Energy & Fuels 2006, 20, 1305-1309 1305

Hydrogen Production by Biomass Gasification with Steam-O2

Mixtures Followed by a Catalytic Steam Reformer and a CO-Shift
System
Maria P. Aznar, Miguel A. Caballero, Jose Corella,*, Gregorio Molina, and
Jose M. Toledo
Chemical and EnVironmental Engineering Department, CPS, 3 Maria de Luna st., UniVersity of Saragossa,
50018 Saragossa, Spain, and Department of Chemical Engineering, UniVersity Complutense of Madrid,
28040 Madrid, Spain

ReceiVed December 21, 2005. ReVised Manuscript ReceiVed February 10, 2006
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This paper studies the effect of adding a CO-shift reactor downstream from a fluidized-bed biomass gasifier
and a steam-reforming catalytic bed. The upstream gasifier was of small pilot-plant scale, 10 (kg of biomass)/
h, so the downstream catalytic reactors, steam-reformer and CO-shift, operated under a real gasification gas.
The main gasifying agent used was H2O-O2 mixtures. Some results are also reported for gasification with air
with some steam. The CO-shift catalytic system used had one high- (HT) and one low-temperature (LT) reactor.
Commercial catalysts were used. CO conversions (eliminations) higher than 90% and a H2 content as high as
Publication Date (Web): March 16, 2006 | doi: 10.1021/ef050428p

73 vol %, dry basis, have been obtained by the CO-shift system. The CO conversion and the increase (up to
14 vol %) of H2 content correlated well with the molar steam/CO ratio in the gasification gas at the inlet of
the HT reactor.

Introduction The high endothermicity of the process of gasification with

Some authors working on biomass gasification believe that
a H2-rich gas could be produced by biomass gasification. This
would be useful for some advanced applications of the produced
gasification gas. Biomass has, on average, only 6 wt % of
hydrogen, which would make it, in principle, of not much
interest for H2 production. Nevertheless, some extra H2 can come
from the cracking of H2O if the biomass is also used as a fuel
to supply the high amount of heat needed to crack the molecule
of H2O. In fact, a raw gasification gas with 48-55 vol %, dry
basis, H2 was generated by biomass gasification with pure steam
in a fluidized bed.1,2 Since this raw gasification gas contains
some CH4, tar, and light hydrocarbons, when a bed of calcined
dolomite (CaOMgO), limestone (CaO), and/or magnesite
(MgO) was used downstream from the gasifier, the H2 content
in the gasification gas was increased to 50-58 vol %, dry basis.3
Given that these minerals have only a small steam-reforming
activity for tar and CH4 elimination, some tar and CH4 still
remains in the gasification gas after the bed of dolomite or
limestone.3 When another more active (nickel-based) steam-
reforming catalyst is added to the two upstream reactors
[biomass gasifier + downstream bed of dolomite], the H2
content in the gasification gas was increased to 55-63 vol %,
dry basis.4
* Corresponding author. E-mail: narvaez@quim.ucm.es.
University Complutense of Madrid. Publishers: London, 1990; Vol 2, pp 2793-2797.
(1) Corella, J.; Aznar, M. P.; Delgado, J.; Aldea, E. Steam gasification
of cellulosic waste in a fluidized bed with downstream vessels. Ind. Eng.
Chem. Res. 1991, 30 (10), 2252-2262.
(2) Herguido, J.; Corella, J.; Gonzalez-Saiz, J. Steam gasification of
lignocellulosic residues in a fluidized bed at a small pilot scale. Effect of
the type of feedstock. Ind. Eng. Chem. Res. 1992, 31 (5), 1274-1282.
(3) Delgado, J.; Aznar, M. P.; Corella, J. Biomass gasification with steam
in fluidized bed: Effectiveness of CaO, MgO, and CaO-MgO for hot raw
gas cleaning. Ind. Eng. Chem. Res. 1997, 36 (5), 1535-1543.
pure steam may be solved in two different ways:
(1) By using a dual fluidized-bed circulating system (DFBCS).
This was the solution adopted first by Prasad and Kuester5 and
BattellesColumbus;6 afterward, in the late eighties, by Herguido
and co-workers;7,8 and more recently, in the late nineties, by
Hofbauer and co-workers.9 These DFBCSs have proved their
technical feasibility, but if several more reactors had to be added
after those circulating systems, the resulting overall process
would become too complex and difficult to operate.
