Energy & Fuels 2004, 18, 713-720

713

Olivine or Dolomite as In-Bed Additive in Biomass

Gasification with Air in a Fluidized Bed: Which Is
Better?
Jose Corella,* Jose M. Toledo, and Rita Padilla
Department of Chemical Engineering, University Complutense of Madrid (UCM),
28040 Madrid, Spain
Received December 1, 2003. Revised Manuscript Received March 12, 2004

The raw gas from a fluidized-bed biomass gasifier should have very low tar, ammonia, and
particulates content, to make it easy to clean for its eventual use in gas engines or gas turbines.
Besides an optimized design and operation of the gasifier, it requires the use of in-bed catalytic
additives. Four available and competitive additives have been compared in this work: a calcined
dolomite (OCaOMg), natural and sintered olivines ((Mg,Fe)2SiO4), and a Ni-olivine catalyst that
was developed at the University of Strasbourg. They were tested under very similar experimental
conditions in two small-scale pilot plants: the first pilot plant was based on a circulating fluidizedbed (CFB) gasifier, and the second pilot plant was based on a bubbling fluidized-bed (BFB) gasifier.
The tar content at the gasifier exit when using dolomite was, on average, only 60% ((10%) of
the tar content when natural or raw olivine was used. This showed that dolomite was 1.40 times
more active than olivine in biomass gasification with air. Nevertheless, dolomite generates 4-6
times more particulates or dust and also some extra NH3 in the gasification gas than olivine.
Under the conditions used in this work (gasification with air), the Ni-olivine catalyst was not
very active for tar elimination and it deactivated very quickly. Much of the data on gasification
gas provided in this paper was obtained under operations similar to those found in commercial
biomass gasifiers.

1. Introduction
It is very difficult to say who was the first person to
use or suggest using dolomite (CaMg(CO3)2) as an
additive in biomass gasification in a fluidized bed.
Already at the International Conference on Thermochemical Biomass Conversion held in 1988 in Phoenix,
AZ, there was the so-called the dolomite group.
Therefore, dolomite is an old and very well-known
additive in biomass gasification. Dolomite has two main
advantages:
(1) Calcined dolomite (OCaOMg) is an inexpensive
and basic-type catalyst that eliminates unwanted tar
using steam and dry (CO2) reforming reactions. Its
effectiveness in tar eliminationssand, therefore, gas
upgradingshas made dolomite the subject of detailed
studies in gasification with pure steam,1,2 with mixtures
of H2O and O2,3 and with air.4,5 In these aforementioned
papers, detailed physicochemical characterization of
* Author to whom correspondence should be addressed. Telephone/
fax: +34-91-394-4164. E-mail: narvaez@quim.ucm.es.
(1) Delgado, J.; Aznar, M. P.; Corella, J. Calcined Dolomite, Magnesite, and Calcite for Cleaning Hot Gas from a Fluidized Bed Biomass
Gasifier with Steam: Life and Usefulness. Ind. Eng. Chem. Res. 1996,
35 (10), 3637-3643.
(2) 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), 15351543.
(3) Perez, P.; Aznar, M. A.; Caballero, M. A.; Gil, J.; Martn, J. A.;
Corella, J. Hot Gas Cleaning and Upgrading with a Calcined Dolomite
Located Downstream from a Biomass Fluidized Bed Gasifier Operating
with Steam-Oxygen Mixtures. Energy Fuels 1997, 11 (6), 1194-1203.

dolomites and in-depth reviews of its workings were

made. For this reason, no more reference on the use of
dolomite in biomass gasification will be made here.
(2) The second benefit of using dolomite is that it
prevents, to some extent, or decreases agglomeration
in a fluidized-bed biomass gasifier when biomass with
a high alkali content is used.6,7
Dolomites also have some disadvantages or unwanted
properties:
(1) After dolomite has been quickly calcined in the
gasifier, it becomes quite soft and erodes easily. It
generates a gasification or raw gas with a high particulate content.8
(2) It is not very active for tar elimination. In fact,
with dolomites, it is very difficult to obtain a tar content
(4) Oro, A.; Corella, J.; Narvaez, I. Performance of Different
Dolomites on Hot Raw Gas Cleaning from Biomass Gasification with
Air. Ind. Eng. Chem. Res. 1997, 36 (9), 3800-3808.
(5) 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.
(6) Zevenhoven-Onderwater, M.; Backman, R.; Skrifvars, B.-J.;
Sjostrom, K. The Ash Chemistry in Fluidized Bed Gasification of
Biomass Fuels. Part II: Ash Behaviour Prediction versus Bench Scale
Agglomeration Tests. Fuel 2001, 80, 1503-1512.
(7) Daavitsainen, J. H. A. A.; Nuutinen, L. H.; Ollila, H. J.; Tiainen,
M. S.; Laitinen, R. S. FB Combustion of Bark and Sawdust in Silica
Sand Bed with Dolomite Addition. A Case Study. In Proceedings of
the 16th International Conference on Fluidized Bed Combustion;
Geiling, D. W., Ed.; American Society of Mechanical Engineers
(ASME): New York, 2001; Paper No. 120.
(8) Gil, J. Advances in the Gasification of Biomass in Fluidized Bed.
Ph.D. Thesis, Universidad de Zaragoza, Spain, 2000 (to be published).

