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Biomass and Bioenergy 24 (2003) 125140

A review of the primary measures for tar elimination


in biomass gasication processes
Lopamudra Devi

, Krzysztof J. Ptasinski, Frans J.J.G. Janssen


Environmental Technology Group, Laboratory of Chemical Reactor Engineering, Eindhoven University of Technology,
Den Dolech 2, P.O. Box 513, 5600 MB Eindhoven, Netherlands
Received 1 February 2002; received in revised form 11 July 2002; accepted 15 July 2002
Abstract
Tar formation is one of the major problems to deal with during biomass gasication. Tar condenses at reduced temperature,
thus blocking and fouling process equipments such as engines and turbines. Considerable eorts have been directed on tar
removal from fuel gas. Tar removal technologies can broadly be divided into two approaches; hot gas cleaning after the
gasier (secondary methods), and treatments inside the gasier (primary methods). Although secondary methods are proven
to be eective, treatments inside the gasier are gaining much attention as these may eliminate the need for downstream
cleanup. In primary treatment, the gasier is optimized to produce a fuel gas with minimum tar concentration. The dierent
approaches of primary treatment are (a) proper selection of operating parameters, (b) use of bed additive/catalyst, and
(c) gasier modications. The operating parameters such as temperature, gasifying agent, equivalence ratio, residence time,
etc. play an important role in formation and decomposition of tar. There is a potential of using some active bed additives
such as dolomite, olivine, char, etc. inside the gasier. Ni-based catalyst are reported to be very eective not only for tar
reduction, but also for decreasing the amount of nitrogenous compounds such as ammonia. Also, reactor modication can
improve the quality of the product gas. The concepts of two-stage gasication and secondary air injection in the gasier are
of prime importance. Some aspects of primary methods and the research and development in this area are reviewed and cited
in the present paper.
? 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Tar removal; Gasication; Bed additive; Gasier design; Catalyst
1. Introduction
With respect to global issues of sustainable energy
and reduction in greenhouse gases, biomass is getting
increased attention as a potential source of renewable
energy. Biomass is not yet competitive with fossil fu-
els. Fossil fuel contributes to the major part of worlds

