Energy Sources

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Hydrogen Production from Biomass by the

Gasification Process

Ayhan Demirbaş

To cite this article: Ayhan Demirbaş (2002) Hydrogen Production from Biomass by the
Gasification Process, Energy Sources, 24:1, 59-68, DOI: 10.1080/00908310252712307

To link to this article: https://doi.org/10.1080/00908310252712307

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Energy Sources, 24:59–68, 2002
Copyright © 2002 Taylor & Francis
0090-8312 /02 $12.00 1 .00

Hydrogen Production from Biomass by the

GasiŽ cation Process

AYHAN DEMÇIRBAŞ
P. K. 216
61035 Trabzon
Turkey

The gasiŽ cation of biomass is a thermal treatment, which results in a high produc-
tion of gaseous products and small quantities of char and ash. Steam reforming of
hydrocarbons, partial oxidation of heavy oil residues, selected steam reforming of
aromatic compounds, and gasiŽ cation of coals and solid wastes to yield a mixture
of H2 and CO (syngas), followed by water-gas shift conversion to produce H2 and
CO2 , are well-established processes. The steam capability can be signiŽ cantly im-
proved by permitting the classical Ni-alumina or Ni-silica/alumina formulations with
Ca and/or K. Three types of catalysts were tested: alumina, aluminosilicate material,
and nickel-supported catalyst.

Keywords biomass, gasiŽ cation, hydrogen, catalyst

GasiŽ cation of solid fuels to yield a mixture of H2 and CO (syngas), followed by

water-gas shift conversion to produce H2 and CO2 , are well-established processes (Patil,
1987). Renewable biomass has also been considered as potential feedstock for gasiŽ cation
to produce syngas; the economics of current processes favor the use of light hydrocarbons
(in natural gas) and coal. An alternative approach to the production of H2 from biomass
begins with fast pyrolysis of biomass (Wang et al., 1997). Production of hydrogen gas by
gasiŽ cation of carbon with superheated steam was reported (Lower, 1963). The reacting
carbon material is charcoal and is obtained from wood (Taheshita et al., 1975; Wienhaus,
1979), palm stones (Rabah et al., 1983), or other domestic waste materials (Constantine,
1983).
A large number of research projects in the Ž eld of thermochemical conversion of
biomass, mainly on pyrolysis, carbonization, and gasiŽ cation, have been carried out. The
problems associated with the realization of the process and utilization of the products
have been recently reviewed (Baker et al., 1987; Demirbaş, 2000a, b; Demirbaş and
ÇaÆglar, 1998; ÇaÆglar and Özmen, 2000). In the literature a large number of experimental
studies concerning the gasiŽ cation of biomass with air and oxygen have been presented.
Extensive research has been carried out on small- and medium-sized air gasiŽ ers to
produce low BTU fuel gas and power (Rapagna et al., 1992; Corella et al., 1991). In the
steaming reactor, hydrogen gas is liberated according to the following reaction at 1225 K:

2C 1 3H2 O 5 3H2 1 CO2 1 CO

Received 5 December 2000; accepted 13 January 2001.

Address correspondence to Ayhan Demirbaş, P. K. 216, TR-61035 Trabzon, Turkey. E-mail:
ayhandemirbas@hotmail.com

59
60 A. Demirbaş

Table 1
Range of the main operating parameters

Temperature Heating rate Solid residence Water/

Process (K) (K/s) Time (s) biomass

Pyrolysis 675–875 0.1–1 600–2000 0.1–2

Fast pyrolysis 975–1225 250–300 1–3 0.2–0.6
Steam gasiŽ cation 975–1225 300–500 0.5–2 0.8–2

