.

Fuel Processing Technology 75 2002 2743

www.elsevier.comrlocaterfuproc
Steam gasification of Cynara cardunculus L.:
influence of variables
J.M. Encinar
)
, J.F. Gonzalez, J. Gonzalez

Departamento de Ingeniera Qumica y Energetica, Uniersidad de Extremadura, 06071, Badajoz, Spain
Received 25 May 2001; received in revised form 16 October 2001; accepted 16 October 2001
Abstract
A study of the steam gasification of Cynara cardunculus L. was carried out in order to
characterise the gas phase with a view to its energy use, analysing the influence of water partial
pressure, particle size, and temperature. The main gases generated were H , CH , CO, and CO ,
2 4 2
with a higher heating value between 10 and 11 MJrN m
3
. The gas in greatest proportion was H ;
2
that in the smallest proportion was methane, which was pyrolytic in origin. Within the range of
variables studied, the particle size had no significant effect on the process. Temperature and water
partial pressure exerted positive effects on the main parameters of the process, increasing the
reaction rate, the gas yield and production, the conversion and the energy generated per kilogram
.
of initial residue Cynara . The experimental results show that the watergas shift reaction is the
main determinant of the composition of the gases. For this reaction, an increase in temperature
leads to a greater formation of CO, and an increase in water partial pressure to a greater formation
of CO . The energy yield of the gasification process presented values between 0.5 and 0.85.
2
Temperature and water partial pressure had a positive effect on this parameter. q2002 Elsevier
Science B.V. All rights reserved.
Keywords: Steam gasification; Cynara cardunculus L.; Temperature; Particle size; Water partial pressure
1. Introduction
The gradual but steady decrease in oil reserves has created a considerable interest in
using alternative sources of energies which are renewable in nature. Among the sources
of renewable energy, biomass has great potential and will play a vital role in the near
future. Thus, the European Union aims to double the contribution of renewable energy
)
Corresponding author. Tel.: q34-924-289-672; fax: q34-924-271-304.
.
E-mail address: [email protected] J.M. Encinar .
0378-3820r02r$ - see front matter q 2002 Elsevier Science B.V. All rights reserved.
.
PII: S0378- 3820 01 00247- 8
( )
J.M. Encinar et al.rFuel Processing Technology 75 2002 2743 28
w x
from the current 5.6%, to 12% in the future 1 . The growing interest in the exploitation
of biomass also reflects its neutrality with respect to greenhouse-gas generation and
w x
other environmental problems 2,3 . Pyrolysis and gasification are the processes habitu-
ally used to transform biomass into useful forms of energy. The pyrolysis of biomass
generally yields three products: gas, tar, and char. In a gasification process, the solid
.
fuels are completely converted except for the ashes in the feed to gaseous products
w x
46 . Indeed, the possibility of obtaining a fuel consisting of clean gases with complete
w x
conversion makes the processes of gasification of biomass more and more attractive 5 .
The gasification of biomass can be studied according to gasifier type, operating
pressure, scale of the process, temperature, presence of catalyst, and gasifying agent
used. Depending on this gasifying agent, the gases produced at the gasifier outlet will
have different compositions. One of the most generally used gasifying agents at a
.
commercial scale is air. This yields an exit gas consisting of N 50 vol.% , H 10
2 2
.
vol.% and, CO, CH , C , C , CO , H O and tars. This composition makes the gas
4 2 3 2 2
only useful for electricity production or heat generation. The exact composition of the
w x
gases depends on the operating variables 7,8 .
When large quantities of hydrogen are required, gasification with air is not appropri-
ate. Hydrogen can be obtained from renewable energy sources through the thermal
conversion of biomass. Catalytic reforming of liquids from the pyrolysis of lignocellu-
losic wastes and direct biomass gasification with steam can be used to obtain CO,
w x
hydrogen or synthetic gas 9,10 . In steam gasification, the product composition is quite