Corresponding author. Tel.: +31-40-2473734; fax: +31-40-


2446653.
E-mail address: l.devi@tue.nl (L. Devi).
total energy consumption. According to the World En-
ergy Assessment report, 80% of the worlds primary
energy consumption is contributed by fossil fuel, 14%
by renewable (out of which biomass contributes 9.5%)
and 6% by nuclear energy sources [1]. A sustainable
energy future requires combination of factors such as
renewable resources and advanced energy technology.
Biomass refers to all organic materials that are
originated from plants. Biomass is being traditionally
used as energy source especially for cooking and
heating particularly in the developing countries.
0961-9534/03/$ - see front matter ? 2002 Elsevier Science Ltd. All rights reserved.
PII: S0961- 9534( 02) 00102- 2
126 L. Devi et al. / Biomass and Bioenergy 24 (2003) 125140
Nomenclature
Daf dry, ash free
ER equivalence ratio: O
2
content of
air supply=O
2
required for complete
combustion
FCC uid catalytic cracking
GR gasifying ratio: (H
2
O + O
2
)=Biomass
[(kg h
1
) (kg
daf
h
1
)
1
]
LHC light hydrocarbons
m
3
o
normal cubic meter
PAH polycyclic aromatic hydrocarbon
RDF refuse derived fuel
SB steambiomass ratio; H
2
O=biomass
[(kg h
1
) (kg
daf
h
1
)
1
]
Dierent biomass conversion processes produce heat,
electricity and fuels. Biomass integrated gasica-
tion/combined cycle systems are of prime importance
as modern technologies [2]. Among all biomass con-
version processes, gasication is one of the promising
ones. The energy eciency in case of gasication
is higher than that of combustion. One of the major
issues in biomass gasication is to deal with the tar
formed during the process. Tar is a complex mixture
of condensable hydrocarbons, which includes single
ring to 5-ring aromatic compounds along with other
oxygen-containing hydrocarbons and complex PAH.
Various research groups are dening tar dierently.
In the EU/IEA/US-DOE meeting on tar measurement
protocol held in Brussels in the year 1998, it was
agreed by a number of experts to dene tar as all
organic contaminants with a molecular weight larger
than benzene [3]. Tar is undesirable because of vari-
ous problems associated with condensation, formation
of tar aerosols and polymerization to form more com-
plex structures, which cause problems in the process
equipment as well as the engines and turbines used in
application of the producer gas. However, the mini-
mum allowable limit for tar is highly dependent on the
kind of process and the end user application. Bui et
al. [4] mentioned that the preferable tar and dust loads
in gases for engines must be lower than 10 mg m
3
o
.
Milne et al. [5] tabulated the tar tolerance limit
for various end use devices, suggested by dierent
researchers.
The present paper discusses the strategies for tar re-
moval and aims to elaborate more on the importance of
primary measures. This paper provides an overview of
primary methods used for tar removal during biomass
gasication. A direct comparison of the data avail-
able for tar in the literature, is very dicult because
of the following reasons; use of dierent operating
conditions, dierent type of gasier used, dierent tar
capturing, sampling and analysing method, and most
importantly the non-consistency in dening tar used
by various researchers. Detailed discussion regarding
the tar denition, tar sampling and analysing methods
are out of the scope of this review, those can be found
in the corresponding references.
2. Tar removal methods
Several approaches for tar reduction have been re-
ported in the literature. A major part of ongoing re-
search deals with the development of ecient meth-
ods for tar removal in an economical and optimized
way. There are some sophisticated options available,
which have claimed to reduce tar amount signicantly.
However, the method must be ecient in terms of tar
removal, economically feasible, but more importantly,
it should not aect the formation of useful gaseous
products. All the methods available can be categorized
in two types depending on the location where tar is re-
moved; either in the gasier itself (known as primary
method) or outside the gasier (known as secondary
method). The following sections describe both meth-
ods with emphasis on the primary method.
2.1. Secondary methods
Secondary methods are conventionally used as
treatments to the hot product gas from the gasier.
The concept of secondary methods is given in Fig. 1.
These methods can be chemical or physical treatment
L. Devi et al. / Biomass and Bioenergy 24 (2003) 125140 127
Application
Gasifier
Syn. gas
+ Tar
Biomass
Gasifier
Air/Steam/O
2
Tar
Removal
Gas
Cleanup
Downstream Cleaning
(Tar; Dust; N, S, halogen compounds)
Tar free gas
Application
Gasifier
Syn. gas
+ Tar
Biomass
Gasifier
Air/Steam/O
2
Tar
Removal
Gas
Cleanup
Downstream Cleaning
(Tar; Dust; N, S, halogen compounds)
Tar free gas
Fig. 1. Tar reduction concept by secondary methods.
Biomass
Gasifier
+
Tar Removal
Air/Steam/O
2
Application
Gasifier
+
Tar Removal
Tar free gas
Gas cleanup
Dust N, S, halogen Compounds
Biomass
Gasifier
+
Tar Removal
Air/Steam/O
2
Application
Gasifier
+
Tar Removal
Tar free gas
Gas cleanup
Dust N, S, halogen Compounds
Fig. 2. Tar reduction concept by primary method.
as follows
tar cracking downstream the gasier either ther-
mally or catalytically,
mechanical methods such as use of cyclone, bae
lter, ceramic lter, fabric lter, rotating particle
separator, electrostatic lter and scrubber.
Although, downstream gas cleaning methods are re-
ported to be very eective in tar reduction, in some
cases they are not economically viable. In addition,
several researchers reported secondary methods to be
very eective in terms of ammonia reduction [6,7]. It
is also observed that production of very clean gas with
a considerably low tar content requires a complex pro-
cess. Narv aez et al. [8] reported a three-step process
that could produce a very clean gas (with very low tar
concentration).
The secondary methods are widely being studied
and are well understood. Since they are out of the
scope of this paper, interested readers are advised to
look into excellent reports by Milne et al. [5] and Neeft
et al. [3].
2.2. Primary methods
Primary methods can be dened as all the mea-
sures taken in the gasication step itself to prevent
or convert tar formed in the gasier. An ideal pri-
mary method concept eliminates the use of secondary
treatments as shown in Fig. 2. Primary methods are
not yet fully understood and yet to be implemented
commercially.
To get the best-quality exit gas, the gasier per-
formance has to be optimized. For an optimized
performance of the gasier, the main attractive factors
are the design and the operation of the gasier. Corella
et al. [9] mentioned that in-bed use of dolomite results
in a similar tar content as using it in downstream cat-
alytic reactor. If the gasier bed is well designed and
operated, the measures taken during the gasication
step can produce a very clean gas with respect to the
end user application, eliminating the use of down-
stream secondary steps. The primary issues include
(a) the proper selection of the operating conditions,
(b) the use of a proper bed additives or a catalyst
during gasication, and (c) a proper gasier design.
128 L. Devi et al. / Biomass and Bioenergy 24 (2003) 125140
2.2.1. Gasication conditions
The operating conditions play a very important
role during biomass gasication in all respects, such
as carbon conversion, product gas composition, tar
formation and tar reduction. The most important in-
uencing parameters include temperature, pressure,
gasifying medium, catalyst and additives (explained
in the next section), equivalence ratio (ER), residence
time, etc. The selection of these parameters also de-
pends on the type of gasier used. A homogeneous
bed temperature prole and a well-functioning bed
uidization are of utmost importance to avoid distur-
bances in the operation of a uidized-bed gasier.
To achieve a high carbon conversion of the biomass
and low tar content in the resultant product gas, a
high operating temperature (above 800

