Professional Documents
Culture Documents
C) in the
gasier is preferred. To produce a relatively clean
gas by increased temperature, several temperature
ranges are reported in the literature. The present pa-
per cites only a few of these works. Temperature not
only aects the amount of tar formed, but also the
composition of tar by inuencing the chemical re-
actions involved in the whole gasication network.
Kinoshita et al. [10] observed during sawdust gasi-
cation in a xed bed gasier that the total number
of detectable tar species decreased with increasing
temperature. Oxygen-containing compounds such as
phenol, cresol and benzofuran exist in signicant
quantities only at temperature below 800
C. They also
conrmed that higher temperature favour the forma-
tion of fewer aromatic tar species without substituent
groups such as benzene, naphthalene, phenanthrene,
etc. Destruction of these aromatic hydrocarbons oc-
curs only at temperatures above 850
C. Yu et al. [11]
performed pyrolysis experiments of birch wood in a
free-fall reactor to observe the temperature eect on
the process and found that an increasing temperature
promotes the formation of gaseous products at the
expense of total tar. More than 40% reduction in tar
yield was reported when the temperature was raised
from 700
C to 900
C to 900
C. By changing
the bed temperature of the bubbling uidized bed
from 700
C to 850
C and 5 g m
3
o
at 800
C
to 900
C to 900
9
Fig. 3. Typical gasication temperature for various feedstock and inuence of temperature change on some critical factors as reported by
Hallgren [16].
dependence of pressure on wood char gasication. The
pressure was raised from 1 to 15 bar of CO
2
and H
2
O
at temperatures of 750
C and 850
C. Increase in CO
2
pressure slightly reduced char gasication whereas
this increased with increasing H
2
O pressure. Pressur-
ized gasication (520 bar) is also being investigated
in the Lund University [19,20]. Wang et al. [19] ob-
served a decrease in the amount of light hydrocarbons
(LHC, lower than naphthalene) as well as that of tar
in the fuel gas with an increasing ER for pressurized
gasication with 100% carbon conversion.
Dierent gasifying agents such as air, steam,
steamoxygen and carbon dioxide have been reported
in the literature. Selectivity of the gasication re-
actions varies with dierent gasifying media, thus
aecting the product gas composition as well as the
heating value. Heating value of the product gas with
air as gasifying medium is lower because of dilution
of the gas by nitrogen. Narv aez et al. [13] reported
a gas composition of 10% H
2
, 14% CO, 15% CO
2
(vol%) from a gasier with gasication temperature
of 800
C and 860
C with GR
of 0.81.2 and a gas residence time of 2 s [26]. They
also compared their work with that of Narv aez et al.
[13] and Herguido et al. [21], which involved gasi-
cation with air and steam, respectively. A relationship
between ER, SB and GR values is mentioned for
the purpose of comparison [27] by the authors of the
paper. Under selected conditions, more tar is formed
with pure steam, than that with steamO
2
mixture
and less with air as gasifying agent. It should be
mentioned at this point that the operating parameters
of the works compared were not exactly the same,
but similar; also the gasiers used were dierent in
design. Hofbauer et al. [28] and Fercher et al. [29]
reported use of a combination of steam and air in a
fast internally uidized bed biomass gasier which
is explained in the following section of this paper.
Air combustion provided the heat required for steam
gasication.
The use of CO
2
as gasifying medium is promising
because of its presence in the gasication atmosphere.
Tar reduction is also enhanced by dry reforming reac-
tions of CO
2
, which is a gasication product. Accord-
ing to Minkova et al. [30], a mixture of steamCO
2
gives highest degree of carbonization for pyrolysis and
gasication of biomass in a horizontal rotating reactor.
