2668 Ind. Eng. Chem. Res.

1998, 37, 2668-2680

Commercial Steam Reforming Catalysts To Improve Biomass

Gasification with Steam-Oxygen Mixtures. 2. Catalytic Tar
Removal
Mara P. Aznar,*, Miguel A. Caballero, Javier Gil, Juan A. Martn, and
Jose Corella
Chemical and Environmental Engineering Department, University of Saragossa, 50009 Saragossa, Spain, and
Chemical Engineering Department, University Complutense of Madrid, 28040 Madrid, Spain

Eight different commercial catalysts, nickel based, for steam reforming of naphthas and of natural
gas are tested in biomass gasification for hot gas cleanup and conditioning. They were
manufactured by BASF AG, ICI-Katalco, UCI, and Haldor Topse a/s. The catalysts were tested
in a slip flow after a biomass gasifier of fluidized bed type at small pilot-plant scale (10-20 kg
of biomass/h). The gasifying agent used is steam-oxygen mixtures. A guard bed containing a
calcined dolomite is used to decrease the tar content in the gas at the inlet of the catalytic bed.
Main variables studied are catalyst type, bed temperature, H2O + O2 to biomass feed ratio, and
time-on-stream. All catalysts for reforming of naphthas show to be very active and useful for
tar removal and gas conditioning (in biomass gasification). 98% tar removal is easily obtained
with space velocities of 14 000 h-1 (n.c.). No catalysts deactivation is found in 48 h-on-stream
tests when the catalyst temperature is relatively high (780-830 C). Using a simple first-order
kinetic model for the overall tar removal reaction, apparent energies of activation (of around 58
kJ/mol) and preexponential factors are obtained for the most active catalysts.

Introduction thermal efficiency of the gasification process were

It is well-known how biomass gasification in fluidized
bed produces a dirty raw gas that has to be cleaned of
tar and particulates for most of its applications. Wet
gas cleaning is usually not desired because it produces
a flow of contaminated condensates of very difficult
disposal and, besides, it cools the flue gas, lowering the
overall thermal efficiency of the biomass-to-electricity
process. Hot dry gas cleaning and upgrading is nowa-
days the best solution which, in turn, has two, at least,
main ways, solutions or processes: using calcined
dolomites (OCaOMg) or related materials and using
steam reforming, nickel-based, catalysts. Calcined do-
lomites are cheap and useful materials, above 800 C,
for this application, but their use and study is here out
of the scope of this paper which is concentrated on the
use of nickel-based catalysts.
Steam reforming catalysts have already proved their
usefulness in biomass gasification for gas upgrading.
They eliminate tars present in the raw flue gas by steam
and dry (CO2) reforming reactions whose mechanism
and reacting network are not well-known nowadays but
which seem similar to the steam reforming of natural
gas and of naphthas. The state-of-the-art and the
institutions working or having worked in this process
of hot gas cleaning with nickel catalysts have been
reported previously (Aznar et al., 1992, 1993; Narvaez
et al., 1997; Alden et al., 1997; Caballero et al., 1997;
Corella et al., 1998; Abatzoglou et al., 1998). In part 1
of this work (Caballero et al., 1997) it was shown how
gas composition (H2, CO, CO2, CH4, C2, steam, ...,
contents), heating value of the gas, gas yield, and
* Author to whom correspondence should be addressed.
University of Saragossa. Fax: + 34 76 76 21 42.
University Complutense of Madrid. Fax: + 34 1 394 41
64.
S0888-5885(97)00672-6 CCC: $15.00 1998 American Chemical Society
Published on Web 06/09/1998
modified by a catalytic bed (nickel-based catalysts)
located in a slip stream downstream of a fluidized-bed
biomass gasifier. Now, in this part, it will be shown in
detail how this catalytic bed eliminates the tars present
in the flue gas and which variables affect this tar
removal. This study is carried out at small pilot-plant
scale with eight different commercial steam reforming
catalysts. Some deactivation studies or lives of the
catalysts are also presented.
Experimental Section
Pilot Plant Used. The present study has been
carried out in a facility which can be considered a small
pilot plant. It is based on a bubbling fluidized bed of
15-cm i.d. and 3.2-m height continuously fed with
biomass near the bed bottom at flow rates of around 10
kg of biomass/h. It has been described previously
(Aznar et al., 1995, 1996, 1997; Gil et al., 1997). For
further comparisons on catalytic tar-removal activities
under different flue gas atmospheres (compositions), it
is clearly stated that the gasifying agent in this work
has always been steam-O2 mixtures. Since there are
thus three main reactants (steam, O2, and biomass), the
following two ratios are needed to describe the reacting
system at the gasifier inlet:
(a) (H2O + O2)/biomass dry and ash-free, (kg/h)/(kg
of daf/h), dimensionless. This gasifying ratio, which will
be here referred to as GR, has an intrinsic meaning
similar to the equivalence ratio used in biomass
gasification with air.
(b) (H2O/O2), (mol/h)/(mol/h), dimensionless.
Gasifying with steam-O2 mixtures, gas quality, and
product distribution at the gasifier exit have been
studied in detail under very different process variables,
and they have been reported previously (Gil et al., 1997).
From that previous study, the intervals selected for the
 Ind. Eng. Chem. Res., Vol. 37, No. 7, 1998 2669