different from that obtained with air. The exit gas no longer contains nitrogen except
.
for a small amount from purges , and the hydrogen content can be as high as 5055
vol.%. Hydrogen, CO and CO are obtained together with significant quantities of CH ,
2 4
C , C and tars. Nevertheless, with a secondary catalytic steam reformer, the light
2 3
hydrocarbons and most of the tar can be converted into hydrogen and CO, thus
w x
increasing the hydrogen content to 7075 vol.% 7,11 . Depending on its composition
the gas produced can be used for a variety of purposes. If the gas is rich in hydrogen, it
can be utilised in fuel cell units for electricity production. If the ratio of CO to hydrogen
is ;1:2, it can be used as a feedstock for FischerTropsch synthesis. Also, if the gas is
w x
enriched with CH , it can be used as a heating fuel 6 .
4
In the steam gasification of a carbonaceous material, several reactions take place
. .
simultaneously, Eqs. 1 5 . The extent to which each reaction is involved depends on
. .
the operating conditions. Reaction 3 requires high temperatures, and reactions 4 and
. . .
5 require high pressures. Hence, reactions 1 and 2 are the main reactions of interest
in steam gasification when the reaction is carried out at atmospheric pressure and
temperatures between 600 and 800 8C.
CqH OmH qCO 1 .
2 2
COqH OmH qCO 2 .
2 2 2
CqCO m2CO 3 .
2
2COq2H mCH qCO 4 .
2 4 2
Cq2H mCH 5 .
2 4
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J.M. Encinar et al.rFuel Processing Technology 75 2002 2743 29
. . .
Reaction 1 is endothermic DHs130.29 kJrmol , and reaction 2 is exothernic
.
DHsy40.28 kJrmol . Therefore, an increase or decrease of the temperature dis-
. .
places reactions 1 and 2 in opposite directions. Consequently, the temperature is an
important variable with regard to the final composition of the gases. In general, it is
well-known that an increase in gasification temperature causes an increase in the
gaseous product yield and a decrease in the tar yield. Low-temperature gasification is an
interesting alternative from the energy point of view, but this process causes a higher tar
yield. Nevertheless, this tar can be eliminated by placing a catalyst in the same reactor
w x
where the biomass gasification is performed 12,13 .
Another important question in connection with the gasification of biomass is the form
in which the raw material is presented. A first possibility is to use the biomass without
prior transformation. Under these conditions there takes place simultaneously a pyrolysis
process and another of gasification that produces activated carbons and energy-rich
gaseous and liquid products. This one-step process is a promising alternative to the
expensive conventional processes for the production of activated carbon and upgraded
fuels. It also offers efficient utilisation of biomass in countries rich in forest or
w x
agricultural residues 1416 . A second possibility is to use as raw material the char
produced during the pyrolysis of the biomass. This char is highly reactive and can be
used separately for various applications. Recently, there has been a great deal of interest
in utilising pyrolysis-derived char for steam gasification to produce gaseous fuel. This
second option is more expensive, but in the process there are only formed gases and the
w x
corresponding ashes 5,6
Besides their renewable nature, biomass residues are far more reactive than coals in
w x
gasification process 17 . For example, the rate of biomass steam gasification is about
410 times greater than that of lignite. This high reactivity of biomass is a consequence
.
of its physical and chemical characteristics. Thus, the volatile content 8090% is at
least twice that of coals. The hydrogenrcarbon and oxygenrcarbon molar ratios range
between 1.31.5 and 0.50.6 respectively, whereas the corresponding values of coals
generally range only between 0.80.9 and 0.10.3. Finally, biomass chars, especially
wood charcoals, have porosities with values from 40% to 50% and a pore size between
20 and 30 mm, in comparison with coals, which have porosities ranging from 2% to

18% and a pore size of around 5 A.

The commercial development of a pyrolysis and gasification process requires abun-
dant and inexpensive raw material to be available. One possibility is to use the
agricultural residues from the industrial transformation of such food crops as maize,
w x
sunflower, etc. 18 . Another is to produce the biomass directly, i.e., to cultivate nonfood
crops for energy. This latter possibility has been considered by the authorities of the
European Union as a solution to the abandonment of traditional croplands. One of the
w x
crops used to produce woody biomass is the cardoon Cynara cardunculus L. 19 . This
plant is being studied experimentally in Spain in order to determine its optimal growth
conditions. The cardoon is a thistle native to the Mediterranean area. It belongs to the
.
Asteraceae family Compositae , which also includes the artichoke, the sunflower, and
the safflower. In the Iberian Peninsula it is well adapted to the climate and can be found
growing wild. Total cultivated biomass production can reach 2030 tons dry matter per
hectare per year, including 20003000 kg of seeds. It is used as fodder, or as biomass
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J.M. Encinar et al.rFuel Processing Technology 75 2002 2743 30
for energy production by combustion, pyrolysis and gasification. Its seeds have a high
protein content, close to 15%, and an oil content of around 25%. This oil is similar in
w x .
composition to sunflower oil 11 , the four principal fatty acids being palmitic 1114% ,
. . .
stearic 3% , oleic 25% and linoleic 56% .
With this background in view, and as the continuation to a previous work in which
w x
the pyrolysis of the cardoon was studied 20 , we carried out a detailed study of the
steam gasification of this plant. Our aim was to characterise the gaseous phase obtained
in the gasification process with a view to its energy use. Finally, we determined the
influence of temperature, particle size, and water partial pressure on the yield, produc-
tion and heating value of the gases, as well as on other parameters of the process.
2. Experimental
The raw material employed was C. cardunculus L. Table 1 lists its main character-
istics: proximate and ultimate analyses, and higher heating value. The experimental

set-up consisted of a cylindrical stainless steel reactor 75-cm length, 4-cm internal
.
diameter, and 4.3-cm external diameter equipped with a heating system, inlets for
.
feeding the carrier gas nitrogen and accessories to collect liquid and gas samples. At its
top, a heat exchanger kept samples at ambient temperature before the start of the run
.
cooling zone , and a suspension system held a basket that contained the residue
samples. The heating system consisted of a ceramic furnace and power source. The
temperature was controlled to "5 8C automatically by means of a computer program.
All experiments were carried out isothermally. The steam generator system consisted of
a pump fed with distilled water, an evaporator and a pre-heater to heat the streams of
steam and nitrogen to the reaction temperature.
The basket was loaded with approximately 5 g of Cynara while positioned in the