10.1021/ef0340918 CCC: $27.50 2004 American Chemical Society

Published on Web 04/09/2004

714

Energy & Fuels, Vol. 18, No. 3, 2004

of <2 g tar/m3n in the raw gas, which is the limit

required to prevent the deactivation by coke of nickelbased catalysts that are located downstream from the
biomass gasifier.9
When considering the advantages and disadvantages,
dolomite is an inadequate additive in biomass gasification. A better additive for this process is still required.
At the end of the 1990s, the idea that another mineral
rocksolivinescould be a better additive than dolomite
was introduced. Olivine has the chemical formula
(Mg,Fe)2SiO4, with a Mg/Fe ratio of 9/1.10-12 Oxides of
magnesium and iron are already known to have some
activity for tar elimination.4 Ignoring the facts that (i)
olivine is not as abundant on Earth as dolomite and (ii)
some countries do not have this mineral (which would
increase its cost, because of its transport to the gasification plant), some scientists started to study olivine as a
possible additive in biomass gasification. These studies
were made with pure and targeted species, such as
naphthalene, in artificial gas atmospheres,13 or in
biomass gasification with pure steam.14 A study on the
performance of olivine in biomass gasification with air
does not yet exist. One of the main objectives of this
paper is to compare the effectiveness of olivine and
dolomite in biomass gasification with air under conditions that are identical or similar to those observed in
possible future commercial applications.
To increase the tar elimination activity of natural
olivine, Kiennemann and Cols., at Strasbourg, introduced some nickel into it, to generate a new Ni-olivine
catalyst.11,15 This catalyst material proved to be active
in biomass gasification with pure steam in a fluidized
bed;15-17 however, no data on its performance as an inbed additive in biomass gasification with air have been
(9) 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.
(10) Courson, C.; Petit, C.; Kiennemann, A. Caraterisations Physicochimiques dune Olivine Naturelle et son Usage en Catalyse Industrielle. J. Phys. IV 2000, 10, 531-540.
(11) Courson, C.; Udron, L.; Petit, C.; Kiennemann, A. Grafted NiO
on Natural Olivine for Dry Reforming of Methane. Sci. Technol. Adv.
Mater. 2002, 3, 271-282.
(12) Courson, C.; Udron, L.; Swierczynski, D.; Petit, C.; Kiennenmann, A. Hydrogen Production from Biomass Gasification on Nickel
Catalysts. Tests for Dry Reforming of Methane. Catal. Today 2002,
76, 75-86.
(13) Abu El-Rub, Z.; Bramer, E. A.; Brem, G. Tar Removal in an
Entttrained Flow Cracker (EFC) with Application to Biomass Gasification. In Pyrolysis and Gasification of Biomass and Waste; Bridgwater,
A. V., Ed.; CPL Press: Newbury, Berks, U.K., 2003; pp 337-346.
(ISBN: 1 872691 77 3.)
(14) Rapagna, S.; Jand, N.; Kiennemann, A.; Foscolo, P. U. SteamGasification of Biomass in a Fluidized-Bed of Olivine Particles. Biomass
Bioenergy 2000, 19, 187-197.
(15) Petit, C.; Courson, C.; Rapagna, S.; Foscolo, P. U.; Kiennemann,
A. Catalyst for the Fluid Bed Gasification of Biomass Contains a
Dispersed Active Metal Phase Containing Nickel on a Support of
Magnesium, Iron, Silicon Oxide Compound. Patent No. WO0189687,
November 2001.
(16) Hofbauer, H.; Rauch, R.; Loeffler, G.; Kaiser, S.; Fercher, E.;
Tremmel, H. Six Years Experience with the FICFB-Gasification
Process. In Proceedings of the 12th European Conference and Technology Exhibition on Biomass for Energy, Industry and Climate Protection
(Amsterdam, June 2002); ETA: Florence, Italy (and WIP, Munich,
Germany), 2002; pp 952-985. (ISBN: 88-900442-5-x.)
(17) Rapagna, S.; Udron, L.; Jand, N.; Courson, C.; Petit, C.;
Kiennemann, A.; Foscolo, P. U. Catalysts Utilized to Improve the
Quality of Biomass Gasification Products. In Proceedings of the 12th
European Conference and Technology Exhibition on Biomass for
Energy, Industry and Climate Protection (Amsterdam, June 2002);
ETA: Florence, Italy (and WIP, Munich, Germany), 2002; pp 952985. (ISBN: 88-900442-5-x.)