Table 1. Some Main Experimental Conditions and Apparent Kinetic Constants for Tar Removal over Several
Commercial Steam Reforming (Ni-Based) Catalysts
kapp,tar
run [(kg h)/ SV [mn3 (wet)/ yH2Oa [mn3 (dry)/ [mn3 (wet)/ [m3 (Tb, wet)/
no. catalyst dp (mm) Tb (C) [m3 (Tb, wet)]] (m3 h)] (vol %) (kg h)] (kg h)] (kg h)]
5 UC C-11-9-062 -0.8 + 0.2 750 0.127 3000 39 5 8 30
6 UC C-11-9-062 -0.82 + 0.2 725 0.122 2700 45 5 9 34
7 UC C-11-9-062 -0.8 + 0.2 735 0.022 5500 31 9 12 46
8 BASF G25-1S -1.0 + 0.2 785 0.031 13800 41 33 55 214
9 nickel A -1.0 + 0.2 800 0.025 11900 46 22 41 175
10 Topse RKS-1 -1.0 + 0.2 785 0.036 10500 43 19 33 129
11 nickel Db -1.0 + 0.2 825 0.033 9700 57 7 16 64
12 nickel E -1.0 + 0.2 770 0.037 12700 55 12 27 103
13 nickel D -1.0 + 0.2 760 0.032 10300 50 15 29 111
14 silica sand -1.0 + 0.2 820 0.080 5300 45 3 7 29
15 nickel B -1.0 + 0.2 790 0.035 9200 40 18 30 118
16 nickel E -1.0 + 0.2 800 0.037 8400 42 21 36 143
20 nickel D -1.0 + 0.2 670 0.025 13100 46 26 47 164
21 nickel B -1.0 + 0.2 630 0.028 13400 47 29 56 183
22 nickel A -1.0 + 0.2 640 0.027 14700 45 25 45 149
23 nickel D -1.0 + 0.2 804 0.021 15000 40 51 85 349
24 nickel D -1.0 + 0.2 780 0.019 16000 44 44 79 333
25 nickel B -1.0 + 0.2 775 0.023 14000 53 23 49 188
26 nickel D -1.0 + 0.2 830 0.020 15000 56 27 62 249
27 nickel A -1.0 + 0.2 790 0.027 13100 45 28 52 201
28 nickel B -1.0 + 0.2 780 0.025 13000 53 29 62 238
29 silica sand -1.0 + 0.2 820 0.029 7500 42 4 7 17
30 nickel A -1.0 + 0.2 800 0.035 12000 52 28 42 132
31 nickel D -1.0 + 0.2 780 0.034 11500 55 22 35 98
a Average steam content in flue gas, from mass balance. b Sintered.