3 y1
.
cooling zone of the reactor. Then a nitrogen gas flow 200 cm min was established.
This flow rate was maintained for at least 1 h to completely purge the system. The
heating system was then activated. Once the prescribed temperature for the experiment
was reached, the basket was lowered into the heating zone at the same time as the steam
generation system was connected. The water flow rate in the pump was set to reach the
water partial pressure required for the experiment. The run time was 90 min, and gas
samples were taken at regular intervals. These samples were collected in 10 50-ml glass
bulb units for later analysis. The heating was then turned off and the basket moved back
Table 1
Proximate and ultimate analysis and higher heating value of C. cardunculus L.
a a
. .
Ultimate analysis wt.% Proximate analysis wt.% HHV
.
MJrkg
C H N S O Fixed Volatile Ash
.
difference carbon matter
46.7 4.8 0.7 0.1 47.7 14.3 77.3 8.4 18.2
a
Oven-dry basis.
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J.M. Encinar et al.rFuel Processing Technology 75 2002 2743 31
to the cooling zone. When room temperature was reached, the charcoal residue
remaining in the basket was weighed.
The gas fraction, mainly H , CO, CO CH , and some low-molecular weight
2 2 4
hydrocarbons such as ethane and ethene, was analysed chromatographically with a 3000
HRGC Konik gas chromatograph equipped with a thermal conductivity detector and a
double injector connected to two columns: 5A 100r120 Molecular Sieve and Porapak
columns of 5-m length, 3-mm diameter. Helium and nitrogen were used as carrier gases,
respectively. Quantitative determination of gases was carried out after calibration curves
were prepared from injection of known volumes of pure gases. An SP-4290 KONIK
integrator was used. More details of the experimental set-up and the procedure employed
w x
can be found in previous papers 16,21 .
3. Results and discussion
The steam gasification of C. cardunculus L. was carried out in a series of trials by
. .
varying the temperature 650800 8C , particle size 0.42-mm diameter and water
.
partial pressure 0.260.82 atm . In a previous work, we had studied the pyrolysis of C.
w x
cardunculus L. 20 , and established that, for the range of temperatures used, the
pyrolysis is complete in 1520 min. Therefore, with the present experimental procedure,
during the first minutes two processes take place simultaneously: pyrolysis and gasifica-
tion. The principal components of the gas phase detected were CO, CO , H , CH , and
2 2 4

small quantities of some hydrocarbons such as ethane and ethene. Nitrogen used as
.
carrier gas was also assayed so that the flow rate of the individual gas components
could be determined by comparison with that of nitrogen. In accordance with the method
w x
t

of Simmons and Sanchez 22 , the integral H CFdt where C is the concentration of a

0
.
given gas component, F the total gas flow rate, and t the reaction time applied to the
experimental data yields the total molar amounts of each component produced during
the run.
Fig. 1 shows the distribution of gases in one gasification experiment. As is observed,
the concentration of each gas reaches a maximum and then declines. Hydrogen presents
the highest concentration, and methane, ethene, and ethane the lowest, disappearing at
20 min of reaction time. The form of the curves seems to indicate that there is an initial
.
period of strong pyrolysis maximum , and that later the gases are generated by means
of the gasification reactions. It should be noted that, under the experimental conditions
employed, in no case was methane detected in the outlet gases after the initial 20 min.
.
This indicates that the gasification process takes place mainly through reaction. 1 and
. . .
2 . The other reactions, such as Eqs. 4 and 5 , which correspond to CO methanation
and carbon hydrogasification, respectively, can be discarded.
In Table 2, the yields of the four main gases are compared between a pyrolysis
w x
experiment 16 and a gasification experiment, and the data regarding the total produc-
tion of ethane and ethene by the end of the reaction are given in a footnote. Both
w x
experiments were carried out 800 8C. As has been shown in previous work 20 , the
pyrolysis of C. cardunculus L. at 800 8C generates gases, liquids and solids. The yield
.
in solids charcoal is approximately 20% of the weight of the raw material, the rest
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J.M. Encinar et al.rFuel Processing Technology 75 2002 2743 32
.
Fig. 1. Concentration profiles of gases produced at 800 8C particle size 0.631 mm, P s0.53 atm .
H2O
being liquids and gases. The pyrolysis process, as has been indicated, is completed in
less than 30 min. After this time, no further changes are observed independently of how
long the experiment is prolonged.
Table 2
.
Gas production in pyrolysis and gasification of C. cardunculus L. molrkg of feed Cynara
a b
t, min Pyrolysis Gasification
H CH CO CO H CH CO CO
2 4 2 2 4 2
5 1.13 1.22 2.34 2.59 1.26 1.13 1.70 1.60
10 3.46 1.77 4.04 3.71 5.23 1.66 3.81 2.96
15 3.83 1.85 4.74 3.89 8.82 1.76 5.48 3.75
20 3.84 1.85 5.09 3.89 12.14 1.80 6.72 4.41
25 3.84 1.85 5.36 3.89 15.07 1.82 7.56 4.93
30 3.84 1.85 5.62 3.89 17.99 1.83 8.40 5.54
40 22.76 1.83 9.35 6.42
50 26.71 1.83 10.02 7.28
60 29.89 1.83 10.57 8.06
75 33.91 1.83 11.23 9.07
90 37.79 1.83 11.87 10.10
a
3