Toledo and Padilla

reported yet. The second objective of this paper is to

discover the usefulness of such an additive in this
process.
Devi et al.18 and Sutton et al.19 recently reviewed the
catalytic additives used in biomass gasification with air
in a fluidized bed. Besides the three additives that have
been tested in this work, there are other additional
additives that could be considered; however, they were
not used in this work for two reasons:
(1) Although commercial in-equilibrium fluidized
catalytic cracking (FCC) catalysts are active for tar
elimination, as Corella et al. proved in the 1980s20 and
Abu-El Rub et al.13 recently confirmed, their small
particle size (60-75 m) makes them elutriate quickly
out of the gasifier. Complex and expensive (twin or dual)
gasifiers would have to be used, similar to the FCC units
or to the Battelle-Columbus gasifier that is currently
in operation in Burlington, VT. In-equilibrium FCC
catalysts decrease the tar content, but fluidized-bed
gasifiers that are more complex and more expensive
than the conventional BFB and CFB gasifiers would
have to be used.
(2) Occasionally, some catalysts (which the current
authors call exotic) appear in the literature. One of
the most recently reported is the Rh/CeO2/SiO2 catalyst
that was developed by Tomishige and Cols. in Japan.21,22
It can decrease the tar content by 99%, but only while
operating under very low biomass throughputs. In
addition, its very high cost has prevented the manufacturing of amounts that are large enough to be tested
in a pilot plant. For this reason, Rh/CeO2/SiO2 was not
used in this work.
Calcined limestones (OCa) and magnesites (OMg)
were studied previously by Corella et al.1,2 and proved
to be active for tar elimination in biomass gasification;
however, they were not as active as calcined dolomites.1,2 For these reasons, and until another realistic
or feasible catalytic additive appears, comparisons
between additives remain confined to those between
dolomite, olivine, and Ni-olivine. This paper compares
the three available and competing additives (dolomite,
olivine, and Ni-olivine) in biomass gasification with air
in a fluidized bed. The data used in this comparison
were obtained from two small-scale pilot plants. Testing
was made under conditions similar to those in commercial fluidized-bed gasifiers, under an actual gasification atmosphere.
2. Experimental Section
2.1. Gasifiers Used. Two different fluidized-bed-type gasifiers were used in this work: a circulating fluidized-bed (CFB)
gasifier and a bubbling fluidized-bed (BFB) gasifier. Biomass
(18) Devi, L.; Ptasinski, K. J.; Janssen, F. J. J. G. A Review of the
Primary Measures for Tar Elimination in Biomass Gasification
Processes. Biomass Bioenergy 2003, 24, 125-140.
(19) Sutton, D.; Kelleher, B.; Ross, J. R. H. Review of Literature on
Catalysts for Biomass Gasification. Fuel Process. Technol. 2001, 73,
155-173.
(20) Corella, J.; Herguido, J.; Gonzalez-Saiz, J.; Alday, J. F.;
Rodrguez-Trujillo, J. L. Fluidized Bed Steam Gasification of Biomass
with Dolomite and with a Commercial FCC Catalyst. In Research in
Thermochemical Biomass Conversion; Bridgwater, A. V., Kuester, J.
L., Eds.; Elsevier: London, 1988; pp 754-765.
(21) Asadullah, M.; Miyazawa, T.; Ito, S.-I.; Kunimori, K.; Tomishige,
K. Catalyst Performance of Rh/CeO2/SiO2 in the Pyrogasification of
Biomass. Energy Fuels 2003, 17 (4), 842-849.
(22) Asadullah, M.; Miyazawa, T.; Ito, S.-I.; Kunimori, K.; Tomishige,
K. Demonstration of Real Biomass Gasification Drastically Promoted
by Effective Catalyst. Appl. Catal., A 2003, 246 (1), 103-116.

In-Bed Additives in Biomass Gasification with Air

Energy & Fuels, Vol. 18, No. 3, 2004 715

Figure 1. Gasifiers used: CFB biomass gasifier (left) and BFB biomass gasifier (right).
Table 1. Main Experimental Conditions in the CFB Biomass Gasifier
Value
condition

C-07

C-09

C-10

C-12

C-15

C-13a

C-13b

C-14a

C-14b

C-16

ERgasifier, first and second air

air partitioning (%)
primary
secondary
bed temperature (C)
temperature after second air addition (C)
u0 at the bed inlet (cm/s)
bed (s)
upper,dilute zone (s)
H/C ratio (at.-g/at.-g)
(H2O/C*)gasifier exit ratio (mol/at.-g)
WHSV of biomass ((kg biomass/h)/kgS+D)

0.39

0.35

0.33

0.34

0.30

0.35

0.33

0.30

0.28

0.32

90.5
9.5
850
903
155
0.33
3.8
1.6
6.4
1.1

90
10
850
900
130
0.39
4.6
1.3
2.7
1.1

90
10
852
936
118
0.60
4.5
1.3
1.5
0.96

93.6
6.4
851
952
130
1.0
5.9
1.3
3.7
0.52

90
10
850
940
80
1.7
8.5
1.7
2.5
0.33

93.4
6.6
851
937
99
1.3
6.2
1.1
3.5
0.33

100
0
851
934
99
1.3
6.2
1.1
3.5
0.33

100
0
855
937
79
1.8
8.7
1.8
2.9
0.31

100
0
851
937
77
2.1
10.3
1.8
2.6
0.31

90
10
855
935
85
1.6
8.5
1.8
3.0
0.32

was continuously fed directly into the bed at the bottom of the
gasifiers. Air was the only gasifying agent used in these
experiments. Some H2O was also present in the gasifying
agent, which originated from the moisture in the biomass and
from the air. The two gasifiers used are depicted schematically
in Figure 1.
2.1.1. CFB Gasifier. The CFB gasifier used is shown on the
left-hand side in Figure 1. It had three different zones (from
the bottom to the top). The first zone had an internal diameter
(i.d.) of 54 mm and was 22 cm high. It was followed by the
second zone (i.d. of 105 mm and 74 cm high) and the third
zone (i.d. of 130 mm i.d. and 140 cm high). A return or
standpipe was located at the bottom of the first cyclone, as
shown in Figure 1 (left).
The main experimental conditions of the CFB gasifier are
given in Table 1. Among these conditions, notice how the
equivalence ratio (ER) used in the gasifier was in the range
of 0.28-0.39. The temperature at the bottom bed was maintained in the range of 850-855 C. Previous experience in
biomass gasification had recommended this level of temperature to be the most appropriate for biomass gasification in a
fluidized bed. Among other advantages, at these temperatures,
no agglomerations or slag formation in the gasifier bed were
observed with the feedstocks used here.