gasifier operation in this work are
0.70 e GR e 1.60
2.0 e (H2O/O2) e 3.0
800 C < gasifier bed temperature < 860 C
In this work the gasifier bed is silica sand only
(without in-bed dolomite), with the corresponding char
produced and existing under the stationary state. One
test or experiment lasted on average 1.2 months (in-
cluding test and feedstock preparation, analysis of the
gas and tar samples, cleaning of the pilot plant, etc, ...).
The running of the pilot plant during one test lasted on
average 20 h (the plant was not able to work under
reaction overnight because of its location in the Uni-
versity), of which about 10 h were under the stationary
state (in all of its reactors, vessels, and equipment). Data
reported here will refer thus only to stationary states.
For catalyst deactivation studies, the plant was stopped
overnight and operated the next day.
Biomass Used. The biomass used as the feedstock
in all tests has been pine (Pinus Pinaster) wood chips
of -5.0 + 1.0 mm. This biomass was always partially
dried until a moisture content of 10-12 wt % existed.
This feedstock did not cause problems in the feeding
system used in the pilot plant. Its physical and chemi-
cal characterization have been reported previously (i.e.,
Narvaez et al., 1996).
Catalytic Reactor. The catalytic reactor was a
downward fixed bed of 4.1-cm i.d. It was described in
detail in part 1 of this work (Caballero et al., 1997). Four
main variables have been studied in this work: catalyst
type, temperature (Tb) of the catalytic bed, gas residence
time expressed as space time () or as space velocity
(SV), and gas atmosphere composition which depends
on the GR value used in the gasifier. Due to the type
and size of the catalytic bed, radial and longitudinal
temperature gradients were foreseen in it. For this
reason temperatures in the bed were measured with
three thermocouples (two in the bed axis and one in the
bed wall, inner side). The temperature used here as
reference (Tb) is the average (arithmetic mean) between
the bed axis and the wall (inner side) at 5 cm (roughly
the middle of the bed height) from the bed inlet.
Several research programs (such as AIR2, JOULE2,
JOULE3) of the European Union (DGXII) are financing
projects on catalytic hot gas cleaning (since the present
one) in which several Institutions from different coun-
tries are participating and have to compare their results.
In periodic and internal meetings among the partners
in these projects, it has been made clear how important
(for comparison purposes) it is to define in the same way
the variables to be further compared. This is the reason
for the units selected and used for and SV in this work.
The activity of the catalysts for the overall tar
elimination will be given by a kinetic constant (kapp,tar).
It is based on or deduced from a first-order kinetic
equation and a single and overall reaction of tar
elimination (Narvaez et al., 1997). The units of this
index (see Table 1, for instance) are also very important
for further comparisons.
Catalysts Used. Eight different commercial steam
reforming catalysts have been tested in this work. They
come from the four main manufactures of this type of
catalyst in the world: BASF AG, ICI-Katalco, Topse
A/S, and United Catalyst Inc. (UC). Four of these
catalysts are for steam reforming of light hydrocarbons
(natural gas), and four are for reforming of heavier
hydrocarbons (naphthas). Their physical (pore volume
and distribution, BET surface area, ...) and chemical
characterization have been shown in detail in part 1 of
this work (Caballero et al., 1997). Due to secrecy
agreements, some catalysts have to be referred as A,
B, C, and D (having been well characterized and
described in part 1 of this work).
Commercial steam reforming catalysts are suminis-
trated as rings (with one or several holes) of about 1-cm
2670 Ind. Eng. Chem. Res., Vol. 37, No. 7, 1998
Figure 1. Tar content in the flue gas in three different locations for run 28 using the nickel B catalyst.
height and 1-cm o.d. Since the catalytic reactor had 4.1-
cm i.d., to avoid big wall effects, these catalysts were
all crushed and sieved until a size of -1.0 + 0.2 mm
(which, was the size always used in this work) was
reached. Crushing of these catalysts is not good, of
course, mainly for the impregnated catalysts, but the
authors had no other solution at hand.
Two other facts concerning the particle size and shape
of the catalysts used have to be taken into account:
(1) The effectiveness factors of the BASF G1-25S
catalyst, for the same reaction, was determined experi-
mentally previously for different particle sizes (Narvaez
et al., 1997). From that work it was deduced that for
particle diameters bigger than around 0.3 mm the
internal diffusion starts to have influence on the overall
process (in the apparent activation energy, for instance).
To compare the intrinsic chemical activity of the cata-
lysts, the size of -1.0 + 0.2 mm was selected. In this
interval of particle sizes the internal diffusion does not
control fully but it starts to have some influence
(Narvaez et al., 1997) and it will have to be taken into
account (in the values obtained for the activation energy,
for instance).
(2) In some gasification processes the flue gas coming
to the catalytic bed can contain some particles (char,
silica sand elutriated from the gasifier, etc., ...). In this
case a honeycomb or monolith catalyst is recommended,
but this shape it is not available in the market yet for
steam-reforming catalysts. So, although monoliths will
be tested when available, only (crushed) commercial
rings were tested here and a filter had to be used before
the catalytic bed.
Some main experimental conditions for the catalytic
bed are shown in the first columns of Table 1. A
noticeable fact is that the steam content (yH2O) in the
flue gas in the catalytic reactor is quite high (clearly
higher than the steam content when biomass gasifica-
tion is carried out with air). The (H2O/C*) ratio was
always high, always higher than 2.0 which is the
minimum value used in commercial steam reformers
(Basini and Piovesan, 1998).
Steam reforming of hydrocarbons such as tars can
generate coke on the catalyst surface, which can deac-
tivate the catalyst. Catalyst deactivation occurs when
the throughput of tars coming to the catalytic bed is
high (Aznar et al., 1993). These authors have given the
limit of about 2 g of tars/mn3 to avoid in this process
catalyst deactivation by coke. Since the tar content in
the raw gas usually has a value higher than this limit
(Gil et al., 1997), it is of basic importance to decrease
this tar content in the flue gas below the said limit of 2
g of tars /mn3. This fact can be achieved in several ways.
The one used in this work was to use a guard bed of
calcined dolomite before the catalytic bed. This guard
bed decreases the tar content in the flue gas until about
0.5-1 g/mn3 (Figure 1). This tar content can now be
easily processed (removed) by the catalytic bed.
Tar Definition, Sampling, Analysis, and Char-
acterization. For comparison purposes tar definition
and measurement (sampling and analysis) has been
standardized very recently, as Corella and Milne et al.
among others claimed (Corella, 1996; Milne et al., 1997).
On March 17-19, 1998, organized by IEA, Thermal
Gasification of Biomass Task, the European Commis-
sion (DGXVII), and U.S. DOE, there was a meeting in
Brussels in which a protocol was accepted for tar
definition and measurement in the field of biomass
gasification. It will be published in June 1998. From
that date tar should have the same meaning and value
worldwide but the present work was made before such
date, and the tar content and even the type of tar
mentioned in this paper can possibly be somewhat
different from the ones from other authors or gasifiers
(Corella, 1996; Milne et al., 1997). Since, the tar
sampling method used here was similar to the most
developed one (as the one used by VTT in Finland)
shown in the said tar protocol meeting held in Brussels,
these authors believe that amounts and conclusions in