Ts800 8C; particle size: 0.631 mm; nitrogen flow rate: 200 cm rmin ethane production: 0.23 molrkg
.
of feed Cynara; ethene production: 0.42 molrkg of feed Cynara .
b
3

Ts800 8C, particle size: 0.631 mm; nitrogen flow rate: 200 cm rmin; P s0.53 atm ethane
H2O
.
production: 0.21 molrkg of feed Cynara; ethene production: 0.43 molrkg of feed Cynara .
( )
J.M. Encinar et al.rFuel Processing Technology 75 2002 2743 33
In gasification experiments the situation should be similar. During the first minutes, a
major quantity of gases should be produced by pyrolysis. Nevertheless, as may be
observed in Table 2, more gases are generated at these same times of reaction in
gasification than in pyrolysis, with the exception of methane. Hence, gasification should
.
be occurring simultaneously with the pyrolysis, since the residue Cynara is in the
.
presence of steam. Once past the initial period 20 min approximately , the gases will
come exclusively from the gasification process, i.e., from the reaction between the steam
and the charcoal resulting from the previous process of pyrolysis. Quantitatively, one
clearly observes that the gasification generates a greater amount of gases that does the
pyrolysis.
. .
Considering reactions 1 5 and the data of Table 2, one may make the following
remarks regarding each of the gases. The quantity of methane, ethane and ethene is
identical in pyrolysis and gasification, and there is no further production of these gases
after 20 min. Therefore, the methane, ethane and ethene have an exclusively pyrolytic
. .
origin, and there is confirmation that reactions 4 and 5 can be ignored. Hydrogen is
the predominant gas. The quantities of this gas, together with those of CO and CO ,
2
. .
point to reactions 1 and 2 as being very important. The stoichiometry of the two
reactions gives the following relationship:
H mol numbersCOmol numberq CO mol number =2 6 . .
2 2
. .
Eq. 6 is satisfied acceptably at large reaction times see Table 2 . This ratifies that
. .
reactions 1 and 2 are the reactions through which the gasification process takes place.

The gases generated by means of pyrolysis which are important at the start of the
.
reaction would not satisfy the above equation.
3.1. Influence of particle size
The particle size is an important parameter that may affect the process rate. Its effect
is related to questions of heat and mass transfer. In particular, its effect on gasification
rates has been described as being very complex: the reaction rate generally rises as the
w x
particle size decreases due to the increase in specific surface area 23 . Changes in
porosity can lead to the opposite tendency, i.e., a drop in reactivity with decreasing
w x
particle size 24 . It is generally assumed, however, that an increase in particle size
causes greater temperature gradients inside the particle so that at a given time the core
w x
temperature is lower than that at the surface 25 . In any event, these circumstances
depend on the degree of porosity of the carbon and, therefore, of the raw material
w x
employed 26 . Consequently, it is necessary to carry out specific experiments with the
raw material being employed. These experiments should be performed under conditions
of maximum rate of chemical reaction, i.e., at the maximum temperature. Then, if the
particle size has no influence, the limitations imposed by heat and mass transfer can be
considered negligible. Table 3 shows the influence of particle size on a group of
characteristic parameters of the process. The temperature selected for these experiments
.
was 800 8C maximum and the water partial pressure 0.53 atm pressures higher than
.
0.53 atm led to conversions of 100% in times less than 90 min . As can be observed,
there is very little difference between the experiments. In the present work, we therefore
( )
J.M. Encinar et al.rFuel Processing Technology 75 2002 2743 34
Table 3
Influence of particle size on yield, production, composition, heating value of gases and conversion of
.
gasification Ts800 8C, P s0.53 atm, reaction times90 min
H2O
.
Parameter Particle size mm
0.40.63 0.631 11.6 1.62
.
Yield of gases kgrkg of Cynara 0.87 0.88 0.89 0.86
Gas molar fraction oven dry basis and H 0.605 0.604 0.604 0.611
2
free of nitrogen CH 0.028 0.029 0.030 0.025
4
CO 0.196 0.190 0.195 0.188
CO 0.161 0.166 0.162 0.166
2
C H 0.003 0.003 0.003 0.003
2 6
C H 0.007 0.007 0.007 0.007
2 4
.
H.H.V. MJrkg of Cynara 15.59 15.76 16.05 15.70
3
.
H.H.V. MJrm N 11.37 11.36 11.24 11.36
.
Gas production molrkg of Cynara H 37.3 37.8 38.1 38.3
2
CH 1.7 1.8 1.9 1.6
4
CO 12.1 11.9 12.3 11.8
CO 9.9 10.4 10.2 10.4
2
C H 0.20 0.21 0.21 0.19
2 6
C H 0.42 0.43 0.41 0.42
2 4
.
Conversion % 97.3 97.2 96.9 97.5
take it that the particle size had no influence on the main parameters, the small
differences obtained probably being due to experimental error. One may therefore
.
assume that inside the particles used in this study with diameters up to 2 mm there was
no temperature gradient to cause heat transfer limitations. These results are in agreement
with work using other residues such as olive and grape bagasse, maize, sunflower,
w x
grapevine, and tobacco 21,27 . Bearing all this in mind, we chose an intermediate
particle size for the rest of the experiments, that between 0.63- and 1-mm diameter.
3.2. Influence of temperature
Table 4 presents the results for the influence of the temperature. One observes that
with increasing temperature there is a major increase in the yield of gases. This increase