They also mentioned that a steamCO
2
mixture pro-
duced the highest activity char, which resulted in high
ash content. Garca et al. [31] investigated CO
2
gasi-
cation in the presence of Ni/Al coprecipitated catalyst
and compared the results with those of steam gasica-
tion [22,23]. CO
2
gasication in the presence of a cat-
alyst transformed tars and also causes a decrease of the
amounts of CH
4
and C
2
-fraction (C
2
H
2
; C
2
H
4
; C
2
H
6
)
as well as an increase in H
2
and CO yields. Also, a
L. Devi et al. / Biomass and Bioenergy 24 (2003) 125140 131
signicant decrease in the CO
2
content was observed
with a CO
2
/biomass ratio of 1.16 indicating that CO
2
itself converts to other products. Deposition of carbon
in the catalyst particles can be avoided to a certain
extent by feeding CO
2
in excess. The main chemical
reactions with CO
2
as gasifying medium are listed
below:
C
n
H
x
+ nCO
2
(x=2)H
2
+ 2nCO; (6)
CH
4
+ CO
2
2H
2
+ 2CO;
H
0
298
= +246:98 kJ mol
1
; (7)
C
2
H
4
+ 2CO
2
2H
2
+ 4CO;
H
0
298
= +292:41 kJ mol
1
; (8)
CO
2
+ H
2
CO + H
2
O;
H
0
298
= +41:16 kJ mol
1
; (9)
CO
2
+ C 2CO;
H
0
298
= +172:46 kJ mol
1
: (10)
Reaction (6) represents dry reforming reaction of tar.
According to Kinoshita et al. [10] residence time
has little inuence on the tar yield, but it signicantly
inuences the tar composition. The residence time
they reported was based on the supercial velocity
of the wet product gases in the gasier. Amounts of
O
2
-containing compounds tend to decrease with in-
creasing residence time. Yields of 1- and 2-ring com-
pounds (except benzene and naphthalene) decrease
whereas that of 3- and 4-ring compounds increases
in the total tar fraction. Corella et al. [9] observed a
decrease in the total tar content when the space time
was increased for biomass gasication with in-bed
use of dolomite. The space time was expressed as
(kg calcined dolomite (kg biomass
daf
h
1
)
1
). The
tar amounted 2 g m
3
o
at space time 1.0 which was
6 g m
3
o
at a space time of 0.1.
In addition to the optimized operational conditions,
presence of some active materials in the gasier can
largely improve the product gas distribution. The fol-
lowing section covers some of the reported literature
on use of bed additives.
2.2.2. Bed additives
Catalytic tar reduction has been extensively re-
ported in the literature [32]. These catalysts include
Ni-based catalysts, calcined dolomites and magne-
sites, zeolites, olivine and iron catalysts. Among all
these only few have been tried as active bed additive
inside the gasier itself during gasication. There is
a great potential of in-bed additives in terms of tar
reduction and thus avoiding complex downstream tar
removal methods. These bed additives act as in situ
catalysts promoting several chemical reactions in the
same gasier. The presence of additives not only inu-
ences the gas composition, but also the heating value
of the product gas. The use of catalytically active ma-
terials during biomass gasication promotes the char
gasication, changes the product gas composition and
reduces the tar yield. Besides these, addition of active
bed materials also prevents the solid agglomeration
tendencies and subsequent choking of the bed.
Limestone was one of the rst additives used in the
gasier to improve the gasication. Walawender et al.
[33,34] performed series of experiments using lime-
stone as bed additive in a uidized bed gasier. They
used a mixture of 25 wt% limestone and 75 wt% silica
sand as a bed material for steam gasication of alpha
cellulose with an intention of predicting the behaviour
of the gasier with increase in temperature [33]. The
researchers also applied the same mixture of bed ma-
terial for steam gasication of manure [34]. Although
no attempt was made to observe the tar formation,
the authors reported that the gas composition, heating
value and yield were all inuenced by the presence
of 25 wt% limestone in the bed. The most important
outcome of their experiments was that the addition of
limestone to the bed of silica sand could prevent ag-
glomeration of the bed [34].
Among all the active materials, dolomite is the most
popular and mostly studied in-bed additive. A lot of
research has been done using this catalyst with regard
to tar cracking in bed as well as in a secondary reactor.