Figure 2. Tar conversion in the catalytic bed vs temperature [s, nickel D][0.019 < < 0.037 (kg h)/m3 (Tb, wet); H2O/O2 ) 2 and 3
mol/mol].
this paper concerning tar can be applied to other
gasification plants.
Although there has been an international agreement
concerning tar as a whole lump, there is still a clear
need for advancement in the definition of other sub-
lumps related to tar. For instance, in catalytic gas
cleaning (this work) it seems clear how there are some
easy-to-destroy (convert) or soft tars and some other
difficult-to-destroy or hard tars. Although these
concepts and/or sublumps are not standardized yet, we
will have to use them in this work.
In this work the flue gas was periodically sampled
(for gas and for condensates) before and after the
catalytic bed and before and after the guard bed. Tars
were measured in the condensates under the method
previously described by Narvaez et al. (1996), which is
very similar to the standard method recently agreed
upon.
The tar composition varies in the guard bed and in
the catalytic bed. Samples of tars were sent to NREL
(Golden, CO) and to KTH (Stockholm, Sweden) to be
characterized by molecular beam mass spectrometry
(Evans and Milne, 1997) and by solid-phase ad-
sorption-desorption (Brage et al., 1997), respectively.
Although this characterization is not fully accomplished
yet for all operation parameters, there are already
useful data available in our plant on this subject. It
can be said thus that the bed of calcined dolomite mostly
eliminates/destroys the soft tars (the tars that can be
easily destroyed such as phenol derivatives) and only
the hard tars (naphthalene and similar PAHs) come now
to the catalytic bed (Caballero et al., 1997). This fact
has to be taken into account when comparing kinetic
constants for tar removal obtained with nickel catalysts
and with calcined dolomites: the reactant (tar) is not
the same (does not have the same composition) in both
beds.
Ind. Eng. Chem. Res., Vol. 37, No. 7, 1998 2671
Results
In most of the figures in this paper (Figures 2-5, ...)
results will be indicated only by a point (, O, 0, ...)
although they should be given by not-small rectangles
(as in the simultaneous paper of Orio et al. (1997), for
instance). In fact, in the catalytic bed there are tem-
perature differences of 10-25 C, and in tar sampling
and analysis there are some errors too. Senents errors
theory (Senent, 1962), based on statistical analysis, has
always been taken into account in this work, but points
instead of rectangles are used in the figures in this
paper because (i) they make such figures clearer and
(ii) using rectangles instead of points do not add more
information and does not modify the conclusions. Sta-
tistics and errors theory have been taken into account
thus, and points shown in Figures 2-5, ..., will have to
be understood as the center of the rectangle in each
measurement.
Tar Conversions (in the Catalytic Bed). From the
measured tar contents in the flue gas at the catalytic
bed inlet and exit, tar conversion (Xtar) in the catalytic
bed was calculated for all catalysts under well-known
experimental conditions. This overall tar conversion
includes all catalytic reactions (for tar removal) as well
as thermal reactions.
Effect of the Bed Temperature. The effect of the
bed temperature is shown in Figure 2 for space times
() of 0.019-0.037 kg of catalysth/m3 flue gas (Tb, wet).
All points correspond to H2O/O2 ratios (in the feeding
system) of 3.0, except two points shown in Figure 2.
Figure 2 shows how tar conversion increases with
temperature in this process. In nearly all experiments
tar conversions higher than 96% were achieved.
Effect of the Gasifying Ratio. The gasifying ratio
[GR, or (H2O + O2)/biomass fed] used in the gasifier has
an effect on tar conversion. Tar conversion depends on
the gasifying ratio (GR) used in the upstream gasifier,
as Figures 2 and 3 clearly demonstrate. The two lines
2672 Ind. Eng. Chem. Res., Vol. 37, No. 7, 1998

Figure 3. Tar conversion in the catalytic bed for different gas atmospheres [770 < Tb < 800 C; 0.019 < < 0.037 (kg h)/m3 (Tb, wet)].