(2) Another solution is to provide some heat for the steam
gasification by adding some oxygen to the steam; that is to say,
to gasify with [H2O + O2] mixtures. In this case, the H2 content
in the raw gasification gas can reach 30 vol %, dry basis, when
(4) Aznar, M. P.; Corella, J.; Delgado, J.; Lahoz, J. Improved steam
gasification of lignocellulosic residues in a fluidized bed with commercial
steam reforming catalysts. Ind. Eng. Chem. Res. 1993, 32, 1-10.
(5) Prasad, B. V. R. K.; Kuester, J. Process analysis of a dual fluidized
bed biomass gasification system. Ind. Eng. Chem. Res. 1988, 27 (2), 304-
310.
(6) Paisley, M. A.; Overend, R. P. The SilvaGas process from future
energy resourcessA commercialization success. In Proceedings of the 12th
European Conference on Biomass for Energy, Industry and Climate
Protection, Amsterdam, The Netherlands, June 17-21, 2002; pp 975-978.
(7) Herguido, J.; Rodrguez-Trujillo, J. L.; Corella, J. Gasification of
biomass with tar cracking catalysts in a circulating multisolid fluidized bed
pilot plant. In Biomass for Energy and Industry, Proceedings of the 5th
International Conference on Biomass, Lisbon, Portugal, Oct 9-13, 1989;
Grassi, G., Gosse, G., dos Santos, G., Eds.; Elsevier Applied Science
(8) Herguido, J.; Corella, J.; Artal, G.; Garca-Bordeje, J. E. Results with
a multisolid circulating dual fluid bed pilot plant for the advanced steam
gasification of biomass. In Biomass for Energy, Industry and EnVironment,
Proceedings of the 6th International Conference on Biomass, Athens, Greece,
April 22-26, 1991; Grassi, G., Colina, A., Zibeta, H., Eds.; Elsevier Applied
Science Publishers: London, 1992; pp 792-796.
(9) Pfeifer, C.; Rauch, R.; Hofbauer, H. In-bed catalytic tar reduction in
a dual fluidized bed biomass steam gasifier. Ind. Eng. Chem. Res. 2004, 43
(7), 1634-1640.

10.1021/ef050428p CCC: $33.50 2006 American Chemical Society

Published on Web 03/16/2006
 1306 Energy & Fuels, Vol. 20, No. 3, 2006
Table 1. H2 Contents (Vol %, Dry Basis) Obtained in the Gasification Gas at the Exit of Different Reactors, for Two Different Gasifying
Agents
fasifying agent
at the gasifiers exit
in-bed/silica sand
in-bed/silica sand + dolomite
gasifier + bed of dolomite
gasifier + bed of dolomite + bed of nickel-based catalyst
only silica sand is used as the in-bed material,10,11 or 45 vol %
H2, dry basis, when there is 40 wt % of calcined dolomite in
the gasifier bed12 which acts as an in-bed steam-reforming
catalyst. However, if a downstream bed of calcined dolomite is
added, then this H2 content increases to 50-52 vol %, dry
basis.13 When another further bed of a steam-reforming nickel-
based catalyst is added, the H2 content in the gasification gas
can be increased to 52-59 vol % H2, dry basis.14,15 Since these
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H2 contents are the basis of the work here reported, they are
summarized in Table 1.
The H2 content in the gasification gas can still be increased
by adding a CO-shift reactor to the above said processes and/
or schemes. The CO-shift catalysts increase the H2 content in
the flowing gas by the exothermic reaction CO + H2O S CO2
Publication Date (Web): March 16, 2006 | doi: 10.1021/ef050428p
+ H2. Although the CO-shift process is well-known in the
chemical industry, when these authors started to present results
in 1998 concerning this approach,16 it was the first time, to the
authors knowledge, that CO-shift reactors were connected to
biomass gasifiers. The resulting overall biomass gasification
process was new at the time. Further, Brown and co-workers17,18
at University of Iowa also connected two CO-shift reactors
downstream from a biomass fluidized-bed gasifier followed by
a guard bed of dolomite and a catalytic steam-reforming bed.