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. With increase in temperature,


the amount of total oxygen-containing components
drastically goes down, the amount of substituted
1-ring and 2-ring aromatics also decrease, but for-
mation of 3- and 4-ring aromatics increases rapidly.
Almost 40% increase in naphthalene content was
reported at 900

C. Similar results were reported by


Brage et al. [12] for gasication of birch wood. Dur-
ing the same experimental time they observed almost
complete reduction of phenol content, a 50% decrease
in toluene content, but a considerable increase in
benzene (from 14 to 24 mg l
1
) and in naphthalene
contents (from 2 to 8 mg l
1
), when the tempera-
ture was raised from 700

C to 900

C. By changing
the bed temperature of the bubbling uidized bed
from 700

C to 850

C, Narv aez et al. [13] observed


an increase in H
2
content from 5 to 10 vol%, CO
content from 12 to 18 vol%, slight decrease in CO
2
content from 16 to 13 vol% and almost no change
in the amount of CH
4
and C
2
H
2
. They observed a
drastic decrease in tar content (about 74% less); the
tar amounts being 19 g m
3
o
at 700

C and 5 g m
3
o
at 800

C. It is also possible to decrease the amount


of tar to a considerably lower value by increasing the
freeboard temperature in case of uidized-bed gasi-
ers [13,14]. Besides tar, temperature also inuences
the formation of NH
3
and N
2
. The level of these two
species in the product gas largely depend on the ther-
mochemical reactions occurring in the gasier and
these reactions are directly related with temperature.
Zhou et al. [15] reported almost 58% decrease in NH
3
content when the temperature was raised from 700

C
to 900

C for sawdust gasication. Over the same


temperature range, NO and HCN were also detected,
but at a much lower level than NH
3
. For leucaena
gasication, an 80% decrease in NH
3
content is re-
ported when the gasier temperature was increased
from 750

C to 900

C. Increases in molecular nitrogen


were observed in the product gas which is basically
due to the thermochemical conversion of NH
3
[15].
However, there are several other factors that limit
the operating temperature. Hallagren [16] mentioned
a typical temperature range for dierent feed materi-
als with respect to various critical factors that largely
inuences the entire gasication system. Besides the
tar content, these factors, as shown in Fig. 3, are
the gas heating value, char conversion and the risk of
sintering.
Several researchers have investigated pressurized
biomass gasication. Knight [17] investigated the ef-
fect of system pressure for biomass gasication. When
the pressure was increased to 21:4 bar, almost com-
plete elimination of phenols was observed for wis-
consin whole tree chips. Although the amount of total
tar decreased, the fraction of PAH increased with in-
creasing pressure. Moilanen et al. [18] studied the
L. Devi et al. / Biomass and Bioenergy 24 (2003) 125140 129
700
O
C 00
O
C 1000
O
C 800
O
C
Agro
fuels
RDF
Woody
Biomass
Coal
Higher Gas heating value Lower
Higher Tar content Lower
Lower Char conversion Higher
Decreasing risk Sintering Increasing risk
700
O
C 00
O
C 1000
O
C 800
O
C
Agro
fuels
RDF
Woody
Biomass
Coal
700
O
C 00
O
C 1000
O
C 800
O
C
Agro
fuels
RDF
Woody
Biomass
Coal
Higher Gas heating value Lower
Higher Tar content Lower
Lower Char conversion Higher
Decreasing risk Sintering Increasing risk
Higher Gas heating value Lower
Higher Tar content Lower
Lower Char conversion Higher
Decreasing risk Sintering Increasing risk