Figure 4. Tar concentration in the flue gas at the exit of the catalytic bed for different GR values and catalysts [770 < Tb < 800 C;
0.019 < < 0.037 (kg h)/m3 (Tb, wet)].

drawn in Figure 2 correspond to the nickel D catalyst,
which showed to be one of the most active and most used
(in this work) catalysts.
Results shown in Figures 2 and 3 indicate that tars
produced at high (>0.95) GR values are more difficult
to convert (destroy) than tars generated at low (<0.95)
GR values.
Tar conversions shown in Figures 2 and 3 are nearly
always higher than 97% (remember they were obtained
with very low space times, equivalent to or very high
space velocities). This makes the tar content in the flue
gas after the catalytic reactor very low as Figure 4
shows. For instance, tar contents in the exit gas of only
5 mg/mn3 are obtained with these catalysts.
Very low tar contents at the exit of the catalytic
reactor are mainly obtained when the upstream gasifier
is operated at low GR values (Figure 4) because the tars
so obtained are easier-to destroy or softer than the
tars obtained when high GR values were used in the
gasifier.
 Ind. Eng. Chem. Res., Vol. 37, No. 7, 1998 2673

Figure 5. Tar conversion vs gas residence time: (a) detail of the high-conversion range; (b) full scale for the conversion, including tests
with an inert solid (silica sand) [630 < Tb < 830 C; H2O/O2 ) 2 and 3 mol/mol] [s, nickel D; - -, nickel B and A; - - -, division between
the two temperature ranges].

Effect of the Gas Residence Time. The effect on
tar conversion of the gas residence time in the catalytic
bed, expressed as space time (), is shown at two
different scales (both useful) in Figure 5 for the different
catalysts. Two lines are drawn in Figure 5a, only for
illustrative purposes, for two levels of temperature for
the nickel D catalyst. All catalysts of steam reforming
of naphthas are very active for tar conversion (elimina-
tion). They need a space time of only 0.020 kg of
catalysth/m3 (Tb, wet) to get conversions of around 98%
(Figure 5a). This value for the space time is equivalent
to a space velocity of around 14 000 h-1 (flow in normal
conditions) or to a residence time lesser than 0.1 s. This
means a very high intrinsic catalytic activity and
usefulness for tar elimination. This space velocity
(14 000 h-1) to get 98% tar conversion is higher than
the ones reported (Caballero et al., 1997) by Chornet et
al. of University of Sherbrooke (Canada) and by Simell
et al. of VTT Energy of Espoo (Finland). This means
that the catalysts used here need less gas residence
2674 Ind. Eng. Chem. Res., Vol. 37, No. 7, 1998
Figure 6. Effect of the gasifying agent-to-biomass ratio on the apparent kinetic constant for tar removal over several commercial steam-
reforming catalysts [H2O/O2 ) 3 mol/mol; 680 < T < 840 C].
time, which, in turn, also means that they are more
active than the ones reported to date by Chornet et al.
and by Simell et al.
Another important fact drawn from the results shown
in Figure 5a,b is that there are no big differences in
activity (tar conversion) among catalysts A, B, D, and
E.
In Figure 5b the same results are presented at full
scale to show the following: (i) Thermal reactions are
important in this process. Tar conversions obtained
with an inert (silica sand) at 820 C are important in
this process. Thermal reactions will have to be taken
into account in a more elaborate reaction network for
tar removal. (ii) There appears a need for further
research (tests) at very low space times to find the trend
or shape of the Xtar- curve at the beginning of the
overall tar removal. To find what happens in this zone,
a range or interval is needed to further develop good
and/or more elaborate reaction networks and kinetic
models.
Comparison of Catalysts with a Kinetic Model
The European Institutions participating in the EU
financed projects on hot gas cleaning Nos. AIR2-CT93-
135 and JOR3-CT95-0053 agreed some years ago to use
the same, easy-to-handle kinetic model for comparison
of results obtained in tar removal with different cata-
lysts. Such a model was previously described (Corella
et al., 1996a,b; Narvaez et al., 1997; Delgado et al.,
1997). It uses the following single first-order (for tar)
kinetic equation:
(-rtar) ) kapp,tarCtar
which can be used in integrated form, working under
piston or plug-flow conditions, as
kapp,tar ) [-ln(1 - Xtar)]/
This kinetic constant (kapp,tar) can be used thus as an
index on catalytic activity for comparison purposes
among different catalysts or experimental conditions,
even though tar was defined in the same way by each
Institution (Milne et al., 1997). Values for kapp,tar found
in this work are shown in the last columns of Table 1.
These values are given in different units because each
Institution working in this field prefers to use different
measurements for the gas flow. Notice how different
the values for kapp,tar can be depending on how the gas
flow is considered/measured, dry or wet.
kapp,tar values for four catalysts are plotted against GR
in Figure 6. To give a rough idea of the pattern, only
three zones are drawn in Figure 6; they are for the most
active catalysts (A, B, D, E), at different gas residence
times.
From the results shown in Figure 6 three important
conclusions are obtained:
(1) Tars generated (in the gasifier) at low GR values
have kapp,tar values higher than tars obtained at high
GR values. Low GR values would produce soft (easy-
to-convert) tars, similar to pyrolysis tars: high GR
values would produce hard tars (with relatively low
kapp,tar values for their destruction).
(2) At relatively small times-on-contact (), values
obtained for kapp,tar are higher than the ones obtained
at elevated values of . This would mean that at the
entry of the catalytic reactor some (soft) tars are
converted very quickly; thus the very hard tars remain
to be removed (destroyed) only with relatively high
residence times. In other words, results in Figure 5
(1) demonstrate how the lump tar behaves in the catalytic
reactor as, at least, two different lumps.
(3) The simple first-order kinetic model given by eq 1
with a single lump (tar) is not good enough, and thus it
should be improved for further works, taking into
(2) account the different reactivities of the components
 Ind. Eng. Chem. Res., Vol. 37, No. 7, 1998 2675