is due first to the production of gases in the initial period of pyrolysis increasing with
.
temperature , and second to the cracking of tars which would also be favoured by
temperature, and third to the increase in reaction rate with temperature. The yield of
gases increases sharply between 700 and 750 8C. This effect has also been observed by
w x
other workers 28 , and seems to be due to the existence of a first period dominated by
.
cracking of the volatile matter, and a second period dominated by reaction 2 the
.
watergas shift reaction . In consonance with this, the conversion also increases with
temperature, reaching values near to 100% at 800 8C.
The molar fractions rise for H and fall for CO , while CH , CO, C H , and C H
2 2 4 2 6 2 4
remain practically constant. As a consequence, the H rCO ratio in the exit gas increases
2
from 2.92 to 3.18 by changing the temperature from 650 to 800 8C. It is well-known that
( )
J.M. Encinar et al.rFuel Processing Technology 75 2002 2743 35
Table 4
Influence of temperature on yield, production, composition, heating value of gases and conversion of
.
gasification particle sizes0.631 mm, P s0.53 atm, reaction times90 min
H2O
.
Parameter Temperature 8C
650 700 750 800
.
Yield of gases kgrkg of Cynara 0.56 0.60 0.82 0.88
Gas molar fraction oven dry basis and H 0.521 0.587 0.600 0.604
2
free of nitrogen CH 0.035 0.029 0.028 0.029
4
CO 0.179 0.171 0.183 0.190
CO 0.254 0.203 0.181 0.166
2
C H 0.003 0.003 0.003 0.003
2 6
C H 0.007 0.006 0.006 0.007
2 4
.
H.H.V. MJrkg of Cynara 7.88 11.59 14.36 15.76
3
.
H.H.V. MJrm N 10.62 10.87 11.11 11.36
.
Gas production molrkg of Cynara H 17.8 28.1 34.8 37.8
2
CH 1.2 1.4 1.6 1.8
4
CO 6.1 8.2 10.6 11.9
CO 8.7 9.7 10.5 10.4
2
C H 0.11 0.14 0.17 0.21
2 6
C H 0.25 0.30 0.35 0.43
2 4
.
Conversion % 85.2 88.1 92.6 97.2
synthesis gases having different levels of H rCO ratios are suitable for different
2
applications. For example, synthetic gas having an H rCO molar ratio in the upper
2
range is desirable for producing hydrogen for ammonia synthesis. Also, this gas can be
used to produce pure hydrogen for fuel cell applications. The production of synthetic gas
having higher H rCO ratios is generally no problem. Besides the high level of the
2
H rCO ratio produced during commercial steam gasification, this ratio is increased
2
further during the watergas shift reaction for the removal of CO. However, it is

generally rather costly to produce synthetic gas having lower H rCO ratios in the
2
. w x
range 12 29 , although synthetic gas having a CO and H composition in this range is
2
highly desirable as feedstock for FischerTropsch synthesis for producing transportation
w x
fuels 6 .
As was remarked above, the watergas shift reaction seems to have a great
importance, particularly at high temperatures. If this reaction dominates the process, it
should also determine the composition of the gas. To know whether the flue gas from
the reactor is in equilibrium or not, the theoretical and experimental equilibrium
constants corresponding to the watergas shift reaction were calculated. Equilibrium
studies are used to predict the maximum possible conversions in any chosen chemical
reacting system. They also serve to estimate how these compositions will change with
the adjustments of the process operating conditions, such as the temperature, the
pressure, and the feed composition. They are also useful to provide an ideal goal against
which to measure improvements, to choose the operating conditions, and to know which
.
of the two mechanisms equilibrium vs. reaction rate are prevalent in the present
w x
gasification system 30 . Fig. 2 shows the theoretical and experimental equilibrium
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J.M. Encinar et al.rFuel Processing Technology 75 2002 2743 36
Fig. 2. Experimental and theoretical equilibrium constants for the watergas shift reaction. Influence of
.
temperature particle size 0.631 mm, P s0.53 atm .
H2O
constants corresponding to the watergas shift reaction. These two constants were
w x
calculated from JANAF tables 31 and from the final composition of the gases,

respectively. The curve corresponding to the thermodynamic equilibrium theoretical

