiesel production by transesterification—a review. Re-
new Sust Energy Rev 2006;10:248–68.
[27] Madras G, Kolluru C, Kumar R. Synthesis of biodiesel in
supercritical fluids. Fuel 2004;83:2029–33.
[28] Ali Y, Hanna MA, Cuppett SL. Fuel properties of tallow
and soybean oil esters. JAOCS 1995;72:1557–64.
[29] Usta N, Ozturk E, Can O, Conkur ES, Nas S, Con AH,
et al. Combustion of biodiesel fuel produced from hazelnut
soapstock/waste sunflower oil mixture in a Diesel engine.
Energy Convers Manage 2005;46:741–55.
[30] Taherzadeh MJ. Ethanol from lignocellulose: physiological
effects of inhibitors and fermentation strategies. PhD.
thesis, Department of Chemical Reaction Engineering,
 ARTICLE IN PRESS
16 A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18
Chalmers University of Technology, Göteborg, Sweden,
1999.
[31] UNDP (United Nations Development Programme). En-
ergy and the challange of sustainability. World energy
assessment, 2000.
[32] IEA (International Energy Agency). Biofuels for transport:
a international perspective. 9, rue de la Fédération, 75739
Paris, cedex 15, France (available from: www.iea.org),
2004.
[33] Hansen AC, Zhang Q, Lyne PWL. Ethanol–diesel fuel
blends—a review. Bioresource Technol 2005;96:277–85.
[34] Demirbas A, Arin G. An overview of biomass pyrolysis.
Energy Sources 2002;5:471–82.
[35] Tran DQ, Charanjit R. A kinetic model for pyrolysis of
Douglas fir bark. Fuel 1978;57:293–8.
[36] Mc Kendry P. Energy production from biomass (part 1):
overview of biomass. Biores Technol 2002;83:37–46.
[37] Bridgwater AV. Renewable fuels and chemicals by thermal
processing of biomass. Chem Eng J 2003;91:87–102.
[38] Maschio G, Lucchesi A, Stoppato G. Production of syngas
from biomass. Biores Technol 1994;48:119–26.
[39] Choudhary TV, Goodman DW. CO-free production of
hydrogen via stepwise steam reforming of methane. J. Catal
2000;192:316–21.
[40] Santos DCRM, Lisboa JS, Passos FB, Noronha FB.
Characterization of steam-reforming catalysts. Braz J
Chem Eng 2004;21:203–9.
[41] Demirbas A. Hydrogen rich gas from fruit shells via
supercritical water extraction. Int J Hydrogen Energy
2004;29:1237–43.
[42] Demirbas MF. Hydrogen from various biomass species via
pyrolysis and steam gasification processes. Energy Sources
Part A 2006;28:245–52.
[43] Jin Y, Datye AK. Phase transformations in iron Fischer–
Tropsch catalysts during temperature-programmed reduc-
tion. J Catal 2000;196:8–17.
[44] Rao VUS, Stiegel GJ, Cinquergrane GJ, Srivastava RD.
Iron-based catalysts for slurry-phase Fischer–Tropsch
process: technology review. Fuel Process Technol 1992;30:
83–107.
[45] Dry ME. Fischer–Tropsch reactions and the environment.
Appl Catal A 1999;189:185–90.
[46] Wu BS, Bai L, Xiang HW, Li YW, Zhang ZX, Zhong B.
An active iron catalyst containing sulfur for Fischer–
Tropsch synthesis. Fuel 2004;83:205–512.
[47] Jothimurugesan K, Goodwin JG, Santosh SK, Spivey JJ.
Development of Fe Fischer–Tropsch catalysts for slurry
bubble column reactors. Catal Today 2000;58:335–44.
[48] Jun KW, Roh HS, Kim KS, Ryu JS, Lee KW. Catalytic
investigation for Fischer–Tropsch synthesis from bio-mass
derived syngas. Appl Catal A 2004;259:221–6.
[49] Demirbas A. Global biodiesel strategies. Energy Educ Sci
Technol 2006;17:27–63.
[50] Tijmensen MJA, Faaij APC, Hamelinck CN, van Hard-
eveld MRM. Exploration of the possibilities for production
of Fischer–Tropsch liquids and power via biomass gasifca-
tion. Biomass Bioenergy 2002;23:129–52.
[51] Dry ME. High quality diesel via the Fischer–Tropsch
process—a review. J Chem Technol Biotechnol 2002;77:
43–50.
[52] Dry ME. Fischer–Tropsch reactions and the environment.