The gas residence time at the bottom of the bed (bed) was
0.33-2.1 s. Finally, the biomass flow rate, which is expressed
as the biomass weight hourly space velocity (WHSV), was
relatively low and was in the range of 0.31-1.1 [(kg biomass
a.r. fed/h)/inventory (kg) of solids (silica sand + additive) in
the gasifier].
2.1.2. BFB Gasifier. The BFB biomass gasifier is shown on
the right-hand side in Figure 1. It had an i.d. of 150 mm and
was 5.2 m high. A throat 30 cm in length with an i.d. of 60
mm was located near the second air feeding point, to facilitate
the mixing of the second air with the rising gas. A standpipe
that was closed at the end by a valve was located at the bottom
of the first cyclone. This standpipe was used to collect, at the
end of the test run, the coarse fly ash that had separated in
the cyclone. Although this gasifier could also operate as a CFB
gasifier, it was operated as a BFB gasifier in all the test runs
for this work.
The operating conditions of the BFB gasifier in these tests
are presented in Table 2. ER values used were quite high: they
were in the range of 0.36-0.48, although this gasifier can also
work with lower ER values. The temperature in the gasifier
bed was maintained at 827-879 C. Space-time of the primary
air in the gasifier bed was 0.84-1.1 s, and the WHSV for the
biomass was relatively low (0.33-0.47 h-1).

716

Energy & Fuels, Vol. 18, No. 3, 2004

Toledo and Padilla

Table 2. Main Experimental Conditions in the BFB Biomass Gasifier

Value
condition

N-86

N-87

N-89

N-93

N-91

N-94

ERgasifier , first and second air

air partitioning (%)
primary
secondary
bed temperature (C)
temperature after second air addition (C)
u0 at the bed inlet (cm/s)
bed (s)
upper,dilute zone (s)
H/C ratio (at.-g/at.-g)
(H2O/C*)gasifier exit ratio (mol/at.-g)
WHSV of biomass ((kg biomass/h)/kgS+D)

0.52

0.40

0.40

0.36

0.36

0.36

89
11
827
936
25
1.1
3.7
2.0
1.9
0.33

89
11
879
941
39
0.84
2.7
1.5
2.7
0.42

100
0
820
885
51
1.0
3.1
2.6
5.3
0.47

100
0
855
911
56
1.0
2.8
2.0
2.7
0.43

100
0
850
902
56
1.0
2.8
2.0
2.7
0.43

100
0
847
892
56
1.0
2.9
2.0
2.7
0.43

Table 3. Feedstock Composition in the CFB Gasifier

Value
property

C-07

component (wt %, dry basis)

residue from olive oil production,
hard cores mainly (orujillo), 1-4 mm
small pine wood chips, 1-5 mm
additive
dolomite, 0.40-0.63 mm
sintered olivine, 0.40-0.63 mm
raw olivine, 0.40-0.63 mm
moisture in the overall feedstock (wt %, a.r.)
feed flow rate (kg a.r./h)

C-09

C-10

C-12

C-15

C-13a,b

C-14a,b

C-16

48.5

48.5

38.8

38.8

38.8

38.4

39.2

97

48.5

48.5

58.2

58.2

58.2

58.6

58.8

3.0

3.0

3.0

3.0

3.0

3.0

29
2.1

21
2.1

19
2.3

21
1.9

20
2.0

12
1.4

3.0
11
1.3

2.0
16
1.9

Table 4. Feedstock Composition in the BFB Gasifier

Value
property
component (wt %, dry basis)
residue from olive oil production,
orujillo, 1-4 mm
small pine wood chips, 1-5 mm
additive
dolomite, 0.40-0.63 mm
raw olivine, 0.40-0.63 mm
moisture in the overall feedstock (wt %, a.r.)
feed flow rate (kg a.r./h)

N-86

100

22
2.7

One may notice that a mixture of six solids was present in

the bed in both the CFB and BFB gasifiers: silica sand, the
additive, the two types of biomass that exist in the feedstock
(as mentioned below), and the corresponding two types of
charred biomass. A seventh and even a eighth solid might be
also added to this list: the chars from the two types of biomass.
This mixture of 6-8 solids fluidized well, as proved in separate
tests that were made in a cold fluidized bed,23 although some
segregation (longitudinal axial profiles) appear in the fluidization of these complex mixtures of solids.24
Some other operating parameters, such as temperature and
gas residence time in the upper portion of the gasifiers, also
have a very important role in the tar content at the gasifier
exit,25 because of the thermal and catalytic reactions that occur
in that zone. This fact was taken into account when the results
obtained from these tests were analyzed.
2.2. Feedstock Used. A mixture of an easy-to-gasify
biomass (small pine wood chips) and a difficult-to-gasify
biomass (orujillo, which is residue from the production of
olive oil) was used as feedstock. The exact amount of each type
(23) Aznar, M. P.; Gracia-Gorria, F. A.; Corella, J. Minimum
Fluidization (umf) and Complete Fluidization (ucf) Velocities for Mixtures of Agricultural and Forest Residues with a Secondary and
Fluidizing Solid. Parts I and II. Int. Chem. Eng. 1992, 32 (1), 95-113.
(24) Aznar, M. P.; Gracia-Gorria, F. A.; Corella, J. Segregation in
the Fluidization of Mixtures of Different Types of Biomass with Silica
Sand. Axial Profiles of Concentration. An. Quim. 1989, 85 (1), 100108.