Source: Maschio et al., 1994

The pyrolysis products divided into a volatile fraction consisting of gases, vapors,
tar components, and a carbon-rich solid residue. The gasiŽ cation of biomass is a thermal
treatment that results in a high production of gaseous products and small quantities of char
and ash (Demirbaş and Güllü, 1998). The pyrolysis of carbonaceous materials refers to
incomplete thermal degradation resulting in char, condensable liquid or tar, and gaseous
products. In its strictest deŽ nition, pyrolysis is carried out in the absence of air. Pyrolysis
may be deŽ ned as that regime in which the same organic matter is degraded by thermal
reactions in the absence of added oxidizing agents to provide a complex volatile phase
and a carbonaceous char containing inorganic components.
Some solids, liquids, and gases are produced in every thermal degradation process,
including gasiŽ cation. However, pyrolysis differs from gasiŽ cation (Maschio et al., 1994)
in that the products of interest are the char and liquids, which as a result of the incomplete
nature of the process retain much of the structure, complexity, and signature of the
raw material undergoing pyrolysis (Table 1). In reference to wood, pyrolysis processes
are alternately referred to as carbonization, wood distillation, or destructive distillation
processes. As generally accepted, carbonization refers to processes in which the char is
the principal product of interest (wood distillation, the liquid; and destructive distillation,
both char and liquid).
A much simpler and therefore, in principle, economically more attractive method
of extracting oil from biomass is (solvent-free) pyrolysis. This procedure eliminates the
need for a solvent recycle stream and has a higher thermal efŽ ciency than the gasiŽ cation
stage of indirect liquefaction processes.
Pyrolysis of biomass is a complex function of the experimental conditions under
which the pyrolysis process proceeds. The most important factors, which affect the yield
and composition of the volatile fraction liberated, are biomass species, chemical and
structural composition of biomass, particle size, temperature (i.e., temperature-time his-
tory), heating rate, atmosphere, pressure, and reactor conŽ guration.

Overview of GasiŽ cation Technology

GasiŽ cation is a century old technology that  ourished quite well before and during the
second world war. The technology disappeared soon after the second world war, when
liquid fuel became easily available. Interest in the gasiŽ cation technology has undergone
many ups and downs during the century. Today, because of increased fuel prices and envi-
ronmental concerns, there is renewed interest in this century old technology. GasiŽ cation
has become more modern and quite a sophisticated technology.
 Hydrogen Production from Biomass 61

The advantage of this technology is a decentralized energy conversion system that

operates economically even for small scale. A gas producer is a simple device consisting
of a usually cylindrical container with space for fuel, air inlet, gas exit, and grate. It can be
made of Ž re bricks, steel, or concrete and oil barrels. The design of the gasiŽ er depends
upon the type of fuel used and whether the gasiŽ er is portable or stationary. The gasiŽ er
alone is of little use. The complete gasiŽ cation system consists of the gasiŽ cation unit
(gasiŽ er), the puriŽ cation unit, and the energy converter-burners or internal combustion
engine.
GasiŽ cation is basically a thermochemical process that converts biomass materials
into their gasesous components. The results of gasiŽ cation are the producer gas, contain-
ing carbon monoxide, hydrogen, methane, and some other inert gases. Mixed with air,
the producer gas can be used in gasoline or diesel engines with little modiŽ cations.
Based on the design of gasiŽ ers and type of fuels used, there exist different kinds
of gasiŽ ers. Portable gasiŽ ers are mostly used for running vehicles. Stationary gasiŽ ers
combined with engines are widely used in rural areas of developing countries for many
purpose including generation of electricity and running irrigation pumps. Technologies
such as biomass gasiŽ cation which allow utilization of biomass fuel are of great impor-
tance.
Theoretically, almost all kinds of biomass with moisture content of 5–35% can be
gasiŽ ed, however, not every biomass fuel can lead to successful gasiŽ cation. Most of the
development work is carried out with common fuels such as coal, charcoal, and wood. It
was recognized that fuel properties such as surface, size, and shape as well as moisture
content, volatile matter, and carbon content in uence gasiŽ cation.
The key to a successful design of the gasiŽ er is to understand the properties and
thermal behavior of the fuel that is fed to the gasiŽ er. Operation of the gasiŽ cation system
demands a knowledgeable and skilled operator. Those interested in this technology must
remember that it requires hard work and tolerence. Compared to conventional systems
such as liquid fuel run engines, biomass gasiŽ cation technology is inconvenient. But it
is economical in many places and may lead to self-reliance in the crucial time of a fuel
crisis.
Coal gasiŽ cation technology is rapidly advancing and being placed into commercial
use. The gasiŽ cation process is attractive because pollutants such as artiŽ cial water gas
made in this way can be reformed to hydrogen (Demirbaş and ÇaÆglar, 1998).