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 with an ER of 0.35. But the tar content


decreases sharply as the ER was increased, being as
low as 2 g m
3
o
. The ER strongly inuences the type
of gasication products. According to Kinoshita et al.
[10], tar yield and tar concentration decreases as the
ER increases because of more availability of oxygen
to react with volatiles in the aming pyrolysis zone.
This eect of ER is more signicant at higher tem-
perature. The ER is very crucial because its higher
value results in lower concentration of H
2
, CO and
higher CO
2
content in the product gas, thus decreas-
ing the heating value of the gas. Although the total tar
concentration decreased by almost 30% when the ER
was increased from 0.22 to 0.32 for a temperature of
700

C, the fraction of PAH increased in the total tar.


The decrease in total tar concentration could be much
higher at higher temperature. Almost all phenols were
converted at an ER of 0.27. Increase in contents of
benzene, naphthalene, 3- and 4-ring compounds were
reported. Narv aez et al. [13] reported a similar trend
with increasing ER for gasication of pine sawdust
at 800

C. A tar content of about 27 g m


3
o
was re-
ported when the ER was increased until 0.45. Also,
they gave a comparison of various experiments with
varying ER by other researchers. According to Zhou
et al. [15], ER does not signicantly inuence the
concentration of nitrogenous products during biomass
gasication. A slight increase in NH
3
(from 310 to
350 ppm) was observed when the ER was increased
from 0.25 to 0.37 at 800

C for sawdust gasication.


In view of lower heating value as well as poor gas
composition, several researchers used pure steam and
they observed a completely dierent product gas dis-
tribution. The steam gasication product is more or
less free from N
2
and more than 50% H
2
in the prod-
uct gas. Herguido et al. [21] reported steam gasica-
tion and the eect of steam/biomass ratio (SB) on the
130 L. Devi et al. / Biomass and Bioenergy 24 (2003) 125140
gasication products. They observed an increase in
H
2
(as high as 60%) and CO
2
(from 10 to 30%) con-
tents, a sharp decrease in CO (from 35 to 10%) con-
tent, a slight decrease in CH
4
content and relatively
no change of C
2
-fractions (C
2
H
2
; C
2
H
4
; C
2
H
6
) when
the SB ratio was increased from 0.5 to 2.5. In spite of
sharp reduction in tar (8% yield at 0.5 SB decreased
to almost nil at 2.5) there was a sharp decrease in the
lower heating value that was attributed by the decrease
in CO. Garca et al. [22,23] used steam as gasifying
agent for pine sawdust using an Ni/Al coprecipitated
catalyst. The catalyst improves the reaction rate of
steam with char and also can participate in secondary
reactions, thus leading to decrease in tar content of the
gas. The high H
2
production during steam gasication
can be attributed by the following chemical reactions:
C
n
H
x
+ nH
2
O (n + x=2)H
2
+ nCO; (1)
CH
4
+ H
2
O 3H
2
+ CO;
H
0
298
= +205:81 kJ mol
1
; (2)
C
2
H
4
+ 2H
2
O 4H
2
+ 2CO;
H
0
298
= +210:07 kJ mol
1
; (3)
CO + H
2
O H
2
+ CO
2
;
H
0
298
=41:16 kJ mol
1
; (4)
C + H
2
O H
2
+ CO;
H
0
298
= +131:29 kJ mol
1
: (5)
The rst reaction represents tar reforming reaction
which contributes to increment in the content of H
2
and CO gases.
Steam gasication is endothermic and hence some-
times requires complex design for heat supply in
the process. Use of some amount of oxygen in the
gasifying medium can provide the necessary heat for
gasication and then the gasier works as an auto-
thermal reactor. In view of that, many researchers
used steamoxygen mixtures for biomass gasication.
Aznar et al. [24] reported more than 85% reduction in
total tar when they increased the (steam+O
2
)/biomass
ratio termed as gasifying ratio (GR) from 0.7 to 1.2.
The researchers also reported that for low GR val-
ues in the gasier produces light tars which can be
easily destroyed using catalyst [25]. Gil et al. [26]
recommended H
2
O=O
2
ratio of around 3.0 (mol/mol)
for steamO
2
mixture for gasication. When the GR
was increased from 0.6 to 1.7, they observed the fol-
lowing changes in gas composition, decrease in H
2
content from 29% to 13%, decrease in CO content
from 50% to 30%, increase in CO
2
content from 14%
to 37%, slight decrease in CH
4
content from 7% to
5% and a change in C
2
hydrocarbons from 3.5% to
2.3% (all percentages are expressed in volume on dry
basis). Tar content of the raw gas sharply decreases
with GR, less than 5 g m
3
o
at a GR of 1.2. The same
researchers also observed that the eect of gasier
bed temperature on tar content is signicant at lower
GR values (1:0). They recommended a gasier
bed temperature between 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. Wang and his coworkers [50] reported