N-87

N-89

N-93

N-91

N-94

50.0

38.8

38.8

38.8

39.2

50.0

58.2

58.2

58.2

58.8

3.0

3.0

30
4.2

18
4.2

3.0
18
4.2

2.0
18
4.2

16
3.5

of biomass in the feedstock is given in Table 3 for the CFB

gasifier and in Table 4 for the BFB gasifier. In the feedstock,
a third component was also present: some additive was fed
in small percentage amounts (2-3 wt %), to replace the
additive that was initially located in the gasifier bed and was
lost by erosion and elutriation from the bed. The exact amount
and type of additive in the feedstock is shown in Tables 3 and
4. The moisture in the overall feedstock is shown in Tables 3
and 4. The feedstock flow rate to the gasifier is also indicated
in Tables 3 and 4 for each test run.
The physicochemical characterization of the two types of
biomass in the feedstock is given in Table 5. Note the high
alkali and nitrogen contents in the orujillo residue that was
obtained from olive oil production.
2.3. Chemical Analysis of the Gasification Gas. Samples
were taken from the exit of the gasifiers, just after the second
cyclone, and were composed of several components: (i) gas,
for standard analysis via gas chromatography (GC) of gases
such as H2, CO, CO2, CH4, and light hydrocarbons; (ii) tar, for
further analysis by the new and recently adopted tar protocol;26
(iii) gas, for ammonia (NH3) content; and (iv) particulates,
using standard methods, with a small thimble filter.
(25) Sanz, A.; Corella, J. Modeling Circulating Fluidized Bed Biomass Gasifiers. 4. Results from a Pseudo-rigorous 1-Dimensional Model
for Stationary State. In Pyrolysis and Gasification of Biomass and
Waste, Proceedings of an Expert Meeting, Strasbourg, France, September 30-October 1, 2002; Bridgwater, A. V., Ed.; CPL Press:
Newbury, U.K., 2003; pp 431-444.

In-Bed Additives in Biomass Gasification with Air

Energy & Fuels, Vol. 18, No. 3, 2004 717

Table 5. Characterization of the Two Types of Biomass Used

small pine
wood chips
proximate analysis (wt %, dry basis)
moisture
ash
volatile matter
fixed carbon
ultimate analysis (wt %, dry basis)
C
H
O
S
N
Cl
lower heating value, LHV (MJ/kg, daf)
ash analysis (wt %)
K2O
Na2O
Al2O3
SiO2
Fe2O3
CaO
MgO

residue from
olive oil production

20
0.7
81
16

13
2.9-5.8
74-84
19.4-19.6

49-50
5.2-5.7
44-45
0
0.10-0.30

52-54
5.0-6.7
34-39
0-0.10
1.1-1.5

18.0-18.4

20-21

6.9
0.30
4.3
25
3.6
25
2.8

27-36
0.4-4.0
2.5-2.9
18-32
1.9-2.3
10-12
3.8-7.0

Table 6. In-Bed Material in the CFB Gasifier

Value
in-bed material
silica sand (70-75 wt %) + dolomite (25-30 wt %)
silica sand (70-75 wt %) + sintered olivine (25-30 wt %)
sintered olivine (100 wt %)
silica sand (70-75 wt %) + raw olivine (25-30 wt %)

C-07

C-09

C-10

C-12

C-15

C-13a,b

C-14a,b

C-16

Table 7. In-Bed Material in the BFB Gasifier and Dust Loading at the Exit of the Gasifier
material
silica sand (70-75 wt %) + dolomite (25-30 wt %)
silica sand (85.5 wt %) + Ni-olivine (14.5 wt %)
silica sand (70-75 wt %) + raw olivine (25-30 wt %)

N-86

N-87

xa

dust loading (g m-3 (nc))

a

N-89

N-93

4.0

4.5

N-91

N-94

0.3

0.8

The bed material used in test N-87 was that previously used in test N-86.

Heat exchangers were positioned at the end of the two small

pilot plants, where most of the H2O present in the flue gas
was condensed and collected. The H2O content in the flue gas
was then measured to obtain an approximate estimate of the
(H2O/C*) ratio at the exit of the gasifier. Except for the H2O,
which was collected at the end of the run, 3-5 samples were
taken during the time of the experiment, and always after the
gasifier attained its steady state. Results shown in this paper
correspond to the weighted average of the results that have
been obtained at different times-on-stream.
Note that the analysis of the samples and the calculations
involved to obtain the results required a substantial effort. A
full test run required, on average, 4 man-months.
2.4. Catalytic Additives in the Gasifier. The characterization of the three catalytic additives used in this work is fully
available. The mixtures used in this work are listed in Tables
6 and 7. The dolomite used was the Norte type, available
from Cantabria in northern Spain and provided by Calcinor.
Details of its physicochemical characterization, after calcination under conditions similar to those existing in atmosphericpressure biomass gasifiers, can be found in the paper by Orio
et al.4 Some of the main properties of the calcined dolomite
used are as follow. A specific surface area of 6.6 m2/g (as
measured via N2 adsorption) or 9.9 m2/g (as measured via
(26) van Passen, S. V. B.; Kiel, J. H. A.; Neeft, J. P. A.; Knoef, H. A.
M.; Buffinga, G. J.; et al. Guideline for Sampling and Analysis of Tar
and Particles in Biomass Producer Gases, Final Report to EC from
Project No. ERK6-CT1999-2000, Report No. ECN-02-090, ECN, Petten,
The Netherlands, November 2002.