Figure 7. Effect of temperature of the catalytic bed on the apparent kinetic constant for tar elimination over different catalysts [0.019
< < 0.037 (kg h)/m3 (Tb, wet); H2O/O2 ) 3 mol/mol].

Figure 8. Arrhenius plot for the overall tar removal reaction with several commercial steam-reforming catalysts [H2O/O2 ) 2 and 3
mol/mol] [s, nickel D; - - -, nickel E, D, and A; - -, :UC; , division between the two zones of GR].

existing in the tar. The following kinetic equation would
fit the data better than eq 1:
(-rtar) ) kapp,tar1Cn1tar1 + kapp,tar2Cn2tar2
with tar1 and tar2 being the sublump soft and hard tars.
The problem now would be to assign or discriminate the
types of molecules present in the tars which are easy-
to-destroy (soft tars) and which are hard-to-destroy
(hard tars). This study remains to be done in a future
work.
(3) kapp,tar values for different catalysts and GR values
are shown at different bed temperatures in Figure 7.
Two zones are shown in this figure, corresponding to
two GR intervals, to show again only the trend in the
ktar-Tb relationship. This relationship is shown in
Arrhenius coordinates in Figure 8. Since each point
2676 Ind. Eng. Chem. Res., Vol. 37, No. 7, 1998

Table 2. Values for the Apparent Activation Energy and Table 4. Kinetic Constants (at t ) 0) for Methane
Preexponential Factor for the Overall Tar Removal Removal over Several Commercial Steam Reforming
Reaction on Some Catalysts Tested and under Some (Ni-Based) Catalysts
Internal Diffusion Influence
kCH4
Eapp kapp,0
run mn3 mn3 mn3
catalyst (kJ/mol) [m3 (Tb, wet)/(kg h)]
no. catalyst (dry)/(kg h) (wet)/(kg h) (Tb, wet)/(kg h)
5 UC C-11-9-062 4 7 26
nickel D 58 ( 18 250 000a 6 UC C-11-9-062 5 9 33
nickel B 58 ( 20 179 000a 7 UC C-11-9-062 6 9 31
BASF G1-25S 58 ( 30 156 000a activity
increasing 8 BASF G25-1S 21 35 116
nickel A 58 ( 22 142 400a 9 nickel A 13 25 96
nickel E 58 ( 24 89 000b 10 Topse RKS-1 38 66 245
11 nickel Da 3 7 26
12 nickel E 29 65 226
13 nickel D 38 76 295
a GR < 0.95. b GR > 0.95.
14 silica sand 0.12 0.26 1
Table 3. Values for the Apparent Activation Energy and 15 nickel B 41 68 248
Preexponential Factor for the Overall Tar Removal 16 nickel E 11 19 76
Reaction on Several Catalysts (under Some Internal 20 nickel D 12 23 75
21 nickel B 13 25 81
Diffusion Influence)
22 nickel A 14 25 80
gasifying agent steam + O2 air (Narvaez steam (Delgado 23 nickel D 37 62 242
(this work) et al., 1997) et al., 1997) 24 nickel D 21 38 127
catalyst nickel D BASF G1-25S calcined dolomite 25 nickel B 30 63 224
Eapp, kJ/mol 58 ( 18 72 ( 12 97 ( 14 26 nickel D 38 86 323
kapp,0, m3 250 000 143 000 (1.2-1.4) 106 a 27 nickel A 19 34 125
(Tb, wet)/
(kg h) 28 nickel B 25 54 208
29 silica sand 0.12 0.24 1
a mn3 (wet)/(kg h). 30 nickel A 22 31 120
31 nickel D 40 80 320
a Sintered.