With these four catalytic reactors after their biomass gasifier,
they obtained a H2 content of 60.8 vol %, N2-free basis, when
the biomass gasification was made with pure steam,17 and 26.7
vol % H2, dry basis, when the gasification was made with air.18
Currently, some more authors (i.e., refs 19 and 20) are working
on this issue, because this approach offers new perspectives and
some more future for biomass gasification.
(10) Aznar, M. P.; Corella, J.; Gil, J.; Martn, J. A.; Caballero, M. A.;
Olivares, A.; Perez, P.; Frances, E. Biomass gasification with steam and
oxygen mixtures at pilot scale and with catalytic gas upgrading. Part I:
Performance of the gasifier. In DeVelopments in Thermochemical Biomass
ConVersion; Bridgwater, A. V., Boocock D. G. B., Eds.; Blackie Academic
& Professional: London, 1997; Vol. 2, pp 1194-1208 (ISBN: 0-7514-
0350-4).
(11) Gil, J.; Aznar, M. P.; Caballero, M. A.; Frances, E.; Corella, J.
Biomass gasification in fluidized bed at pilot scale with steam-oxygen
mixtures. Product distribution for very different operating conditions. Energy
Fuels 1997, 11 (6), 1109-1118.
(12) Olivares, A.; Aznar, M. P.; Caballero, M. A.; Gil, J.; Frances, E.;
Corella, J. Biomass gasification: Produced gas upgrading by in-bed use of
dolomite. Ind. Eng. Chem. Res. 1997, 36 (12), 5220-5226.
(13) Perez, P.; Aznar, M. P.; Caballero, M. A.; Gil, J.; Martin, J. A.;
Corella, J. Hot gas cleaning and upgrading with a calcined dolomite located
downstream a biomass fluidized bed gasifier operating with steam-oxygen
mixtures. Energy Fuels 1997, 11 (6), 1194-1203.
(14) Caballero, M. A.; Aznar, M. P.; Gil, J.; Martn, J. A.; Frances, E.; reaction using MOS2 catalyst following biomass gasification. In Proceedings
Corella, J. Commercial steam reforming catalysts to improve biomass
gasification with steam-oxygen mixtures. 1. Hot gas upgrading by the
catalytic reactor. Ind. Eng. Chem. Res. 1997, 36 (12), 5227-5239.
(15) Aznar, M. P.; Caballero, M. A.; Gil, J.; Martn, J. A.; Corella, J.
Commercial steam reforming catalysts to improve biomass gasification with
steam-oxygen mixtures. 2. Catalytic tar removal. Ind. Eng. Chem. Res.
1998, 37 (7), 2668-2680.
(16) Caballero, M. A.; Aznar, M. P.; Gil, J.; Martn, J. A.; Corella, J.
CO-shift catalytic beds after a biomass gasifier and a steam-reforming
catalytic reactor to get new and interesting exit gas compositions. In Biomass
for Energy and industry, proceedings of the 10th European Conference and
Technology Exhibition, Wurzburg, Germany, June 1998; Kopetz, H., Weber,
T., Palz, W., Chartier, P., Ferrero, G. L., Eds.; C.A.R.M.E.N.: Rimpar,
Germany, 1998; pp 1789-1793.
Aznar et al.
pure H2O H2O + O2
48-55 (refs 1 and 2) 30 (refs 10 and 11)
45 (ref 12)
50-58 (ref 3) 50-52 (ref 13)
55-63 (ref 4) 52-59 (refs 14 and 15)
This paper addresses the effect of locating one or two CO-
shift catalytic beds downstream from a two-step gasification
process: fluidized-bed gasifier with in-bed dolomite + reactor
with a steam-reforming nickel-based catalyst. The approach,
system, and/or process here studied is, therefore, very similar
to that recently published by Brown and co-workers.17,18 The
main difference between both systems is that, in this work, a
guard bed of dolomite is not used downstream from the gasifier,
as we used in the past.21 Instead, we locate the dolomite in the
same fluidized-bed gasifier, which provides very similar results22
and avoids the use of one reactor, the guard bed, in the complex
overall process. So, the scheme of the process studied here is
the following:
The main results presented in this work were obtained using
steam-O2 mixtures as the gasifying agent. Nevertheless, since
the authors currently operate the gasifier with air (+ some H2O
from the moistures of the biomass and of the air), the CO-shift
reactor was also operated with air (+ H2O) in the upstream
gasifier. Some results will, therefore, also be shown here using
air (+ some H2O) as the gasifying agent.