mercury porosimetry) is observed. The dolomite has an average

pore diameter of 1.630 and an apparent (skeletal) density
of 3.0 g/cm3, as measured via mercury porosimetry. The Fe2O3
content in this dolomite is low: 0.12-0.14 wt %.
The Ni-olivine catalyst used for this work contained 3.7 wt
% nickel and was provided by Kiennemann and Cols. from the
University of Strasbourg, France. The properties of this
catalyst can be found in papers on the subject that were
published by the French team led by Courson, Petit, and
Kiennemann.10-12
Sometimes a problem appears in the literature concerning
olivine: very often, it is not stated whether the olivine used
was calcined or not. This greatly affects the final physical
properties of the olivine. Magnolithe GmbH, Austria, provided
the olivine(s) used in this work. This company supplies natural
or raw uncalcined olivine and sintered olivine that is calcined
at 1500 C. Their physical characterizations, which were
performed by these authors at UCM, are shown in Table 8,
together with that of an olivine calcined at (only) 900 C, which
is the maximum temperature used in fluidized-bed biomass
gasifiers. Table 8 shows that the olivine calcined at 900 C
has properties that are very similar to those of raw olivine.
The calcined olivine, sintered at 1500 C, has no internal
surface area with all of its pores closed; this can be considered
to be a dead material. One can conclude that raw and
sintered olivines are two different additives, and this fact may
explain some discrepancies found in the literature on this
process.

718

Energy & Fuels, Vol. 18, No. 3, 2004

Toledo and Padilla

Table 8. Characterization of the Olivine Used as an In-Bed Material

Value
raw
(not calcined)

property
BET surface area
micropore area
external surface area
BJH adsorption cumulative surface area of
pores 1-3000 in diameter
single-point adsorption total pore volume of
pores <1140 in diameter at P/P0 ) 0.98
micropore volume
BJH adsorption cumulative pore volume of
pores 1-3000 in diameter
adsorption average pore diameter (4V/A by BET)
BJH adsorption average pore diameter (4V/A)

calcined
at 900 C

sintered
at 1500 C

7.66 m2/g
0.97 m2/g
6.69 m2/g
12.5 m2/g

7.64 m2/g
1.04 m2/g
6.60 m2/g
12.5 m2/g

0.087 m2/g

0.017 cm3/g

0.041 cm3/g

0.0005 cm3/g
0.021 cm3/g

0.0005 cm3/g
0.045 cm3/g

93
67

221
144

0
0

Table 9. Average Gas Composition at the Exit of the CFB Gasifier

sintered olivine
gas composition (%, dry basis)
H2
CO
CO2
CH4
C2Hn
N2
tar content (mg m-3 (nc))
NH3 content (ppmv)

dolomite

raw olivine

C-07

C-09

C-10

C-12

C-15

C-13a

C-13b

C-14a

C-14b

C-16

5.5
5.0
14.1
2.0
0.5
72.5
7830

15.5
13.9
15.4
2.7
0.2
52.3
2990
2370

17.8
18.0
12.1
3.1
0.3
48.7
13670
5000

17.2
16.8
13.1
3.2
0.2
49.5
2270
2275

18.5
16.2
12.5
3.0
0.3
49.5
1950
1950

10.6
13.3
10.8
2.5
0.25
62.6
4220
460

9.7
12.3
9.5
2.1
0.2
66.1
4480

16.2
17.3
13.2
3.6
0.3
49.4
1800
610

18.9
18.1
12.7
3.7
0.3
46.3
2540
1500

13.5
12.6
11.7
2.7
0.2
59.3
4650
1650

Table 10. Average Gas Composition at the Exit of the BFB Gasifier
Ni-olivine
gas composition (%, dry basis)
H2
CO
CO2
CH4
C2Hn
N2
tar content (mg m-3 (nc))
NH3 content (ppmv)

dolomite

raw olivine

N-86

N-87

N-89

N-93

N-91

N-94

15.3
14.1
9.5
3.3
0.4
59.6
3720

8.9
12.0
10.9
1.9
0.7
65.7
5000
1975

14.2
12.5
16.1
3.5
0.9
52.8
1260
2490

14.6
12.9
14.0
3.7
0.8
54.0
1600
3200

13.2
12.1
13.6
4.0
1.8
55.3
1860
910

14.5
13.0
14.0
3.8
1.4
53.3
2300
1200

3. Results
Gas composition and the tar and NH3 contents in the
raw gas at the exit of the CFB and BFB gasifiers, and
in the experiments considered for this paper, are given
in Tables 9 and 10, respectively. The dust or particulates
content in the raw gas for some experiments is shown
in Table 7. Analysis of these data made it possible to
infer and compare the performance of the three in-bed
additives that have been used in this paper.
3.1. Nickel-Olivine Catalyst. This catalytic additive
was only tested in two experiments (tests N-86 and
N-87; see Table 7) in the BFB gasifier. It was mixed
with silica sand, in a proportion of 14.5 wt %/85.5 wt %
(Ni-olivine/silica sand). The reason for the relatively low
percentage of Ni-olivine catalyst in the mixture was
because the authors obtained only 2 kg of the catalyst
from the producer. The percentage of the catalyst in the
in-bed mixture was a determining factor for the tar
content in the gas that was produced in biomass
gasification with steam.16 The low percentage of catalyst
in the gasifier bed used in this work may explain the
relatively high tar content (3720 mg m-3 (nc)) in the
gasification gas that was obtained in test N-86 (see
Table 10). It is a high value, when compared with the
tar content obtained in the same gasifier using dolomite