GasiŽ cation Process

The essence of the gasiŽ cation process is the conversion of solid carbon fuels into carbon
monoxide by a thermochemical process. The gasiŽ cation of solid fuel is accomplished
in an air sealed, closed chamber under slight suction or pressure relative to ambient
pressure. The gasiŽ cation process in general is explained in this section.
GasiŽ cation is quite a complex thermochemical process. Splitting of the gasiŽ er into
strictly separate zones is not realistic, but nevertheless conceptually essential. GasiŽ cation
stages occur at the same time in different parts of the gasiŽ er.

Drying
Biomass fuels consist of moisture ranging from 5 to 35%. At temperatures above 373 K,
the water is removed and converted into steam. In the drying, fuels do not experience
any kind of decomposition.
62 A. Demirbaş

Pyrolysis
Pyrolysis is the thermal decomposition of biomass fuels in the absence of oxygen. The
ratio of products is in uenced by the chemical composition of biomass fuels and the
operating conditions. The heating value of the gas produced during the pyrolysis process
is low (3.5–8.9 MJ/m3 ). It is noted that no matter how the gasiŽ er is built, there will
always be a low temperature zone where pyrolysis takes place generating condensable
hydrocarbon.

Oxidation
Introduced air in the oxidation zone contains, besides oxygen and water vapors, inert
gases such as nitrogen and argon. These inert gases are considered to be nonreactive
with fuel constituents. The oxidation takes place at temperatures of 975 to 1275 K.
Heterogenous reaction takes place between oxygen in the air and solid carbonized
fuel, producing carbon monoxide. Plus and minus signs indicate the release and supply
of heat energy during the process, respectively:

C1 O2 ® CO2 1 406 MJ/kmol

In reaction, 12.01 kg of carbon are completely combusted with 22.39 m3 of oxygen

supplied by air blast to yield 22.26 m3 of carbon dioxide and 393.8 MJ of heat.
Hydrogen in fuel reacts with oxygen in the air blast, producing steam.
1
H2 1 O2 ® H2 O 1 242 MJ/kmol
2

Reduction
In the reduction zone, a number of high temperature chemical reactions take place in
the absence of oxygen. Assuming a gasiŽ cation process using biomass as a feedstock,
the Ž rst step of the process is a thermochemical decomposition of the lignocellulosic
compounds with production of char and volatiles. The principal gasiŽ cation reactions
that occur in reduction are mentioned below (Maschio et al., 1994; Demirbaş, 2000b).

Boudouard reaction:
CO2 1 C5 2CO 172.6 MJ/kmol. (1)

Water-gas reaction:

C1 H2 O 5 CO 1 H2 131.4 MJ/kmol. (2)

Water shift reaction:

CO2 1 H2 5 CO 1 H2 O 1 41.2 MJ/kmol. (3)

Methane production reaction:

C1 2H2 ® CH4 1 75 MJ/kmol. (4)

Main reactions show that heat is required during the reduction process. Hence the temper-
ature of gas goes down during this stage. If complete gasiŽ cation occurs, all the carbon
 Hydrogen Production from Biomass 63

is burned or reduced to carbon monoxide, a combustible gas, and some other mineral
matter is vaporized. The remains are ash and some char (unburne d carbon). The following
reactions also occur during the gasiŽ cation process:

C1 CO2 5 2CO; (5)

CH4 1 H2 O 5 CO 1 3H2 . (6)

The main gaseous products from biomass are (Wang et al., 1997) the following:

Pyrolysis of Biomass ® H2 1 CO2 1 CO 1 Hydrocarbon Gases; (7)

Catalytic Steam Reforming of Biomass ® H2 1 CO2 1 CO; (8)
GasiŽ cation of Biomass ® H2 1 CO2 1 CO 1 N2 . (9)