Appl Catal A General 1999;189:185–90.
[53] Vosloo AC. Fischer–Tropsch: a futuristic view. Fuel
Process Technol 2001;71:149–55.
[54] Jager B. Proceedings of the fifth natural gas conversion
symposium, Taormina, Italy. September 1998.
[55] Dry ME. Present and future applications of the Fischer–
Tropsch process. Appl Catal A: General 2004;276:1–3.
[56] Dry ME. The Fischer–Tropsch process: 1950–2000. Catal
Today 2002;71:227–41.
[57] Anderson RB. The Fischer–Tropsch synthesis. New York:
Academic Press; 1984.
[58] Dong Y, Steinberg M. Hynol—an economical process for
methanol production from biomass and natural gas with
reduced CO2 emission. Int J Hydrogen Energy 1997;22:
971–7.
[59] Specht M, Bandi A, Baumgart F, Murray CN, Gretz J. In:
Proceedings of the fourth international conference on
greenhouse gas control technologies. 1999.
[60] Larson ED, Jin H. In: Overend R, Chornet E, editors.
Proceedings of the fourth biomass conference Americas,
Kidlington, UK, 29 August. Amsterdam: Elsevier; 1999.
[61] Lee K-W, Kim S-B, Jun K-W, Choi M-J. In: Williams DJ,
Durie RA, McMullan P, Paulson CAJ, Smith AY, editors.
Proceedings of the fifth international conference green-
house gas control technology, Cairns, Australia, 13 August
2000. CSIRO; 2001.
[62] Bukur DB, Nowicki L, Manne RV, Lang X. Activation
studies with a precipitated iron catalysts for the Fischer–-
Tropsch synthesis. J Catal 1995;155:366–75.
[63] Li S, Krishnamoorthy S, Li A, Meitzner GD, Iglesia E.
Promoted iron-based catalysts for the Fischer–Tropsch
synthesis: design, synthesis, site densities, and catalytic
properties. J Catal 2002;206:202–17.
[64] Schulz H. Short history and present trends of FT synthesis.
Appl Catal A General 1999;186:1–16.
[65] Stelmachowski M, Nowicki L. Fuel from the synthesis
gas—the role of process engineering. Appl Energy 2003;74:
85–93.
[66] Davis BH. Overview of reactors for liquid phase Fischer–
Tropsch synthesis. Catal Today 2002;71:249–300.
[67] Prins MJ, Ptasinski KJ, Janssen FJJG. Exergetic optimisa-
tion of a production process of Fischer–Tropsch fuels from
biomass. Fuel Proc Technol 2004;86:375–89.
[68] Balat M. Sustainable transportation fuels from biomass
materials. Energy Edu Sci Technol 2006;17:83–103.
[69] Demirbas A. Biogas potential of manure and straw
mixtures. Energy Sources Part A 2006;28:71–8.
[70] Adeeb Z. Glycerol delignification of poplar wood chips in
aqueous medium. Energy Educ Sci Technol 2004;13:81–8.
[71] Theander O. In: Overand RP, Mile TA, Mudge LK,
editors. Fundamentals of thermochemical biomass conver-
sion. New York: Elsevier Applied Science Publisher; 1985.
[72] Berg C. Towards a world ethanol market? Ratzeburg,
Germany: F.O. Licht Commodity Analysis; 1988.
[73] Du W, Xu Y, Liu D, Zeng J. Comparative study on lipase-
catalyzed transformation of soybean oil for biodiesel
production with different acyl acceptors. J Mol Catal B:
Enzymat 2004;30:125–9.
[74] Baltz RA, Burcham AF, Sitton OC, Book NL. The recycle
of sulfuric acid and xylose in the prehydrolysis of corn
stover. Energy 1982;7:259–65.
[75] Castro FB, Hotten PM, Ørskov ER. The potential of
dilute-acid hydrolysis as a treatment for improving the
 ARTICLE IN PRESS
A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18
nutritional quality of industrial lignocellulosic by products.
Anim Feed Sci Technol 1993;42:39–53.
[76] Sokhansanj S, Turhollow A, Cushman J, Cundiff J.
Engineering aspects of collecting corn stover for bioenergy.
Biomass Bioenergy 2002;23:347–55.
[77] Kim S, Dale BE. Life cycle assessment of various cropping
systems utilized for producing biofuels: bioethanol and
biodiesel. Biomass Bioenergy 2005;29:426–39.