or raw olivine (see Table 10). This result indicates that

the Ni-olivine catalyst is not very active for tar elimination in biomass gasification with air.
Hofbauer et al.16 and Rapagna et al.,17 using the same
catalyst, reported better results than those reported
above for this work. This is only an apparent discrepancy and is due to, at least, two clear factors:
(1) They used a higher percentage of the Ni-olivine
catalyst in the bed and they did not mix it with silica
sand (which has only a small tar cracking activity),
as in the case of this work. Instead, they mixed it with
olivine, which has a higher tar cracking activity than
silica sand.
(2) Nickel has a very well-known activity in steam
reforming reactions of natural gas, light and heavy
naphthas, etc. Nickel seems to dissociate the H2O in
OH radicals, which opens or cuts the rings of the
polyaromatic hydrocarbons (which are the typical and
most-abundant species in tar) one by one. This mechanism was recently described by Corella et al.27
H2O is an important reactant in the tar elimination
reactions with nickel-containing catalysts and its con(27) Corella, J.; Caballero, M. A.; Aznar, M. P.; Brage, C. Two
Advanced Models for the Kinetics of the Variation of the Tar Composition in Its Catalytic Elimination in Biomass Gasification. Ind. Eng.
Chem. Res. 2003, 42 (13), 3001-3011.

In-Bed Additives in Biomass Gasification with Air

centration affects the rate of these reactions. Because

Hofbauer et al.16 and Rapagna et al.17 gasified with pure
steam, the H2O content in the gas in their gasifiers was
much higher than the H2O content reported in this
paper. The gasification for this paper was done with air,
with only a small amount of H2O, which came from the
moisture in the air and the biomass. After analyzing
and comparing all these results, it was concluded that
the Ni-olivine catalyst can be active and is, therefore,
useful in biomass gasification with pure steam. However, it showed very little activity in biomass gasification
with air when it was mixed with silica sand, rather than
olivine, and with small percentages of Ni-olivine.
This poor performance by Ni-olivine was further
accentuated when the same batch of catalyst was used
in another experiment (test N-87). In this experiment,
the tar content at the gasifier exit increased to 5000 mg
m-3 (nc), which is similar to that obtained with pure
silica sand under the same operating conditions in the
gasifier.28 This result indicated that the catalyst was
already deactivated in the second experiment (test
N-87). The deactivation of the Ni-olivine catalyst in the
biomass gasifier may occur because of different and
simultaneous causes, such as coking or loss of the active
(nickel) component by attrition or by transfer to the char
found in the gasifier bed. The most important cause of
deactivation is not known; however, the conclusive fact
is that Ni-olivine became deactivated, requiring periodic
regeneration, as reported by Rapagna et al.17 This would
imply a need to work with dual or twin fluidized-bed
gasifiers. The Ni-olivine catalysts might be useful in
that case; however, for biomass gasification with air in
a BFB or CFB gasifier (not a dual fluidized-bed gasifier),
the Ni-olivine catalyst cannot be recommended.
3.2. Sintered Olivine versus Natural Olivine.
Table 9 shows the results obtained in the CFB gasifier
that was operated with sintered olivine (tests C-07,
C-09, and C-10) and with raw or natural olivine (tests
C-13a and b, C-14a and b, and C-16). Although the
experimental conditions were not exactly the same, it
was very soon appreciated how sintered olivine was
much less active, if at all, than natural or raw olivine
(see Table 9). When using sintered olivine, the average
tar content for the three experiments, shown in Table
9, was 7000-8000 mg m-3 (nc)), whereas for the raw
olivine, this was 2800-4000 mg m-3 (nc)). No further
discussion is needed here: the sintered olivine lost all
its pore structure (Table 8) and was not active. It
behaved similar to silica sand: only thermal tarelimination reactions were relevant in this case.
Two conclusions were deduced from these results: (i)
sintered and natural olivine behave in very different
ways, so they must be considered to be two different
additives; and (ii) further research on additives in
biomass gasification should be made, and this was done,
with natural or raw olivine.
3.3. Natural or Raw Olivine versus Dolomite.
3.3.1. Tar Content. The comparison between these two
natural additives concentrated on the tar content at the
gasifier exit, because the small differences in the gas
(28) Gil, J.; Caballero, M. A.; Martn, J. A.; Aznar, M. P.; Corella, J.
Biomass Gasification with Air in a Fluidized Bed: Effect of the InBed Use of Dolomite under Different Operation Conditions. Ind. Eng.
Chem. Res. 1999, 38 (11), 4226-4235.

Energy & Fuels, Vol. 18, No. 3, 2004 719

composition (the H2, CO, CO2, CH4, ... contents) can be

attributed to different and simultaneous causes as
noncatalytic reactions. The tar content at the gasifier
exit is dependent on many variables, such as temperature and gas residence time in the different zones of
the gasifier, feedstock composition and moisture, and
equivalence ratio (ER) used. This was recently analyzed
and modeled by Sanz and Corella.25 All the experimental conditions that affect the final tar content were not
exactly the same in all test runs. The tar content
obtained with each additive, and shown in Tables 9 and
10, were compared with pairs of values, considering all
the small possible variations of the experimental conditions in that pair of experiments. These detailed comparisons resulted in the same conclusions as when all
the experiments with a given additive were considered
together.
The experiments performed with dolomite in the CFB
gasifier were tests C-12 and C-15, and those performed
with raw olivine were tests C-13a and b, C-14a and b,
and C-16 (see Tables 6 and 9). In the BFB gasifier,
experiments N-89 and N-93 involved dolomite and
experiments N-91 and N-94 involved raw olivine (see
Tables 9 and 10). Recall that each value for the tar
content that appears in Tables 9 and 10 is the average
of 3-5 tar samplings (and analysis) made at different
times-on-stream. After averaging the results in Table
9 for tar content, it was deduced that, in the CFB
gasifier,

weighted average tar content

) 2100 mg m-3 (nc)
(when using dolomite)
) 3500 mg m-3 (nc)