Hydrogen gas was produced on a pilot scale by steam gasiŽ cation of charred cellu-
losic waste material. The gas was freed from moisture and carbon dioxide. The beneŽ cial
effect of some inorganic salts such as chlorides, carbonates, and chromates on the reac-
tion rate and production cost of the hydrogen gas was investigated (Rabah and Eldighidy,
1989). Steam reforming C1 C5 hydrocarbons, nafta, gas oils, and simple aromatics are
commercially practiced, well-known processes. Steam reforming of hydrocarbons, partial
oxidation of heavy oil residues, selected steam reforming of aromatic compounds, and
gasiŽ cation of coals and solid wastes to yield a mixture of H2 and CO (syngas), followed
by water-gas shift conversion to produce H2 and CO2 , are well-established processes.
When the objective is to maximize the production of H2 , the stoichiometry describing
the overall process is

C n Hm 1 2nH 2 O ® nCO2 1 [2n 1 (m 2) ]H2 . (10)

The simplicity of Equation (10) hides the fact that in a hydrocarbon reformer the
following reactions take place concurrently:

Cn Hm 1 nH2 O 5 nCO 1 [n 1 (m2) ]H2 . (11)

At normal reforming conditions, steam reforming of higher hydrocarbons (Cn Hm )

is irreversible (Equation (10)), whereas the methane reforming (Equation (6)) and the
water-shift conversion (Equation (3)) reactions approach equilibrium. A large molar ratio
of steam to hydrocarbon will ensure that the equilibrium for Equations (10) and (11)
is shifted toward H2 production. The hydrogen yields were obtained by use of three
different processes as given in Table 2 (Wang et al., 1997).

Catalyst in GasiŽ cation

The effect of catalyst on gasiŽ cation products is very important. Table 3 shows the com-
position of the gas produced in the pyrolysis reactor (Demirbaş et al., 1996). Gaseous
products leaving the pyrolysis reactor contained mainly CO, CO2 , H2 , CH4 , light hydro-
carbons, and some other organic vapors. The use of the catalyst did not affect the gas
yields, but the composition of the gases was strongly in uenced. The content of H2 and
CO2 increased, while that of CO decreased; a drastic reduction in the content of organic
compounds could also be observed. Because the char yields remained almost constant
64 A. Demirbaş

Table 2
Comparison of hydrogen yields were obtained by use of three different processes

Hydrogen yield Hydrogen energy contents/

Processes (w) biomass energy content

Pyrolysis 1 catalytic reforming 12.6 91

GasiŽ cation 1 shift reaction 11.5 83
Biomass 1 steam 1 except heat 17.1 124
(theoretical maximum)
Source: Wang et al., 1997

compared to an equivalent noncatalytic thermal run, the increase in the content of hy-
drogen was probably due to the in uence of the catalyst on the shift reaction (Maschio
et al., 1994):

CO 1 H2 O 5 H2 1 CO2

The powdered K2 CO2 catalyst (1–3 wt% of moisture-free biomass) used in the catalytic
gasiŽ cation runs was mixed with the biomass in the reaction chamber. The catalyst shows
a destructive effect on the organic compounds, and H2 and CO2 form at the end of the
steam gasiŽ cation (catalytic steam reforming) process.
Spiro et al. (1984) examined the boudouard catalysts. The effect of the addition of
inorganic salts such as nitrates, perchlorates, and chromatres was investigated (MEICL,
1983). It has been reported that the use of energy recovered from  uidized bed combustors
provided the most energy-efŽ cient solution (Sneyd, 1984).
The main problem in the steam reforming of carbonaceous substances is carbon for-
mation. Three types of carbon may be formed: whiskers, encapsulating deposits (“poly-
mer”), and pyrolytic carbon (Wang et al., 1997). Carbon formation is related to the
kinetics, and hence the selectivity, of the catalyst. In steam reforming, adsorption of
hydrocarbons on the metal sites (Ni is commonly used) is followed by dehydration
and cracking. This results in smaller CxHx adsorbed fragments that can polymerize to
unwanted intermediates and from coke. These reactions complete with reactions with

Table 3
Average chemical composition of gaseous products from the precipitate from
black liquor at different temperatures

Gas composition (% by volume)