[78] Kumar A, Cameron JB, Flynn PC. Pipeline transport and
simultaneous saccharification of corn stover. Biores Tech-
nol 2005;96:819–29.
[79] Biodiesel from vegetable oils via transesterification in
supercritical methanol. Energy Convers Manage 2002;43:
2349–56.
[80] Ghadge SV, Raheman H. Process optimization for
biodiesel production from mahua (Madhuca indica) oil
using response surface methodology. Biores Technol
2006;97:379–84.
[81] Krammer P, Vogel H. Hydrolysis of esters in subcritical
and supercritical water. Supercrit Fuids 2000;16:189–206.
[82] Saka S, Kusdiana D. Biodiesel fuel from rapeseed oil as
prepared in supercritical methanol. Fuel 2001;80:225–31.
[83] Kusdiana D, Saka S. Kinetics of transesterification in
rapeseed oil to biodiesel fuels as treated in supercritical
methanol. Fuel 2001;80:693–8.
[84] Demirbas A. Biodiesel fuels from vegetable oils via
catalytic and non-catalytic supercritical alcohol transester-
ifications and other methods: a survey. Energy Convers
Manage 2003;44:2093–109.
[85] Balat M. Biodiesel from vegetable oils via transesterifica-
tion in supercritical ethanol. Energy Educ Sci Technol
2005;16:45–52.
[86] Demirbas A. Biodiesel production from vegetable oils via
catalytic and non-catalytic supercritical methanol transes-
terification methods. Progress Energy Combus Sci 2005;31:
466–87.
[87] Bala BK. Studies on biodiesels from transformation of
vegetable oils for diesel engines. Energy Edu Sci Technol
2005;15:1–45.
[88] Ma F, Hanna MA. Biodiesel production: a review. Biores
Technol 1999;70:1–15.
[89] Zhang Y, Dub MA, McLean DD, Kates M. Biodiesel
production from waste cooking oil: 2. Economic assessment
and sensitivity analysis. Biores Technol 2003;90:229–40.
[90] Canakci M, Van Gerpen J. Biodiesel production from oils
and fats with high free fatty acids. Trans ASAE
2001;44:1429–36.
[91] Bender M. Economic feasibility review for community-
scale farmer cooperatives for biodiesel. Biores Technol
1999;70:81–7.
[92] Vasudevan P, Sharma S, Kumar A. Liquid fuel from
biomass: an overview. J Sci Ind Res 2005;64:822–31.
[93] Ouellette N, Rogner H-H, Scott DS. Hydrogen-based
industry from remote excess hydroelectrıcıty. Int J Hydro-
gen Energy 1997;22:397–403.
[94] Iwasa N, Kudo S, Takahashi H, Masuda S, Takezawa N.
Highly selective supported Pd catalysts for steam reforming
of methanol. Catal Lett 1993;19:211–6.
[95] Takezawa N, Shimokawabe M, Hiramatsu H, Sugiura H,
Asakawa T, Kobayashi H. Steam reforming of methanol
over Cu/ZrO2. Role of ZrO2 support. React Kinet Catal
Lett 1987;33:191–6.
17
[96] Demirbas A, Gullu D. Acetic acid, methanol and acetone
from lignocellulosics by pyrpolysis. Energy Educ Sci
Technol 1998;1:111–5.
[97] Phillips VD, Kinoshita CM, Neill DR, Takashi PK.
Thermochemical production of methanol from biomass in
Hawaii. Appl Energy 1990;35:167–75.
[98] Brown HP, Panshin AJ, Forsaith CC. Textbook of wood
technology, vol. II. New York: McGraw-Hill; 1952.
[99] Sorensen HA. Energy conversion systems. New York:
Wiley; 1983.
[100] Grassi G. Modern bioenergy in the European Union.
Renew Energy 1999;16:985–90.
[101] Gullu D, Demirbas A. Biomass to methanol via pyrolysis
process. Energy Convers Manage 2001;42:1349–56.
[102] Demirbas A. Mechanisms of liquefaction and pyrolysis
reactions of biomass. Energy Convers Manage 2000;41:
633–46.
[103] Chmielniak T, Sciazko M. Co-gasification of biomass and
coal for methanol synthesis. Appl Energy 2003;74:393–403.
[104] Rowell RM, Hokanson AE. Methanol from wood: a
critical assessment. In: Sarkanen KV, Tillman DA, editors.
Progress in biomass conversion, vol. 1. New York:
Academic Press; 1979.
[105] Hao XH, Guo LJ. A review on investigation of hydrogen
production by biomass catalytic gasification in supercritical
water. Huagong Xuebao 2002;53(3):221–8 [in Chinese].