Experimental Facility Used
Gasifier. The gasifier used was a bubbling fluidized bed of
15 cm i.d. and 3.2 m height, continuously fed with biomass
near the bed bottom. The feeding system had two hoppers with
two locks and two screw feeders of 6 cm diameter. This gasifier
usually worked with biomass flow rates of 10 kg/h. The in-
gasifier-bed material was a mixture of 70-80 wt % silica sand
and 20-30 wt % calcined dolomite. Silica sand + calcined
dolomite (13 kg) were used in each test, equivalent to a (bulk,
fixed) bed height of 50 cm. The superficial gas velocity (gasifier
conditions) at the bed inlet typically used was 45 cm/s. Some
(17) Brown, R. C.; Sadaka, S. S.; Norton, G.; Xu, M.; Bown, N.
Thermochemical production of hydrogen from biomass. In Proceedings of
the 2nd World Conference on Biomass for Energy, Industry and Climate
Protection, Rome, May 10-14, 2004; Van Swaaij, W. P. M., Fjallstrom,
T., Helm, P., Grasi, A., Eds.; ETA-Florence: Florence, Italy, 2004; pp
1144-1147 (ISBN: 88-89407-01-2).
(18) Zhang, R.; Brown, R. C.; Suby, A. Thermochemical generation of
hydrogen from Switchgrass. Energy Fuels 2004, 18 (1), 251-256.
(19) Ederer, H. J.; Fritsch, T.; Henrich, E.; Mas, C. Water-gas-shift-
of the 2nd World Conference on Biomass for Energy, Industry and Climate
Protection, Rome, May 10-14, 2004; Van Swaaij, W. P. M., Fjallstrom,
T., Helm, P., Grasi, A., Eds.; ETA-Florence: Florence, Italy, 2004; pp 918-
920 (ISBN: 88-89407-01-2).
(20) Effendi, A.; Hellgardt, K.; Zhang, Z.-G.; Yoshida, T. Optimising
H2 production from model biogas via combined steam reforming and CO
shift reactions. Fuel 2005, 84, 869-874.
(21) Narvaez, I.; Orio, A.; Aznar, M. P.; Corella, J. Biomass gasification
with air in an atmospheric bubbling fluidized bed. Effect of six operational
variables on the quality of the produced raw gas. Ind. Eng. Chem. Res.
1996, 35 (7), 2110-2120.
(22) Corella, J.; Aznar, M. P.; Gil, J.; Caballero, M. A. Biomass
gasification in fluidized bed: Where to locate the dolomite to improve
gasification? Energy Fuels 1999, 13 (6), 1122-1127.
 Hydrogen Production by Biomass Gasification
other details concerning the gasifier can be found in refs 10
and 11. It must be pointed out that the total tar content in the
raw gasification gas under these experimental conditions was
relatively low, of the order of only 2 g/Nm3.23 This is a key
limit to get a good performance, high life, of the catalytic
reactors located downstream from the gasifier.15
Feedstock. An easy-to-feed and easy-to-gasify feedstock was
selected for the research presented in this paper: small pine
(Pinus pinaster) wood chips. This type of biomass has a content
of sulfur and of nitrogen of only a very few ppms. Its full
characterization, including its detailed elemental analysis, was
published previously.10,11 It may be repeated here that its H2
content was 5.7 wt %.
A 2-3 wt % of the overall mass flow rate was calcined
dolomite. It was continuously fed, mixed with the biomass, to
replace the dolomite eroded and carried out of the gasifier by
elutriation.
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Catalytic Reactors. After the gasifier and before the heat
exchanger, a slip flow was taken from the gasification raw gas
and sent to several catalytic reactors connected in series, as
indicated in refs 10 and 11. The first catalytic reactor contained
a commercial steam-reforming nickel-based catalyst to eliminate
Publication Date (Web): March 16, 2006 | doi: 10.1021/ef050428p
most of the tar present in the gasification gas, correspondently
increasing the H2 content in it. At the exit of this reactor (inlet
of the high-temperature (HT) shift reactor) the tar content was
only 10-30 mg/Nm3 (for more details on the gas composition
in that location, see ref 15). This low tar content did not
deactivate the downstream CO-shift catalysts, at least in the few
hours on stream of each test.