Temperature
(K) H2 CO CO2 CH4

295–675 11.3 6 0.9 29.0 6 0.8 26.5 6 0.4 13.1 6 0.7

295–825 14.1 6 0.8 40.8 6 0.5 19.9 6 0.4 12.7 6 0.6
295–825a 31.7 6 1.9 18.7 6 0.7 30.1 6 0.6 8.5 6 0.3
295–925 18.4 6 0.5 36.0 6 0.4 15.9 6 0.5 14.7 6 1.1
295–925a 36.4 6 0.7 14.6 6 0.3 32.3 6 0.6 9.9 6 0.4
a 3% K CO of the samples used as catalyst.
2 3
Source: Demirbaş and ÇaÆglar, 1998
 Hydrogen Production from Biomass 65

adsorbed water species. The catalyst must supply enough adsorbed H2 O derived species,
mainly OH and H, which must have sufŽ cient surface mobility to reach the adsorbed
hydrocarbon derived species and react with them (Demirbaş and ÇaÆglar, 1998). The
steam capability can be signiŽ cantly improved by promoting the classical Ni-alumina
or Ni-silica/alumina formulations with Ca and/or K (Wang et al., 1997). Three types
of catalysts were tested by Corte et al. (1985): alumina, aluminosilicate material, and
nickel-supported catalysts.

Suitability of Some Biomass Fuels

The quality of the producer gas depends upon several factors including type of fuel. The
assessment of suitability of some of the important biomass fuels for gasiŽ cation is given
below:
Charcoal
Wood
Sawdust
Peat
Agricultural residues

Charcoal
Charcoal is a product of wood carbonization (absence of air). By burning around 4 tons
of Ž rewood, 1 ton of charcoal is produced. Charcoal offers twice as much heat as is
produced by wood. Using an efŽ cient charcoal oven or cookstove can compensate for
energy lost during the conversion of wood to charcoal. Unlike Ž rewood, it burns slowly
and does not produce any smoke. Good quality charcoal does not contain any tar, hence
it is quite feasible for all kinds of gasiŽ ers. Charcoal is also low in mineral matter and
does not disintegrate easily. Compared to other biomass fuels, charcoal is costly. An
important disadvantage is that during conversion of wood into charcoal, more than 50%
of the energy is lost. This is a notable factor for those developing countries that are
suffering in an energy crisis.

Wood
The main combustible components of wood are cellulose, hemicelluloses, and lignin,
which are compounds of carbon, hydrogen, and oxygen. Other minor combustible com-
ponents in wood are fats, resins, and waxes. The major noncombustible component of
wood is water, which makes up to 50% of freshly cut wood. Though the ash content is
low (< 1%), because of high oxygen content, the caloriŽ c value is low (16–20 MJ/kg).
Next to charcoal, wood is quite a suitable fuel for Ž xed bed gasiŽ ers. As wood
contains high volatile matter, an updraft gasiŽ er system produces gas containing tar,
which needs to be cleaned out before use in engines. Cleaning of gas is a difŽ cult
and labor-intensive process. Hence wood is not suitable in updraft gasiŽ er coupled with
internal combustion engines. However, the gas containing tar from an updraft gasiŽ er
can be used for direct burning.

Sawdust
Unpellatized sawdust leads to the problems of excessive tar production, inadmissable
pressure drop, and lack of bunker  ow. Such problems can be minimized by the use
66 A. Demirbaş

of densiŽ ed (briquetted or pelletized) sawdust (Demirbaş and Şahin, 1998). A reduc-

tion in the volume of the sawdust also provides a technological beneŽ t, so the material
could be transported and stored more economically than is possible at present. Small
sawdust particles can be used in  uidized gas producers to produce burning gas. If
this gas is to be used in internal combustion engines, a fairly good clean-up system is
essential.

Peat
Peat is the Ž rst stage of coal formation. It is not strictly a coal, or it can be termed as
the most immature coal. Freshly mined peat contains 90% moisture and 10% solid. It
cannot be utilized unless air dried to reduce moisture content to 30% or less. Its heating
value (around 20 MJ/kg) is slightly greater than wood.
As peat contains a very high level of moisture and ash, it creates problems in the
gasiŽ cation process.