Karlsson et al. [35] reported the successful demon-
stration of biomass IGCC process (VEGA Gasica-
tion with combined cycle) which involved dolomite
as bed material. The tar content observed was about
12 g m
3
o
of light tars (excluding benzene) and 100
300 mg m
3
o
of heavy tars. Rapagn a et al. [36] also
mentioned the use of calcined dolomite directly in
the gasier and observed improvements in the gas
yield. Corella et al. [37] reported that the use of cal-
cined dolomite inside the gasier could decrease the
tar amount from 6.5 (without dolomite) to 1:3 wt%.
132 L. Devi et al. / Biomass and Bioenergy 24 (2003) 125140
The two research groups in Spain (University of Com-
plutense and University of Saragossa) have done sev-
eral experiments with in-bed use of dolomite. Narv aez
et al. [13] suggested that addition of calcined dolomite
(15 wt% of the biomass feed) improves the quality
of the product gas. Their experiments resulted in a
tar reduction of about 40% with addition of 3% cal-
cined dolomite to biomass feed. A 10 wt% of calcined
dolomite is reported to be sucient by Olivares et al.
[38] for signicant improvement of the gas quality
as well as tar reduction. The elimination of tar over
calcined dolomite is mostly due to steam and dry
reforming reactions.
Corella et al. [9] observed almost no dierence in
the lower heating value of the gas produced by us-
ing in-bed dolomite and that of downstream use of
dolomite. The increase in H
2
production compensated
the CO decrease; also there was hardly any variation
in the CH
4
and C
2
H
n
amounts in the product gas. The
tar content in the product gas with the use of in-bed
dolomite was signicantly reduced and this reduc-
tion is more or less comparable to using downstream
dolomite. Besides the use of active additive in the
bed, the researchers also observed that the gasifying
medium plays a very important role in tar reduction,
which has already been discussed in the previous sec-
tion of this paper. An amount of 2030 wt% dolomite
(rest being silica sand) in the gasier was reported to
reduce the tar content as low as 1 g m
3
o
at an ER
of 0.3 [14]. The authors also studied the inuence of
several operating parameters in combination with use
of in-bed dolomite and found that a proper selection
of parameters in addition to dolomite can signicantly
enhance production of a clean gas. Although dolomite
has been proven to be a very eective bed additive in
terms of tar reduction, it has some critical limitations.
Dolomite is softer and thus gets eroded by the silica
sand particles. Also, some dolomite particles break
during the calcination and give rise to a large produc-
tion of nes. So, there is a great problem of carry over
of solids from the bed.
An alternative of dolomite can be naturally occur-
ring particles of olivine, which is a mineral containing
magnesium, iron oxide and silica. Olivine is advanta-
geous in terms of its attrition resistance over that of
dolomite. Rapagn a et al. [39] investigated the catalytic
activity of olivine and observed that it has a good per-
formance in terms of tar reduction and the activity
is comparable to calcined dolomite. They reported
more than 90% reduction in average tar content, the tar
amounted 2:4 g m
3
o
compared to 43 g m
3
o
with only
sand. The authors also performed experiments with
olivine as the bed material and a LaNiFe trimetallic
perovskite catalyst in a secondary reactor. The com-
bined action of the materials was very promising; a
gas with around 0:3 g m
3
o
of tar was produced [40].
Ros en et al. [41] reported the use of olivine as a bed
material for pressurized gasication (0.41:0 MPa) of
birch.
Mudge et al. [42] studied the catalytic steam
gasication of biomass using alkali carbonate and
Ni-based catalyst at the Pacic Northwest Laboratory
(PNL). Supported Ni catalysts were found to be very
eective in producing high yields of synthesis gas
[42,43]. Baker et al. [44] studied a number of cat-
alysts (Ni=Al
2
O
3
; K
2
O
3
; NiCuMo=SiO
2
Al
2
O
3
) for
pressurized steam gasication of bagasse and wood
to produce synthesis gas for methanol and ammonia
production in a laboratory-scale gasier. The catalytic
gasication resulted in increase in the gas yield at
the expense of tar and char. They also carried out
gasication tests in a 1-t d
1
uidized-bed process
development unit (PDU) using the same catalysts.
They observed severe deactivation of the Ni-based
catalyst due to carbon deposition [44].