(when using olivine)

For the BFB gasifier, it was deduced from Table 10 that

weighted average tar content

(when using dolomite)
) 1500 mg m-3 (nc)
) 2100 mg m-3 (nc)

(when using olivine)

From these two comparisons, the following conclusions

were made:
(1) Dolomite was somewhat more active for in-bed tar
elimination than raw olivine. Less tar content was
obtained when using dolomite than when using raw
olivine.
(2) As a rough estimate and for a gasifier operating
in both cases under similar conditions, it was postulated
from these results that the tar content at the gasifier
exit when using dolomite was only 60% (( 10%) of the
tar content obtained when raw olivine was used.
It can also be added that the BFB gasifier, with both
additives, generated less tar content than the CFB
gasifier, because it was operated at higher ER values,
as was previously shown.
3.3.2. Ammonia Content. In regard to NH3 content in
the gasification gas, there are many factors affecting its
production, one of them being the type of additive used.
The results shown in Tables 9 and 10 indicate that the
NH3 content in the gasification gas is higher with
dolomite than with olivine. Nevertheless, the differences
between the two additives are not as clear as those for
tar content. The presence of iron oxides in the additive
could have a role in the synthesis of NH3, because they

720

Energy & Fuels, Vol. 18, No. 3, 2004

catalyze the reaction of N2 and H2. The dolomite used

had an Fe2O3 content (0.12 wt %) that was lower than
that in the olivine (7.5-8.5 wt %). So, the Fe2O3 content
does not seem to be a determining factor in the NH3
amount in the gasification gas. A more-probable reason
on the influence of the additive might be that if the
dolomite was more active for tar cracking than olivine,
dolomite would crack more N-tars than the olivine,
thus generating more NH3. However, the authors do not
like to postulate a definitive reason for this result, which
requires further research.
3.3.3. Particulate Content. The results obtained with
the BFB gasifier for particulate or dust content in the
raw or gasification gas with both additives, as shown
in Table 7, are self-explanatory. With raw olivine, the
content of particulates in the gasification gas was clearly
less than that observed when dolomite was used.
Because the two in-series cyclones used in both gasifiers
were very similar to each other, the reason for this
result is clear and was already known by many authors: Calcined dolomite is very soft and generates
many more small particles (which are carried out of the
gasifier by the gas) than when olivine is used.
3.3.4. Agglomeration. Additives also have a significant
role in the agglomerating tendencies in the gasifier bed
when high-alkali-content biomass types are used. Regarding this aspect, no meltings or agglomerations were
detected in the gasifiers with these two additives. The
reason why the agglomeration problem did not appear
in this work is attributed not only to the performance
of these two additives but also to the fact that the
temperatures used in the gasifier beds were not very
high (always <900 C; see Tables 1 and 2).
4. Final Conclusion
At one point in time, additives have to be located in
the gasification plant; now, the cost of each additive
must be known first. In some scenarios and/or countries,
there may or may not be quarries or mines for one of
these additives. It would be unrealistic to use a given
additive in a gasification plant if it had to be transported
over long distances. Leaving aside this basic and key
fact, and only concentrating on the physicochemical
performance of the additives compared here, it was
concluded that both dolomite and olivine have one
positive and one negative property. Dolomite was shown
to be 1.40 times more effective for in-bed tar removal
than the raw olivine, but it generated 4-6 times more
particulates in the gasification gas than olivine. It was

Toledo and Padilla

therefore impossible to say which additive was better.

If tar content were the only determining criterion, then
dolomite was better than olivine. If the particulates
content were the key factor, olivine was better than
dolomite. Another conclusion, which is not very good
news for those working with biomass gasification in
fluidized beds, is that natural olivine and dolomites are
not the optimal additives. A better additive should be
discovered and used in the future.
Acknowledgment. The authors express their gratitude to Prof. Kiennemann and Cols. (Strasbourg), Magnolithe GmbH (St. Lorenzen, Austria), and Mr. Heraclio
Varona (Calcinor, Spain), for providing samples of their
Ni-olivine, olivines, and dolomite, respectively. Rafi
Fernandez is acknowledged for assistance with the
experimental work. This work was performed under the
NOVACAT Project No. NNE5-2000-0098 of the EC, DG
Research, Directorate J. The authors wish to thank the
European Commission for its financial support.
Note Added after ASAP Posting. This article was
released ASAP on April 9, 2004 with the units of
measurement for the tar content in test N-87 (Section
3.1) incorrectly listed in the text as mg N-1 m-3. The
correct units should be mg m-3 (nc). The correct version
was posted on April 15, 2004.
Nomenclature
D ) additive
ER ) equivalence ratio, defined as the air-to-fuel ratio used
in the gasifier divided by the air-to-fuel ratio for the stoichiometric combustion (dimensionless)
(H/C) ) ratio of hydrogen to carbon in the feedstock
(at.-g/at.-g)
(H2O/C*) ) ratio of steam to carbon-to-be-reformed
(mol/at.-g)
n or nc ) normal conditions (273 K and 1 atm (1.013 105
Pa)) for the gas
S ) silica sand
u0 ) superficial gas (air) velocity at the inlet (bottom) of the
gasifier (cm/s)
WHSV ) weight hourly space velocity for the biomass in the
gasifier [kg biomass a.r./h kg of material (S +D) in the gasifier]
bed ) space-time of the gas in the bed (s)
freeboard ) space-time of the gas in the freeboard of the BFB
gasifier (s)
upper,dilute zone ) space-time in the upper part, dilute zone, of
the CFB gasifier (s)
EF0340918