Agricultural Residues
If wood is scarce and costly, more abundant or accessible but otherwise less favored
fuels are used instead. Agricultural residues are basically biomass materials that are by-
products of agriculture. This includes cotton stalks, wheat and rice straw, coconut shells,
maize and jowar cobs, jute sticks, rice husks, etc.
Many developing countries have a wide variety of agricultural residues in ample
quantities (Küçük and Tunç, 1999). Hazelnut shell, coconut shells, and maize cobs have
been successfully tested for Ž xed-bed gasiŽ ers; they are unlikely to create any problems.
Most cereal straws have an ash content above 10% and present a slagging problem in
downdraft gasiŽ ers. Rice husk with ash contents above 20% is difŽ cult to gasify.

GasiŽ cation for Energy Supply

Rural areas in developing countries are characterized by disperse population and a lack
of infrastructure. Energy is the basic means in improving the living standard and produc-
tivity.
A gasiŽ er-engine system combined with a generator provides electrical energy for
lighting and other household purposes. A small-scale gasiŽ er system (10–30 kw) would
be appropriate for a multitude of village applications in developing countries.
GasiŽ ers, when integrated with engines, provide mechanical power that can be used
for running automobiles and many other stationary machinery. The use of downdraft
gasiŽ ers fueled with wood or charcoal to power cars, lorries, buses, trains, boats, and
ships has already proved its worth in the past. Before and during the second world war,
gasiŽ ers were largely used to power vehicles.
Research in the past shows that compared to gasiŽ ers fueled with wood or agri-
cultural residues, charcoal gasiŽ ers present fewer operational problems and are being
recommended for village level applications. Microscale gasiŽ cation systems (1–10 kw)
can be used by small and medium farmers for providing power to irrigation systems. The
equipment shall be small, cheap, simple, and transportable.
If Ž rewood is available in sufŽ cient amounts without any danger to the forest, the
gasiŽ er can serve as an option for energy supply in remote areas. Because of great concern
for conservation of forests and availability of fossil fuels, gasiŽ cation is not seen as a
 Hydrogen Production from Biomass 67

universally applicable technology, but rather as a component within a range of available

regenerative energies. It can be a valuable supplement to wind, solar, and hydro powers.

Economy
Today the least expensive way of making hydrogen is through the steam reforming of
natural gas. The resulting cost of hydrogen is typically about 5–6 US$/GJ when made
from natural gas at a price of 3 US$/GJ (Kaarstad and Audus, 1997). About 95% of
all hydrogen used in the world goes to produce ammonia (50%), petroleum processing
(37%), and methanol (8%). Most of the hydrogen for making these three products is both
produced and consumed within the plant fences.
Cheaper feedstocks can be used, which include biomass residues. The intregrated
system, however, can avoid the costs of entirely condensing the vapors to produce liquid
fuel and transporting the liquid fuel to the hydrogen facility. Because of the low sulfur
content of biomass and liquid fuel from the biomass, a sulfur removal system is not likely
to be required. The current selling price of H2 in industry is generally between $5/GJ and
$14/GJ, depending on the size of the production facility. This range is for hydrogen as
produced by the plant: puriŽ ed but not compressed or stored. For a conceptual process,
the cost of hydrogen has been estimated to be $7.70/GJ for the base case (production
capacity: 35.5 tons of hydrogen per day) (Wang et al., 1997).
The running cost of the generated hydrogen was carried out by processing 10 tons
of the biomass. The biomass was received at a price of $4 ton 1 . It was transported by
truck for $16. The cost of 1 kg of puriŽ ed hydrogen is only $0.68 (Rabah and Eldighidy,
1989).

Conclusion
GasiŽ cation of solid fuels to yield a mixture of H2 and CO, followed by a water-gas
shift conversion to produce H2 and CO2 , are well-established processes.
Renewable biomass has also been considered as potential feedstock for gasiŽ cation
to produce syngas; the economics of current processes favor the use of light hydrocarbons
(in natural gas) and coal. An alternative approach to the production of H2 from biomass
begins with fast pyrolysis and gasiŽ cation of biomass.
Production of hydrogen gas by biomass gasiŽ cation with steam is enhanced by the
addition of some inorganic salts to the reacting species. Kinetically, the reaction is a
chemically controlled process.

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