.
values decreases with temperature as corresponds to an exothermic reaction. When the
temperature increases, the reaction shifts to the left and the equilibrium constant
diminishes. The experimental values are below the theoretical ones, indicating that
equilibrium was never reached under the present experimental conditions, although as
the temperature rose the difference decreased markedly. These results agree with those
w x
reported by Chang 32 , who estimates that the equilibrium of the watergas shift
reaction will be reached at temperatures near 1350 K. Other authors also obtain similar
results, although the temperature at which the theoretical and experimental constants
w x
coincide is different. Hence, Herguido et al. 33 conclude that at 750 8C the experimen-
tal values of the gas composition approach the equilibrium values, and the gas
w x
composition is then governed by the water-shift reaction. Prasad and Kuester 30
conclude that only at temperatures )1100 K does the water-shift reaction determine the
gas composition. Also, these authors state that there is a dependence between the
product gas composition and the hydrogen-to-oxygen ratio in the feedstock: higher
H rCO gas yields could be obtained with feedstock having a higher HrO ratio. The
2
HrO ratio could therefore be used for future modeling studies and for feedstock
selection.
( )
J.M. Encinar et al.rFuel Processing Technology 75 2002 2743 37
The relatively small changes in molar fractions of the gases means that the heating
value on a 1 m
3
N basis remained almost constant. On a per kilogram of Cynara basis,
however, the heating value increased markedly with temperature as a consequence of the
.
increase in the yield of gases especially H and CO . Under these conditions, the
2
heating value of the gases was much higher than that obtained in pyrolysis. For example,
at 800 8C the value was 15.76 MJrkg of Cynara as against the 4.33 MJrkg of Cynara
obtained in pyrolysis. This former value is also greater than the total heating value of the
. w x
pyrolysis including gases and charcoal , which was 10.33 MJrkg at 800 8C 20 .
3.3. Influence of water partial pressure
Five experiments were performed with water partial pressures of 0.26, 0.45, 0.53,
0.69 and 0.82 atm. The temperature was set at 700 8C and the particle size between
0.63- and 1-mm diameter. Table 5 presents the influence of this variable on a group of
characteristic parameters. The yield of gases and the conversion increase with the partial
pressure of water, which is a consequence of the increase in reaction rate. The
production of CH , C H and C H remain constant and independent of the water
4 2 6 2 4
. .
partial pressure. This thus proves that reactions 4 and 5 do not take place under the
experimental conditions employed and that these gases are formed during the pyrolysis
of the biomass. The molar fractions of H and CO increase, while that of CO
2 2
diminishes. This behaviour, together with the same trend shown by the production of
gases, reflects the growing importance of the watergas shift reaction as the water
partial pressure increases. This tendency is illustrated in Fig. 3 where the production of
CO is plotted vs. time. Clearly, the moles of CO formed increase with the water
2 2
.
partial pressure, i.e., reaction 2 seems to control the production of gases. Therefore,
steam being the major source of hydrogen during steam gasification, an increase in the
water partial pressure resulted in higher production of hydrogen. Due to this higher
production of hydrogen, the H rCO ratio in the exit gas increases from 3.26 to 8.55 by
2
changing the water partial pressure 0.27 to 0.82 atm. Such synthetic gas is suitable for
hydrogen production. As has been indicated, synthetic gas having an H rCO molar ratio
2
in the range 12 is highly desirable as feedstock for FischerTropsch synthesis. The
data of Table 5 seem to indicate that a synthetic gas having an H rCO molar ratio of
2
about 1.0 could be obtained by carrying out the experiments at a very low water partial
pressure. By controlling the input of steam, which is the predominant source of
hydrogen, one can adjust the molar ratio of H rCO in the synthetic gas to the desired
2
w x
value 6 .
Besides the aforementioned applications, the gas produced may be directly used as
fuel. Table 5 shows the heating value per unit volume of gas and per kilogram of
Cynara. The heating values based on 1 m
3
N present a decreasing tendency. This is a
consequence of the increase in the CO molar fraction and the decrease in that of CO.
2
On the per kilogram of Cynara basis, the heating value first increases and then
stabilises. This behaviour reflects the increase in the production of gases, and the
increase in the production of CO , whose contribution to the total heating value is null.
2
Table 5 also gives the values of the theoretical and experimental equilibrium
. .
constants corresponding to reactions 1 and 2 . Both situations are far from equilib-
(
)
J
.
M
.
E
n
c
i
n
a
r
e
t
a
l
.
r
F
u
e
l
P
r
o
c
e
s
s
i
n
g
T
e
c
h
n
o
l
o
g
y
7
5
2
0
0
2
2
7