A number of other metal oxide catalysts such as
V
2
O
5
, Cr
2
O
3
; Mn
2
O
3
; Fe
2
O
3
, CoO, NiO, CuO, MoO
3
on Al
2
O
3
were tested by Yoshinori et al. [45] for
wood gasication to produce methanol synthesis gas.
All these metal oxides produced high yields of gas,
but the gas composition strongly varied depending on
the type of metal oxide used. MoO
3
, CoO and V
2
O
5
produced higher amount of CO
2
, whereas NiO, Cr
2
O
3
and Fe
2
O
3
produced relatively low amounts of CO
2
.
The most suggested favourable gasication catalyst
was NiO=Al
2
O
3
, which could produce a gas with a
H
2
=CO ratio close to 2.0, also observed to produce
only traces of total olens. Although these authors did
not quantitatively measure the tar amount, their results
showed that the additives greatly improve the overall
product distribution and the gas heating value. Sev-
eral other researchers reported in-bed use of Ni-based
catalysts. Bilbao et al. [46] observed that addition of
50 wt% of the NiAl catalyst to bed material (sand),
increases hydrogen production up to 62% with con-
siderable decrease in the methane content. The same
L. Devi et al. / Biomass and Bioenergy 24 (2003) 125140 133
Ni/Al coprecipitated catalyst was also observed to be
very eective for CO
2
gasication of biomass [23] The
ratio of catalyst weight and biomass ow rate signi-
cantly inuences the product gas distribution.
The major problem with Ni-based catalysts is fast
deactivation due to carbon deposition on the catalyst
and poisoning due to the presence of H
2
S. These prob-
lems can be avoided to some extent by increasing the
temperature [7,47]. In view with the experiences of
PNL, in bed use of Ni catalyst is not an attractive op-
tion. Baker et al. [48] and Mudge et al. [49] reported
that the lifetime of the Ni catalysts could be extended
by placing it in a secondary bed instead of using it in
the gasier. Placing the NiCuMo on SiAl
2
O
3
and Ni
on -alumina catalysts in a secondary uidized-bed
reactor downstream the gasier, they observed no de-
activation for 3040 h tests.
Ni-based catalysts are also very eective for NH
3
reduction. Wang et al. [47] reported that NH
3
can
be decomposed eectively with an Ni-based catalyst
above 800
C, pressure
of 12 bar and a space time of 3 s. Their observation
was that the amounts of light hydrocarbons have a
negative eect on NH
3
decomposition. Mojtahedi et
al. [51] investigated Ni/alumina and Ru/alumina cat-
alyst for NH
3
decomposition in a synthesis gas mix-
ture. The same catalysts were studied for ammonia
and tar decomposition in an actual biomass gasica-
tion system [6]. These catalysts are less eective in
terms of NH
3
reduction in the presence of tars. Simell
et al. [7] also observed that Ni/alumina catalyst is ef-
fective for NH
3
as well as tar reduction. The authors
observed that NH
3
decomposition could be enhanced
with iron-containing materials over a temperature of
900
C) Time (s)
Cellulose 1.02.0 Steam 600800 1.261.54 Limestone Walawender et al. [33]
Wood Steam 750 K
2
CO
3
Douglas et al. [52]
Pine sawdust 8.5 1.0 Steam 750 Dolomite Corella et al. [37]
FCC
Pine sawdust 1025 4.00.8 Air 800 0.6 Dolomite Narv aez et al. [13]
Pine chips 1012 5.01.0 Steam=O
2
795835 Dolomite Olivares et al. [38]
Pine sawdust 10 Steam 700 0:4 NiAl Bilbao et al. [46]
Pine sawdust 10 CO
2
700 NiAl Garca et al. [23]
Pine chips Air;steam/O
2
800850 Dolomite Corella et al. [9]
Pine chips 1015 Air 800845 Dolomite Gil et al. [14]
FCC
Almond shell 7.9 1.1 Steam 770820 Olivine Rapagn a et al. [39]
Dolomite
Birch 68 1.03.0 O
2
N
2
700900 Silver sand Ros en et al. [41]
Olivine
Pine/bagasse Steam 750 30 Ni-based Baker et al. [44]
7. catalytic tar reduction depends on gasication
conditions.