95% conversion of NH
3
along with 89% conversion
of light hydrocarbons, which they dened as C
2
H
6
,
C
6
H
6
; C
7
H
8
and C
9
H
8
, with Ni-based catalyst in a
secondary reactor at a temperature of 874

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. It should be noted that all above-mentioned


studies on catalytic NH
3
decomposition were carried
out in external reactors as secondary treatment of the
hot gas from the gasier.
Douglas et al. [52] used 8 wt% potassium carbon-
ate as bed additive impregnated on wood for steam
gasication in a uidized bed gasier at operating
temperature of 750

C. They observed a reduction of


phenolic tar compounds by a factor of 5 and PAH by
a factor of about 10. It is observed that alkali metals,
especially potassium, act as a promoter in unzipping
the cellulose chains during the thermal decomposition
of woody biomass, thus eecting the product gas
distribution.
Corella et al. [37] also reported the use of
in-equilibrium FCC catalyst as bed additive for steam
gasication of pine sawdust. This catalyst contained
zeolite in a silicaalumina matrix, and was once used
from oil reneries. The experiment was done by feed-
ing the catalyst to biomass feed (biomass=FCC = 10)
and 20% reduction in tar content was reported. How-
ever, this catalyst was rapidly deactivated by coke
deposition and the catalyst particles were entrained
out of the bed just in a few seconds. The authors
performed some more experiments with in-bed use
of the same catalyst at a higher temperature range
(800820

C) and observed almost a 60% decrease in


tar content with the in-bed use of 5% in-equilibrium
FCC catalyst [14]. Besides cracking, hydrocracking
might be a possible reason of tar decomposition.
Another inexpensive material can be char and it has
also been widely reported in the literature. Char is
not only a cheap and available material, but also it is
indigenously produced inside the gasier itself. Char
has been reported to be used in secondary tar cracking
reactors by several researchers [53,54]. Chembuku-
lam et al. [55] reported that cracking over a char bed
at a temperature of 950

C resulted in almost com-


plete decomposition of tar and pyroligneceous liquor
into gases of low caloric value. It should be noted
that char itself gets converted during the gasication
process, and hence there may be need of external
continuous supply of char into the gasier. Several
researchers reported use of char in two-stage gasi-
er which is explained in the next section of this
paper.
Based on the reported literature, the following gen-
eral observations can be made with the addition of
active bed material during gasication
1. a change in product gas distribution,
2. a decrease in tar amount,
3. an increase in hydrogen production,
4. a slight decrease in the amount of CO and increase
in the amount of CO
2
,
5. an almost no variation in the amount of CH
4
,
6. problems regarding catalyst deactivation and
carryover of nes were severe,
134 L. Devi et al. / Biomass and Bioenergy 24 (2003) 125140
Table 1
In-bed additives used by researchers under dierent operating conditions
Feed Feed properties Operating conditions Additive Reference
Moisture (%) Size (mm) Gasif. agent Temp (

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. Narv aez et al. [13] performed few exper-


iments with secondary air injection in the freeboard
of uidized-bed gasier. They observed a tempera-
ture rise of about 70