Downstream from the catalytic steam-reforming reactor, there
were one or two reactors with commercial CO-shift catalysts.
Two types of tests were made: with only one CO-shift catalyst
and with a combination of high- and low-temperature catalysts.
When two shift reactors were used, the first one was a high-
temperature (HT) reactor and the second one was a low-
temperature (LT) reactor. The CO-shift catalytic reactors had
4.1 cm i.d. and 63 cm total height. Before the test itself, the
shift reactors were externally heated by two ovens of 1.5 kW
to get the desired level of temperature in each bed. When the
whole gasification plant reached steady state, these external
ovens were switched off. So, both CO-shift beds operated under
near-adiabatic conditions, which is a well-known and/or recom-
mended operation for CO-shift catalytic reactors (i.e., ref 24).
Between the HT and the LT beds, there was some cooling to
decrease by 200-250 C the temperature of the gas before
entering the LT reactor. In some of the latest tests, some
preheated steam was also introduced between the steam-
reforming and the HT CO-shift catalytic reactor to increase the
H2O/CO ratio in the flowing gas.
Because of the size of the CO-shift catalytic reactors,
temperature gradients could be important. So, three thermo-
couples were placed in each bed, two in the axis and one in the
wall, inner side. Of course, temperatures in the shift reactors
were carefully controlled during each test to avoid catalyst
sintering (which occurs at 350 C with the low-temperature
catalyst and at 550 C with the high-temperature one).
To keep constant the H2O/CO ratio and the gas composition
at the inlet of the CO-shift reactor was not difficult in this
facility, because the upstream gasifier operated without troubles.
(23) Corella, J.; Li, G.; Toledo, J. M. Experimental Conditions to get
less than 2 g tar/Nm3 in a Fluidized Bed Biomass Gasifier. Presented at the
14th European Conference on Biomass for Energy Industry and Climate
Protection, Paris, France, Oct 17-21, 2005.
(24) Rase, H. F. Case study 105: The CO-shift reactor. Chemical Reactor
Design for Process Plants; John Wiley: New York, 1977; Vol. 2.
Energy & Fuels, Vol. 20, No. 3, 2006 1307
It was, therefore, easy to avoid variations with time-on-stream
of temperature in shift reactors.
Two important operation parameters, temperatures and hourly
space velocity, in the two CO-shift beds were as follows.
catalyst T (C) SV (Nm3, wet gas/(m3 h))
inlet exit
HT 350 480 1300-2700
LT 200 260 4600-5100
CO-Shift Catalysts. Commercial CO-shift catalysts were
provided by ICI Katalco (U.K.) and BASF AG (Germany). They
were tested with their commercial sizes and shapes.
High-Temperature (HT) CO-Shift Catalyst. Two different
commercial HT catalysts were used: ICI 15-5 and BASF K6-
11. Their composition is a mixture of iron and chromium oxides
and is similar to that used by Brown and co-workers18 The
catalysts were used in their commercial shape, pellets 5.4 mm
diameter 3.6 mm high for the ICI catalyst and tablets of 6
6 mm for the BASF one. These catalysts require an initial
reduction of the iron oxide (Fe2O3) to magnetite (Fe3O4). The
essential features of the reduction are that steam must be present
and that the CO content of the reducing gas should be less than
a limiting value, which could overheat the catalyst. On a wet-
gas basis, CO should typically be <15% vol. Steam must be
present to prevent overreduction (i.e., Fe forming). Metallic iron
is undesirable because it catalyzes the following reactions:
CO + 3H2 S CH4 + H2O (1)
2CO S CO2 + C (2)
Besides, the coke (C) formed would deactivate the HT catalyst
not only by coking but also by formation of iron carbide (FexCy).