4
3
3
8
Table 5

Influence of water partial pressure on yield, production, composition, heating value of gases and conversion of gasification particle sizes0.631 mm, Ts700 8C,
.
reaction times90 min
.
Parameter Water partial pressure atm
0.27 0.45 0.53 0.69 0.82
Yield of gases 0.46 0.51 0.60 0.63 0.64
.
kgrkg of feed charcoal
Gas molar fraction oven dry H 0.612 0.591 0.587 0.638 0.660
2
basis and free of nitrogen CH 0.040 0.028 0.029 0.029 0.020
4
CO 0.187 0.168 0.171 0.107 0.077
CO 0.148 0.201 0.203 0.216 0.238
2
C H 0.005 0.003 0.003 0.002 0.003
2 6
C H 0.009 0.008 0.006 0.007 0.006
2 4
.
H.H.V. MJrkg of Cynara 8.57 9.36 11.59 11.51 11.25
3
.
H.H.V. MJrm N 11.90 11.50 10.87 10.89 9.97
.
CqH OmCOqH 1 K 1.58 1.58 1.58 1.58 1.58
2 2 theoretical
y2 y2 y2 y3 y4
K 4.84=10 1.53=10 1.25=10 2.54=10 5.25=10
experimental
K rK 32.6 103.3 126.4 622.0 3009.5
theor. exp.
.
COqH OmCO qH 2 K 1.65 1.65 1.65 1.65 1.65
2 2 2 theoretical
K 0.429 0.334 0.291 0.270 0.213
experimental
K rK 3.85 6.63 5.67 6.11 7.75
theor. exp.
Gas production H 19.9 22.9 28.1 30.8 32.5
2
.
molrkg of Cynara CH 1.3 1.1 1.4 1.4 1.0
4
CO 6.1 6.5 8.2 5.2 3.8
CO 4.8 7.8 9.7 10.4 11.5
2
C H 0.15 0.13 0.14 0.12 0.13
2 6
C H 0.29 0.32 0.30 0.34 0.31
2 4
.
Conversion % 84.0 86.1 88.1 90.1 92.3
( )
J.M. Encinar et al.rFuel Processing Technology 75 2002 2743 39

Fig. 3. Production of CO . Influence of water partial pressure particle size 0.631 mm, temperatures
2
.
700 8C .
rium, and the separation increases even more with the water partial pressure. Neverthe-
.
less, in the case of reaction 2 the experimental and theoretical values are much closer
. .
than in reaction 1 , so that reaction 2 will be primarily responsible for the final
composition of the gases. It should also be noted that the steamrbiomass ratio was
always very high. This ratio was increased from 0.66 to 8 by changing the water partial
pressure from 0.27 to 0.82 atm. Consequently, in our gasifier the steam partial pressure
.
in the denominator of the expression corresponding to K for reactions 1 and
experimental
..
2 is much greater than that of the other components 1.814 times that of H , which
2
.
is the component in greatest proportion in the dry gas . Therefore, the experimental
conditions used lead to the values of K being smaller than those corresponding
experimental
to equilibrium, and this difference becomes more pronounced as the water partial
pressure increases. The reaction temperature is, however, only 700 8C. Under these
conditions, as was seen in the previous section, the exit gases have a composition very
far from that corresponding to equilibrium. In sum, high water partial pressures
. .
displaced reaction 1 to the right giving CO and H . Later, reaction 2 will also move
2
to the right yielding CO and H as end products as is confirmed by the experimental
2 2
results.
3.4. Molar ratio COrCO , hydrogen balance, and energy ealuation
2
. .
If the two main reactions of the process are indeed Eqs. 1 and 2 , knowing the
evolution of the COrCO molar ratio will allow one to obtain information on the
2
( )
J.M. Encinar et al.rFuel Processing Technology 75 2002 2743 40
.
Fig. 4. Molar ratio COrCO . Influence of temperature particle size 0.631 mm, P s0.53 atm .
2 H2O
relative importance of the two reactions. Fig. 4 shows this ratio for the experiments at
different temperatures. The molar ratio first decreases with reaction time to later stabilise
at a certain value, which increases with increasing temperature. This could be due both
. .
to the exothermal character of reaction 2 DHsy40.28 kJrmol and to the endother-
. . .
mal character of reaction 1 DHs130.29 kJrmol . Reaction 1 would therefore
.
displace to the right with increasing temperature, and reaction 2 to the left. The final
result would be a greater formation of CO, just as is observed experimentally. Another
.
possible cause could be the contribution of secondary reactions, such as Eq. 3 , which
starts to be significant at 800 8C. Fig. 5 shows the molar ratio COrCO for the
2
experiments at different water partial pressures. The temporal evolution is similar to that
of Fig. 4. Now the final COrCO value decreases as the water partial pressure
2
. .
increases. Reactions 1 and 2 are favoured by the increase in water partial pressure.
. .
Reaction 1 can only take place in the gassolid interface. Reaction 2 can take place
in both the gassolid interface and the gas phase. Therefore, it seems that the watergas
shift reaction is primarily responsible for the composition of the gases. This reaction
when displaced to the right would reduce the quantity of CO and increase that of CO ,
2
in agreement with the experimental observations.
..
As was indicated above, the stoichiometric relationship Eq. 6 should be fulfilled in
a process in which there is only gasification. Table 6 lists the results of the application
.
of Eq. 6 to all the experiments. On observes that the values of DH are generally
2
greater than zero, i.e., more H is generated than theoretically expected. The explanation
2
of these results requires one to consider the initial period of pyrolysis. During pyrolysis,
( )
J.M. Encinar et al.rFuel Processing Technology 75 2002 2743 41