C and a tar reduction from 28 to


16 g m
3
o
. They expected that with longer size gasi-
ers the temperature rise in the freeboard due to air
injection could be higher, thus a higher possibility of
lower tar content in the gas.
Two-stage gasier design has been reported to
be very eective in producing clean gas. The basic
concept of this design is to separate the pyrolysis
zone from the reduction zone. A two-stage gasier is
equivalent to two single-stage gasiers. Tars formed
during the pyrolysis (rst stage) are decomposed in
the reduction zone (second stage). A two-stage gasi-
er has been studied in the Asian Institute of Tech-
nology (AIT), Thailand, and it resulted in a gas of tar
content about 50 mg m
3
o
, about 40 times less than a
single-stage reactor under similar operating conditions
[4]. This concept involves two levels of air intakes.
The high temperature achieved in the second zone due
to the addition of a secondary air helps in reducing the
tar level to a considerably lower value. Fig. 4 repre-
sents the two-stage gasication concept applied in the
AIT. It was observed that most of the tars were formed
during the warm-up period. This could be avoided by
lling the gasier with a bed of char just above the
primary air inlet. The gasier was loaded with char
before ignition. It was reported that char lling al-
most totally eliminates tar formation during start-up
in the reactor. Further modication was done by
L. Devi et al. / Biomass and Bioenergy 24 (2003) 125140 135
Pyroly
(1
st
stage)
Reduction zone
(2nd stage)
Biomass Feed
Tar free gas
Secondary air
Primary air
Pyrolysis gas ,Tar
G
a
s
i
f
i
e
r
Pyroly
(1
st
stage)
Reduction zone
(2
nd
stage)
Biomass Feed
Secondary air
Primary air
Pyrolysis gas ,Tar
Pyroly
(1
st
stage)
Reduction zone
(2nd stage)
Biomass Feed
Tar free gas
Secondary air
Primary air
Pyrolysis gas ,Tar
G
a
s
i
f
i
e
r
Pyrolytic zone
(1
st
stage)
Reduction zone
(2
nd
stage)
Biomass Feed
Secondary air
Primary air
Pyrolysis gas ,Tar
Fig. 4. Two-stage gasication concept (Asian Institute of Tech-
nology, Thailand).
Bhattacharya et al. [57] in such a way that char was
produced inside the gasier itself, thus avoiding input
of external charcoal for subsequent experiments. For
this purpose, an extra primary air inlet above the origi-
nal air supply was added. The researchers coupled the
char gasier with the original two-stage gasier and
reported that this design could produce considerably
low tar content (19 mg m
3
o
) producer gas.
Successful operation of this type of gasier largely
depends on how stable the pyrolysis zone is [4]. The
stabilization of this zone is dependent on the balance
between downward solid movement and upward ame
propagation. If the wood particles move faster than
the ame propagation, the pyrolysis zone reaches the
second air intake thus making the whole system to act
like single-stage gasier. If ame propagation upward
exceeded wood consumption, both stages remained in
stable operation. The ame propagation control was
done by adjustments of the airow by changing the
width of the second air inlet.
Another two-stage gasier designed at the Tech-
nical University of Denmark is a combination of
pyrolysis of the biomass feed with subsequent partial
oxidation of the volatile products in presence of a
charcoal bed as shown in Fig. 5 [58,59]. Henriksen
Fig. 5. Two-stage gasier (Technical University of Denmark).
et al. [58] reported the successful demonstration of
this type of gasier (50 kW) for straw gasication.
Brandt et al. [59] also mention the same reactor design
(100 kW) for gasication of wood chips. The char
and the volatile pyrolysis products from the pyrolysis
unit entered the top of the gasication unit where the
gases were mixed with the preheated steam and air
starting partial combustion. The char is transported to
the char gasication unit. Allowing the gases to pass
through the bed of char, signicant tar reduction in
the total tar content (15 mg m
3
o
) has been reported.
Lower amounts of tar are attributed to the partial
combustion of the pyrolytic gases as well as the cat-
alytic eect of the charcoal bed. The char conversion
was measured to be 7090%.
Susanto et al. [60] developed a cocurrent moving
bed gasier with internal recycle and separate com-
bustion zone of pyrolysis gas. Their aim was to pro-
duce a design suitable for scaling up a downdraft gasi-
er maintaining a low tar content in the product gas.
This system was able to produce a clean gas with tar
content as low as 0:1 g m
3
o
. This gasier concept is
represented in Fig. 6. In this design, biomass is rst
pyrolysed and the produced char enters the reduction
zone. The volatile pyrolysis gases are mixed with the
gasifying air and burnt in an internal separate pre-
combustion chamber. The ue gas from this cham-
ber then acts as the gasifying medium for the gasier.
136 L. Devi et al. / Biomass and Bioenergy 24 (2003) 125140
Combustor
Counter-current
Reduction zone
Co-current
Reduction zone
Drying +
Pyrolysis zone Injector
G
a
s
i
f
i
e
r
Biomass Air
Product gas
C
h
a
r
I
n
j
e
c
t
e
d