If there are high sulfur contents (g100 ppm) in the process
gas, these catalysts are converted to the sulfided (FeS) form,
which is less active than magnetite. With the pine wood chips
used as feedstock in this work, the sulfur content in the
gasification gas was well below this concentration and no
halogens were present in the gas. Since the shift reaction is
exothermal, care was taken to avoid a big temperature rise,
which could occur because of the relatively high CO content at
the inlet of this bed.14
Low-Temperature (LT) CO-Shift Catalyst. The low-temper-
ature CO-shift catalyst used, coded K3-110, was provided by
BASF. It consists of copper and zinc oxide on alumina and was
used in its commercial shape, tablets of 5 3 mm. This catalyst
is also similar to that used by Brown and co-workers,18 although
they used a lower space velocity (1200 h-1). More details on
these catalysts can be found in ref 25 and in the booklets
provided by the corresponding catalyst manufacturers.
Tar and Gas Sampling and Analyses. Tar sampling and
analysis were made under conditions similar to those indicated
in the so-called tar protocol.26 Samples of gas and of tar were
taken periodically (every 0.5-1.0 h) before and after the CO-
shift reactors. This enabled us to know the variation of the gas
composition and of the tar content in the gasification gas due
to the CO-shift reactors. The tar content at the inlet of the HT
CO-shift reactor was dependent on the gasifying ratio (GR),
defined11 as (H2O + O2)/biomass, used in the upstream gasifier,
and on the temperature and type of the steam-reforming (Ni-
(25) Rase, H. F. Handbook of Commercial Catalysts: Heterogeneus
Catalysts; CRC Press: Boca Raton, FL, 2000; Chapter 19.3.
(26) van Passen, S. V. B.; Kiel, J. H. A.; Neeft, J. P. A.; et al. Guideline
for sampling and analysis of tar and particles in biomass producer gas;
Report No. ECN-C-02-090; ECN: Petten, The Netherlands, Nov 2002.
 1308 Energy & Fuels, Vol. 20, No. 3, 2006
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Figure 1. CO conversion (with different CO-shift catalysts) vs the
H2O/CO ratio in the gas at the inlet of the HT CO-shift reactor.
Publication Date (Web): March 16, 2006 | doi: 10.1021/ef050428p
Figure 2. CO content in the gas at the exit of the CO-shift system vs
H2O/CO ratio in the gas at the inlet of the HT CO-shift reactor.
based) catalyst used before the CO-shift reactor. This tar content,
as previously said, was very low (10-30 mg/Nm3).15
Results
The variation of the gasification gas composition due to the
CO-shift reactors has been studied for four different experi-
mental variables: (i) the use of one or two shift reactors, (ii)
the type of gasifying agent (air and H2O-O2 mixtures) used in
the upstream gasifier, (iii) the temperature of reference in the
shift reactors, and (iv) the H2O/CO ratio at the inlet of the HT
shift reactor.
Variation of the CO Content, CO Conversion. The molar
H2O/CO ratio in the gasification gas at the inlet of the HT shift
reactor was demonstrated to be a good parameter to correlate
the results. The CO conversion by the CO-shift reactors
increases as that H2O/CO ratio increases, as Figure 1 shows.
CO conversions (eliminations) of 90% were achieved in this
work for [steam/CO] g 2; see Figure 1. It is believed that even
higher CO conversions could be obtained at steam/CO ratios
higher than those used in this work.
To give an idea of the CO content in the gas at the exit of
the LT shift reactor, that CO content is shown in Figure 2. A
CO content as low as 2.6 vol. % was obtained for [H2O/CO] )
2.4.
Aznar et al.
Figure 3. Increase of the hydrogen content vs temperature at the exit
of the HT shift bed (for different CO-shift catalysts).
Figure 4. Increase of the hydrogen content in the flowing gas vs steam-
to-CO ratio in the gas at the inlet of the CO-shift reactor.
H2 Content. An increase between 0.8 and 14 vol % of the
H2 content in the gas was observed. Figure 3 shows such
increases in terms of temperature of reference in the axis of the
HT catalytic bed.
The increase of the H2 content in the gas also correlates with
the H2O/CO ratio in the gas, as Figure 4 shows. An increase of
12-14 vol % was obtained for [H2O/CO] g 2.
Remembering that, at the exit of the upstream steam-
reforming catalytic reactor, under optimized conditions, there
was 59 vol % H2 (see Table 1), with this increase of 12-14
vol % by the CO-shift system, then a total of 71-73 vol %,
dry basis, was the maximum H2 content measured at the exit
of the shift reactor. The dispersion of points in Figures 1-4 is
due to the possible different temperature and/or type of CO-
shift catalyst used in each test.