[106] Yoshida T, Oshima Y, Matsumura Y. Gasification of
biomass model compounds and real biomass in super-
critical water. Biomass Bioenergy 2004;26:71–8.
[107] Matsumura Y, Minowa T. Fundamental design of a
continuous biomass gasification process using a super-
critical water fluidized bed. Int J Hydrogen Energy
2004;29:701–7.
[108] Demirbas MF. Producing hydrogen from biomass via non-
conventional processes. Energy Explor Exploit 2004;22:
231–9.
[109] Bowen DA, Lau F, Zabransky R, Remick R, Slimane R,
Doong S. Techno-economic analysis of hydrogen produc-
tion by gasification of biomass. NREL 2003 progress
report. USA: National Renewable Energy Laboratory
[110] Wang D, Czernik S, Chornet E. Production of hydrogen
from biomass by catalytic steam reforming of fast pyrolysis
oils. Energy Fuels 1998;12:19–24.
[111] Demirbas A. Fuel Properties of charcoal derived from
hazelnut shell and the production of briquets using
pyrolytic oil. Energy 1999;24:141–50.
[112] Hall DO, Rosillo-Calle F, Williams RH, Woods J. Biomass
for energy: supply prospects. In: Johansson TB, Kelly H,
Reddy AKN, Williams RH, editors. Renewable energy—
sources for fuels and electricity. Washington, DC: Island
Press; 1993.
[113] Azar C, Lindgren K, Andersson BA. Global energy
scenarios meeting stringent CO2 constraints—cost-effective
fuel choices in the transportation sector. Energy Policy
2003;31:961–76.
[114] European Commission, (EC). Promoting biofuels in
Europe. Bruxelles, Belgium: European Commission, Direc-
torate-General for Energy and Transport; 2004. B-1049.
Available from: http://europa.eu.int/comm/dgs/energy_
transport/index_en.html.
[115] Demirbas A. Bioenergy, global warming, and environmen-
tal impacts. Energy Sources 2004;26:225–36.
 ARTICLE IN PRESS
18 A. Demirbas / Progress in Energy and Combustion Science 33 (2007) 1–18
[116] Kapdi SS, Vijay VK, Rajesh SK, Prasad R. Biogas
scrubbing, compression and storage: perspective and
prospectus in Indian context. Renew Energy 2005;30:
1195–202.
[117] Encinar JM, Beltran FJ, Ramiro A, Gonzalez JF.
Pyrolysis/gasification of agricultural residues by carbon
dioxide in the presence of different additives: influence of
variables. Fuel Proc Technol 1998;55:219–33.
[118] Wang D, Czernik S, Montane D, Mann M, Chornet E.
Biomass to hydrogen via fast pyrolysis and catalytic steam
reforming of the pyrolysis oil or its fractions. Ind Eng
Chem Res 1997;36:1507–18.
[119] Babu BV, Chaurasia AS. Heat transfer and kinetics in the
pyrolysis of shrinking biomass particle. Chem Eng Sci
2004;59:1999–2012.
[120] Babu BV, Chaurasia AS. Dominant design variables in
pyrolysis of biomass particles of different geometries in
thermally thick regime. Chem Eng Sci 2004;59:611–22.
[121] Babu BV, Chaurasia AS. Pyrolysis of biomass: improved
models for simultaneous kinetics and transport of heat,
mass, and momentum. Energy Convers Manage 2004;45:
1297–327.
[122] Babu BV, Chaurasia AS. Parametric study of thermal and
thermodynamic properties on pyrolysis of biomass in
thermally thick regime. Energy Convers Manage 2004;45:
53–72.
[123] Di Blasi C. Modeling and simulation of combustion
processes of charring and non-charring solid fuels. Progress
Energy Combus Sci 1993;19:71–104.
[124] Di Blasi C. Analysis of convection and secondary reaction
effects within porous solid fuels undergoing pyrolysis.
Combus Sci Technol 1993;90:315–40.
[125] Di Blasi C. Modelling the fast pyrolysis of cellulosic
particles in fluid-bed reactors. Chem Eng Sci 2000:
5999–6013.
[126] Chaurasia AS, Babu BV. Influence of product yields,
density, heating conditions, and conversion of biomass.
J Arid Land Stud 2004;14S:159–62.
[127] Bridgwater AV. Renewable fuels and chemicals by thermal
processing of biomass. Chem Eng J 2003;19:87–102.