Table 5. Values for the Apparent Activation Energy and

Preexponential Factor for the Overall Methane Removal
Reaction for Different Catalysts Tested
kapp,0
catalyst Eapp (kJ/mol) [m3 (Tb, wet)/(kg h)]
BASF G1-25-S 62 ( 18 456 000
nickel E 62 ( 18 342 000
nickel D 62 ( 18 334 000
nickel B 62 ( 20 300 000
nickel A 30 ( 18 101 000

Figure 9. Effect of the space time and gasifying agent-to-biomass
ratio on the apparent kinetic constant for tar removal over
different commercial steam-reforming catalysts [760 < Tb < 810
C].
means around 6-8 men-months, there are only a few
points for some catalysts. It is difficult then to draw a
line in this figure for some catalysts.
After careful analysis and averaging of the results
obtained for the different catalysts, the best possible
fitting for all catalysts gave an apparent activation
energy (Eapp) of 58 kJ/mol. This (averaged) value for
Eapp (with some error, of course) was the one selected
for all the catalysts tested. The preexponential factors
(kapp,0) of the Arrhenius equation (for this selected value
of Eapp), calculated for all catalysts, are shown Table 2.
For the same Eapp value, kapp,0 is a good index for
comparing catalytic activities. Table 2 gives thus the
ranking found in this work for the catalysts, according
to their activities for tar elimination.
Values of Eapp and kapp,0 obtained in this work for the
most active catalyst, nickel D, are compared in Table 3
with other ones previously obtained for the same overall
reaction (tar removal) on different catalysts in gasifica-
tion with air. The lowest value for Eapp found in this
work (58 kJ/mol compared to 72 and 97 kJ/mol; Table
3) would indicate that nickel D catalyst is more active
than the BASF G-25S catalyst used by Narvaez et al.
(and than a calcined dolomite, of course).
Comparison of catalytic activities for tar removal is
presented in Figure 9 in another way. kapp,tar is given
there at different values of and GR. Figure 9 shows
the differences between catalysts and how nickel D is
the most active in our process.
Catalytic Activity for the Simultaneous CH4
Removal
For some applications of the produced gas, such as
its application in fuel cells, methane and other light
hydrocarbons present in the flue gas should be also
removed from the flue gas. Methane conversions on
these catalysts were shown in part 1 of this work
(Caballero et al., 1997). Using now a first-order (for
methane) kinetic model similar to the one given by eq
1, a kinetic constant for methane removal (kCH4) can also
be calculated by
kCH4 ) [-ln(1 - XCH4)]/ (4)
kCH4 values obtained in this work for different cata-
lysts and with eq 4 are shown in Table 4. These kCH4
 Ind. Eng. Chem. Res., Vol. 37, No. 7, 1998 2677

Figure 10. Arrhenius plot for the methane removal reaction (at t ) 0) over the commercial steam-reforming catalysts used in this work
[s, nickel D; - -, nickel B; --, nickel A; , UC].

Figure 11. Effect of the time-on-stream on the apparent kinetic constant for tar elimination over the nickel A, B, and D catalysts at high
temperature (780-830 C) [0.019 < < 0.037 (kg h)/m3 (Tb, wet)].

values are plotted in Figure 10 according to the Arrhe- Catalyst Life

nius equation. Some lines are drawn in this figure for
some catalysts. After a careful and similar analysis to
the tar removal reaction, an apparent energy of activa-
tion (Eapp) for methane removal of 62 kJ/mol was
selected for all catalysts. Using now the Arrhenius
equation, the preexponential factors were found. They
are shown in Table 5. This table shows the ranking of
catalysts for methane removal.
As was explained before, several tests were made for
the same catalyst in several days to get data on the
catalysts activity vs time-on-stream. So, tests of 45
h-on-stream under the stationary state were made for
the most active (regarding tar removal) catalysts. The
activity of some catalysts for tar removal, given by their
kapp,tar , is shown in Figures 11 and 12 at two different
temperature levels. At relatively high (780-830 C)
2678 Ind. Eng. Chem. Res., Vol. 37, No. 7, 1998

Figure 12. Effect of the time-on-stream on the apparent kinetic constant for tar elimination over the nickel A, B, D, and E catalysts at
low temperature (670-770 C) [0.019 < < 0.037 (kg h)/m3 (Tb, wet)].

Figure 13. Methane conversion vs time-on-stream for different catalysts at a relatively high temperature (780-830 C) in the catalytic
bed.

temperature there is not a noticeable deactivation
(Figure 11), but at low temperature (670-770 C) the
deactivation is important (Figure 12). This fact can be
explained in the following way: at high temperatures
(780-830 C) the overall rate of coke-removal (from the
catalyst surface) reactions by steam and dry (CO2)
gasification is higher than the rate of the coke-forming
reactions. So, no buildup of coke appears on the
catalysts surface and there is not deactivation in short
(45 h) periods of time. At low temperatures the coke
formation rate would be higher than the coke removal
one, and a net buildup of coke would appear, generating
a catalyst deactivation. Of course, to find out if the
catalyst is deactivated by the few parts per million of
H2S present in the flue gas, long-term tests would be
required but they are, at present, out of the realm
possibility of these authors.
Methane conversion in the catalyst bed was simul-
taneously measured at different times-on-stream. This
is shown in Figure 13. Some catalysts lose very soon