Fig. 5. Molar ratio COrCO . Influence of water partial pressure particle size 0.631 mm, temperatures
2
.
700 8C .
the gases do not satisfy any stoichiometric relationship. The hydrogen produced would
be in addition to that generated by gasification. It is also possible that a part of the CO
.
generated in pyrolysis reacts according to reaction 2 , and generates more H . Table 6
2
also lists the ratio between the energy contained in the gases and the energy contained in
Table 6
Relationship between the energy contained in the gases and the energy contained in the initial residue
.
Cynara , and hydrogen balance: influence of particle size, temperature, and water partial pressure
. .
T 8C P Particle size Energy gases r DH
H2O 2
. . .
atm mm Energy Cynara
800 0.53 0.40.63 0.86 q5.4
800 0.53 0.631 0.87 q5.1
800 0.53 11.6 0.88 q5.4
800 0.53 1.62 0.86 q5.7
650 0.53 0.631 0.43 y5.7
700 0.53 0.631 0.64 q0.5
750 0.53 0.631 0.79 q3.2
700 0.27 0.631 0.47 q4.2
700 0.45 0.631 0.51 q4.8
700 0.69 0.631 0.63 q4.8
700 0.82 0.631 0.62 q5.7
( )
J.M. Encinar et al.rFuel Processing Technology 75 2002 2743 42
.
the initial residue Cynara , i.e., the energy yield of the gasification process. This yield,
referring to the full 90-min duration of the experiment, clearly increases with tempera-
ture. In the case of increasing water partial pressure, there is first an increase of the yield
followed by stabilisation. The particle size, as was to be expected, had no influence. The
values of the yields are typical of biomass gasification process using steam. The average
values vary between 70% and 80%. The rest of the biomass is used to provide the
necessary heat in the gasification reactions.
4. Conclusions
In the steam gasification of C. cardunculus L. the main product consists of a mixture
of H , CO, CO and CH gases. Other gases, such as C H and C H are also formed
2 2 4 2 6 2 4
but in very small amounts. The majority component is H , whose production is 10 times
2
higher than that obtained in pyrolysis under equal conditions of temperature.
Methane, ethane and ethene are generated only in the first 20 min. The production of
these gases is independent of the water partial pressure. These circumstances seem to
indicate that these gases have an exclusively pyrolytic origin.
Hence, under the present experimental conditions, the steam gasification of Cynara
. .
takes place by reactions 1 and 2 , the latter being the most important in determining
the production and composition of the gases due to its closeness to equilibrium. Other
. .
reactions of methane formation such as Eqs. 4 and 5 do not take place or are
negligible.
Within the range of variables studied, the particle size had no significant effect on the
.
process. These experiments, carried out at 800 8C maximum experimental temperature ,
show that the limitations imposed by mass and heat transfer are negligible. The results
were thus obtained under the control of the chemical reaction.
Temperature and water partial pressure exert a positive effect on the main parameters
of the process, increasing the reaction rate, the gas yield and production, the conversion,
.
and the energy generated per kilogram of initial residue Cynara . From an energy
viewpoint, the heating value of the gases generated in the process is about 1011
MJrm
3
N.
The H rCO ratio in the exit gas varies between approximately 3 and 8. This
2
synthetic gas is suitable for the generation of hydrogen or to use as fuel. The
experimental results suggest that smaller H rCO ratios can be obtained by operating at
2
low water partial pressures.
. .
The experimental equilibrium constants corresponding to reactions 1 and 2 differ
from the theoretical values. This shows that equilibrium is never reached under the
.
present experimental conditions. Nevertheless, the constant of reaction 2 is much
closer to the theoretical value, which indicates that this reaction is primarily responsible
for the composition of the gases. As was to be expected, increasing the temperature
leads to a greater formation of CO, and increasing the water partial pressure to a greater
formation of CO .
2
The energy yield of the gasification process is between 0.5 and 0.85. Temperature
and water partial pressure have a positive effect on this parameter.
( )
J.M. Encinar et al.rFuel Processing Technology 75 2002 2743 43
Acknowledgements
The authors would like to express their gratitude to the AJunta de ExtremaduraB for
the financial support received to perform this study, through the project IPR98B038.
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