CH4 Content. Methane is not a desirable product for this
process. The presence of metallic iron in the catalyst promotes
the undesirable reaction CO + 3H2 S CH4 + H2O at
temperatures below 500 C. It produces methane as a byproduct
and consumes hydrogen. The metallic iron could be formed by
an overreduction of the HT CO-shift catalyst, according to Fe3O4
+ 4H2 S 3Fe + 4H2O, or from not having enough steam
content present in the inlet gas during operation. In that case,
Fe3O4 + 4CO S 3Fe + 4CO2.
An increase in the CH4 content of 0-0.4 vol % was detected
in some tests; see Figure 5. This figure shows a nil content
 Hydrogen Production by Biomass Gasification
Figure 5. Increase of the CH4 by the CO-shift system (for different
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catalysts).
increase in some runs or a negligible increase in others. The
CH4 formation was avoided in the final tests by adding some
steam before the HT shift reactor and working at the inlet of
the HT shift reactor at [H2O/CO] g 2.
Publication Date (Web): March 16, 2006 | doi: 10.1021/ef050428p
Experimental Results vs Equilibrium
The composition of the outlet gas from the LT shift reactor
was compared in all tests with that corresponding to the
thermodynamic equilibrium and given by
( )
yCO2yH2
260 C
K) ) 75 (3)
yCOyH2O at equilibrium
K is 75 at the most-often-reached temperature, which in this
work, at the exit of the LT shift reactor, is 260 C. At the other
hand, in one of the best experiments, when the H2 content was
the maximum obtained value (73 vol %) in this work, the
experimental data provided the following:
( )
yCO2yH2
) 15 (4)
yCOyH2O experimental
Comparing these two values (75 and 15), it may be deduced
that the gas composition obtained was, therefore, still somewhat
far from equilibrium. It indicates that still better results could
be obtained from a further and improved experimentation.
Energy & Fuels, Vol. 20, No. 3, 2006 1309
Conclusions
(i) The use of two CO-shift reactors downstream from a
fluidized-bed biomass gasifier, gasifying with steam-O2 mix-
tures, and a catalytic steam reformer generated an exit gas with
73 vol % H2, dry basis, and only 2.6 vol % CO (the remaining
is CO2 and small amounts of O2 and CH4). This 73 vol % H2
seems a very high value, but it corresponds, in these tests, to
0.14 (kg of H2)/(kg of biomass daf). It is also noticed, for
possible further economic evaluations, that, since the gasifi-
cation was carried with H2O-O2 mixtures, the amount of O2
required in these tests was 0.30 (kg of O2)/(kg of biomass
daf).
(ii) The H2O/CO ratio in the gas at the inlet of the HT shift
reactor is a very important parameter in this process, and it
correlates well with the results obtained here.
(iii) CO conversions (eliminations) >90 vol % have been
obtained.
(iv) To get CO conversions >90%, high (g2) steam/CO ratios
are needed at the inlet of the HT shift reactor.
(v) From the experience gained in this research, the authors
believe that an improved design and operation of the CO-shift
catalytic reactors, with an optimized temperature profile, could
still improve the results presented here. In fact, the thermody-
namic equilibrium constant at 260 C (exit temperature of the
LT shift reactor) is 75, and the similar ratio calculated with
experimental results is only 15, indicating that there are still
some possible further improvements.
(vi) With such a low tar content (on average, in these tests,
20 (mg of tar)/Nm3) in the gasification gas entering the HT
CO-shift catalytic reactor, there was no deactivation of the shift
catalysts after 10 hours on stream.
(vii) The overall gasification process (advanced fluidized-
bed gasifier + steam-reforming bed + two CO-shift reactors)
is complex and could result with the produced H2 having a high
cost.
(viii) Nevertheless, the overall gasification process described
in this work was operated without major technical problems.
For these authors, the process is technically feasible.
Acknowledgment. We are grateful to Javier Gil and Juan-
Antonio Martn for their help in performing some experiments. We
are also grateful to BASF AG and ICI-Katalco for providing
samples of their catalysts.
EF050428P