g
a
s
F
l
u
e
g
a
s

1
F
l
u
e
g
a
s

2
R
e
m
a
i
n
i
n
g
(
F
r
o
m
r
e
d
u
c
t
i
o
n
z
o
n
e
)
Recycle
gas
Flue gas
C
h
a
r
Recycle gas=
Volatile +
Injected gas
Combustor
Counter-current
Reduction zone
Co-current
Reduction zone
Drying +
Pyrolysis zone Injector
G
a
s
i
f
i
e
r
Biomass Air
Product gas
C
h
a
r
I
n
j
e
c
t
e
d

g
a
s
F
l
u
e
g
a
s

1
F
l
u
e
g
a
s

2
R
e
m
a
i
n
i
n
g
(
F
r
o
m
r
e
d
u
c
t
i
o
n
z
o
n
e
)
Recycle
gas
Flue gas
C
h
a
r
Recycle gas=
Volatile +
Injected gas
Fig. 6. Moving-bed gasier with internal recycle.
The ue gas is divided into two parts, one part be-
ing fed to rst reduction zone. This recycle gas ows
countercurrently with the solid feed and char, thus en-
abling a more complete pyrolysis of the solids upon
entering the reduction zone. The second part is sent
Combustion
Zone
Gasification
Zone
Biomass
Steam Air
Product gas Flue gas
Heat
Bed material, char
Bed material
Gasifier
Combustion
Zone
Gasification
Zone
Biomass
Steam Air
Product gas Flue gas
Heat
Bed material, char
Bed material
Gasifier
Fig. 7. Fast internally circulating uidized-bed gasication concept.
to gasify the remaining char in the second reduction
zone, thus providing more complete gasication. The
main cause reported by the researchers for tar reduc-
tion in such design is due to the fact that the tar ow
is premixed with air prior to combustion and all tars
must pass through hot ame. Also they mentioned that
any tar that might have escaped from the hot combus-
tion chamber is subsequently converted over the char
in the combustion zone. A recycle ratio of 0.60.9 is
suggested to be optimal with regard to clean gas pro-
duction as well as good gasication eciency.
Several attempts have been made to develop new
uidized gasication techniques in view of better
eciency as well as quality fuel gas. A two-stage
uidized gasier which is a fast internally circulat-
ing uidized-bed gasier (FICFB), was reported and
observed to produce a gas with higher caloric value
and nearly free of N
2
[28,29,61]. This gasier concept
is shown in Fig. 7. The uidized-bed gasier was di-
vided into two zones, a gasication zone with steam
as the uidizing medium and a combustion zone with
air. Between these two zones, a circulation of bed
material is created and those bed material acts as heat
carrier from combustion to gasication zone. The
biomass is fed into the gasication zone and the bed
material together with char produced circulates to the
combustion zone. In the combustion zone the charcoal
L. Devi et al. / Biomass and Bioenergy 24 (2003) 125140 137
Biomass
Tar free
gas
Secondary
Method
Optional
Application
Pre
Treatments
Milling
Drying
Gasification
+
Primary
Methods
Gas
Cleanup
Primary methods:
Gasification conditions
Additives/Catalysts
Gasifier design
Secondary methods:
Mechanical Separation
Thermal Cracking
Catalytic Cracking
Separators for:
Particles, N, S and
halogen compounds
Prime Movers
Fuel Cells
Liquid Fuels
Chemicals
Clean
gas
Biomass
Tar free
gas
Secondary
Method
Optional
Application
Pre
Treatments
Milling
Drying
Gasification
+
Primary
Methods
Gas
Cleanup
Primary methods:
Gasification conditions
Additives/Catalysts
Gasifier design
Secondary methods:
Mechanical Separation
Thermal Cracking
Catalytic Cracking
Separators for:
Particles, N, S and
halogen compounds
Prime Movers
Fuel Cells
Liquid Fuels
Chemicals
Clean
gas
Fig. 8. Tar removal approach in biomass gasication.
is burnt. The exothermic reaction in the combustion
zone provides the energy for the endothermic gasi-
cation reactions with steam. They observed that total
tar amounted about 1 g m
3
o
that can be reduced to a
lower value with the addition of some catalyst as bed
additives. Fercher and his coauthors [29] performed
several experiments to nd the eect of olivine parti-
cles in the same gasier. The addition of olivine de-
creases the tar content of the product gas, but also it
depends on the gasication temperature. A total tar
amount of about 0:5 g m
3
o
was observed for wood
gasication with olivine at a temperature of 800

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.
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