(in about 20 h) some activity for this reaction. So, there
would be a selective deactivation: Some catalysts
become deactivated for the methane-reforming reaction,
but they maintain their activity for the tar-reforming
reactions. This fact can be further investigated in a
future work.
Conclusions
The most important conclusions are, in short, as
follows:
1. Commercial steam reforming catalysts for naph-
thas are more active for tar removal (in a flue gas
coming from a biomass gasifier) than the commercial
steam reforming catalysts for light hydrocarbons (natu-
ral gas, methane).
2. The effectiveness of these catalysts in this process
(that is to say, the activity for tar removal) is so high
that no important differences appear between the four
commercial catalysts for reforming of naphthas tested
in this work. The differences in activity between the
catalysts tested are shown in Table 2.
3. Experimental variables with effects on the tar
removal conversion are temperature (of the catalytic
bed), space time or space velocity, catalyst particle size,
and gas atmosphere composition, which, in turn, de-
pends on the gasifying ratio used in the upstream
gasifier.
4. Using a single overall reaction with a first-order
kinetic equation, an apparent activation energy of 58
kJ/mol for the overall tar removal reaction fits the
experimental results.
5. Using only one lump (tar) and a single first-order
kinetic equation is not a good enough model. The
kinetic constant of such model depends thus on several
parameters such as space time (Figure 6) and flue gas
composition or gasifying ratio (Figure 7). These two
facts (not correct for a kinetic constant) cannot be
explained with such a model. A model with at least two
sublumps (like soft and hard) for tars is needed to
explain the results obtained here.
6. At relatively high (780-830 C) temperatures
there is no catalyst deactivation in a test of 45 h-on-
stream under the stationary state. Long-term (more
than 200 h, at least) tests are needed to check the
feasibility of these catalysts in a biomass gasification
process at a commercial scale.
7. It is confirmed in this work that the tar content in
the flue gas coming to the catalytic bed has to be low
enough (the authors propose 2 g of tars/ mn3 as the limit)
to avoid catalyst deactivation by coke.
Acknowledgment
This work was carried out under the JOULE III
Program of the EU DG-XII, Project No. JOR3-CT95-
0053. The authors thank the European Commission for
its financial support. Work was also done under the
Spanish DGES-financed Project No. PB96-0743. Dis-
cussions on the use of commercial steam reforming
catalysts for this process with Dr. Martyn V. Twigg of
Johnson Matthey in Royston (England), with Mr. Harald
Shafer and Roland Spahl of BASF AG, Ludwigshafen
(Germany), and with P. E. Hojlund Nielsen of Haldor
Topse A/S of Lyngby (Denmark) have been very fruitful
for us. Tar composition analyses made by Dr. K.
Sjostrom and colleagues at KTH (Sweden) and by R.
Evans at NREL, Golden, CO (USA), are recognized. The
Ind. Eng. Chem. Res., Vol. 37, No. 7, 1998 2679
invoice of samples of catalysts by BASF AG (Ludwig-
shafen, Germany), ICI-Katalko (Billingham, Cleveland,
U.K.), Haldor Topse A/S (Lyngby, Denmark), and
United Catalyst Inc. (Louisville, KY) is also gratefully
acknowledged.
Nomenclature
Ctar ) tar content in the flue gas (mg/mn3)
daf ) dry, ash free
dp ) particle diameter of the catalyst (mm)
Eapp ) apparent activation energy for tar removal (kJ/mol)
Eapp ) apparent activation energy for methane removal
(kJ/mol)
H2O/C* ) steam to carbon-to-be-reformed (CH4 + C2 + ...
+ tars) ratio in the flue gas at the inlet of the catalytic
reactor, mol of H2O/atomic g of C
GR ) gasification ratio at the gasifier inlet, defined as
[(H2O + O2)/biomass daf fed], dimensionless, (kg/h)/(kg/
h)
kapp,tar ) apparent kinetic constant for tar removal (m3 (Tb,
wet)/(kgh))
kCH4 ) apparent kinetic constant for methane removal (m3
(Tb, wet) /(kgh))
kapp,0 ) preexponential factor for kapp,tar (m3 (Tb, wet)/(kgh))
kapp,0 ) preexponential factor for kCH4 (m3 (Tb, wet)/(kgh))
Q ) gas flow rate (m3 (Tb,wet)/h)
rtar ) rate of tar elimination (mg of tar/kg of catalysth)
SV ) space velocity in the catalytic reactor [mn3 wet/(hm3)]
t ) time on stream (h)
Tb or Tbed ) temperature measured in the center of the
catalytic bed (C)
W ) weight of catalyst (kg)
XCH4 ) methane conversion (dimensionless)
Xtar ) tar conversion (dimensionless)
yH2O ) steam content in the flue gas (dimensionless)
Greek Symbols
) space time, defined as W/Q [(kg h)/[m3 (Tb, wet)]]
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Received for review September 18, 1997
Revised manuscript received April 24, 1998
Accepted April 24, 1998
IE9706727