A summary of some of the research work done using
bed additives is given in Table 1.
2.2.3. Gasier design modication
Reactor design is very crucial for gasication in
terms of eciency, heating value of the product gas
and also for tar formation. Modication of the gasier
design can be very eective in producing clean gas.
Some attempts have been reported in this regard and
are observed to be successful in tar reduction.
Secondary air injection to the gasier results in a
signicant tar reduction. A higher temperature could
be attained due to the secondary air injection in the
gasier. Pan et al. [56] injected secondary air just
above the biomass feeding point in the uidized bed.
They reported that an optimal secondary to primary
air ratio of about 20% is sucient to reduce 88:7 wt%
of the total tar for a gasication temperature range of
840880
C.
3. Remarks and conclusion
An optimized gasication process can produce a
considerably clean gas, thus eliminating the need of
downstream hot gas cleaning. This approach is termed
as ideal primary method by the authors, and shown
in Fig. 2. According to this concept all tars should be
prevented or eliminated in the gasier itself and this
way no additional after treatments for tar removal is
required. The following factors are most important as
primary measures:
1. A proper selection of operating parameters (spe-
cially temperature, gasifying medium, ER and resi-
dence time) can simplify the entire gasication chain.
2. Addition of some active bed materials has been
proven to be eective. But there are a number of fac-
tors that have to be taken into account when selecting
the bed materials. These bed additives should be eco-
nomically available, attrition resistant, and of course
active and selective in terms of tar reduction. Among
all additives used so far dolomite, olivine and char are
important and there is need for further research to
develop other cheap additives.
3. The modications made in the gasier design
must be easily implementable. Most of the attempts
made to modify the gasier design claimed to produce
a clean gas. Moreover, few factors should be kept
in mind while designing the entire gasication chain:
it should be environmental friendly, should be able
to produce a gas of high heating value with low tar
content, and it should be economically feasible.
However, the type of treatments that have to be
used in the gasication chain highly depends on the
end-use applications. The rst step for process selec-
tion for biomass gasication must be to evaluate the
future application. Depending on the application of the
gas produced, it must be decided whether a primary or
secondary tar removal method or a combination
of both should be applied. This approach is shown in
Fig. 8.
Although primary measures are of potential impor-
tance for the gasication chain as a whole, but they
cannot solve the purpose of tar reduction without ef-
fecting the useful gas composition and heating value.
Combination of proper primary measures with down-
stream methods is observed to be very eective in all
respect. More research is required for developing an
ecient primary technique (combination of optimal
operational parameters, bed additives and reactor de-
sign) which would be sucient to produce a clean
138 L. Devi et al. / Biomass and Bioenergy 24 (2003) 125140
gas and eliminating the need of downstream tar re-
moval techniques. Also, more attention must be paid
to reduce other contaminants such as NH
3
, HCN, HCl,
H
2
S, etc. in combination with tar reduction.
References
[1] Rogner HH, Popescu A. An introduction to energy. In:
Goldemberg J (Chair), editor. World energy assessment:
energy and the challenge of sustainability. New York: United
Nations Development Programme, 2000.
[2] Bridgwater AV. The technical and economic feasibility
of biomass gasication for power generation. Fuel
1995;74(5):63153.
[3] Neeft JPA, Knoef HAM, Onaji P. Behaviour of tar in biomass
gasication systems. Tar related problems and their solutions.
Novem Report No. 9919. Energy from Waste and Biomass
(EWAB), The Netherlands, 1999.
[4] Bui T, Loof R, Bhattacharya SC. Multi-stage reactor for
thermal gasication of wood. Energy 1994;19(4):397404.
[5] Milne TA, Evans RJ. Biomass gasication tars: their nature,
formation and conversion. NREL, Golden, CO, USA, Report
no. NREL/TP-570-25357, 1998.
[6] Mojtahedi W, Ylitalo M, Maunula T, Abbasian J. Catalytic
decomposition of ammonia in fuel gas production in
pilot-scale pressurized uidized-bed gasier. Fuel Processing
Technology 1995;45:22136.
[7] Simell P, Kurkela E, St