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Biomass and Bioenergy 24 (2003) 125 140

A review of the primary measures for tar elimination


in biomass gasi cation 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 gasi cation. Tar condenses at reduced temperature,
thus blocking and fouling process equipments such as engines and turbines. Considerable e3orts have been directed on tar
removal from fuel gas. Tar removal technologies can broadly be divided into two approaches; hot gas cleaning after the
gasi er (secondary methods), and treatments inside the gasi er (primary methods). Although secondary methods are proven
to be e3ective, treatments inside the gasi er are gaining much attention as these may eliminate the need for downstream
cleanup. In primary treatment, the gasi er is optimized to produce a fuel gas with minimum tar concentration. The di3erent
approaches of primary treatment are (a) proper selection of operating parameters, (b) use of bed additive/catalyst, and
(c) gasi er modi cations. 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 gasi er. Ni-based catalyst are reported to be very e3ective not only for tar
reduction, but also for decreasing the amount of nitrogenous compounds such as ammonia. Also, reactor modi cation can
improve the quality of the product gas. The concepts of two-stage gasi cation and secondary air injection in the gasi er 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; Gasi cation; Bed additive; Gasi er 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 fuels. Fossil fuel contributes to the major part of worlds

Corresponding author. Tel.: +31-40-2473734; fax: +31-402446653.


E-mail address: l.devi@tue.nl (L. Devi).

total energy consumption. According to the World Energy 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: S 0 9 6 1 - 9 5 3 4 ( 0 2 ) 0 0 1 0 2 - 2

126

L. Devi et al. / Biomass and Bioenergy 24 (2003) 125 140

Nomenclature
Daf
ER
FCC
GR

dry, ash free


equivalence ratio: O2 content of
air supply=O2 required for complete
combustion
Iuid catalytic cracking
gasifying ratio: (H2 O + O2 )=Biomass
[(kg h1 ) (kg daf h1 )1 ]

Di3erent biomass conversion processes produce heat,


electricity and fuels. Biomass integrated gasi cation/combined cycle systems are of prime importance
as modern technologies [2]. Among all biomass conversion processes, gasi cation is one of the promising
ones. The energy eKciency in case of gasi cation
is higher than that of combustion. One of the major
issues in biomass gasi cation 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 de ning tar di3erently.
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 de ne tar as all
organic contaminants with a molecular weight larger
than benzene [3]. Tar is undesirable because of various problems associated with condensation, formation
of tar aerosols and polymerization to form more complex structures, which cause problems in the process
equipment as well as the engines and turbines used in
application of the producer gas. However, the minimum 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 m3
o .
Milne et al. [5] tabulated the tar tolerance limit
for various end use devices, suggested by di3erent
researchers.
The present paper discusses the strategies for tar removal 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
gasi cation. A direct comparison of the data avail-

LHC
mo3
PAH
RDF
SB

light hydrocarbons
normal cubic meter
polycyclic aromatic hydrocarbon
refuse derived fuel
steambiomass ratio; H2 O=biomass
[(kg h1 ) (kg daf h1 )1 ]

able for tar in the literature, is very diKcult because


of the following reasons; use of di3erent operating
conditions, di3erent type of gasi er used, di3erent tar
capturing, sampling and analysing method, and most
importantly the non-consistency in de ning tar used
by various researchers. Detailed discussion regarding
the tar de nition, 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 reported in the literature. A major part of ongoing research deals with the development of eKcient methods for tar removal in an economical and optimized
way. There are some sophisticated options available,
which have claimed to reduce tar amount signi cantly.
However, the method must be eKcient in terms of tar
removal, economically feasible, but more importantly,
it should not a3ect the formation of useful gaseous
products. All the methods available can be categorized
in two types depending on the location where tar is removed; either in the gasi er itself (known as primary
method) or outside the gasi er (known as secondary
method). The following sections describe both methods with emphasis on the primary method.
2.1. Secondary methods
Secondary methods are conventionally used as
treatments to the hot product gas from the gasi er.
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) 125 140

Tar
Removal

Syn. gas
Biomass

127

Tar free gas

Application

Gasifier
+ Tar
Gas
Cleanup
Air/Steam/O2
Downstream Cleaning
(Tar; Dust; N, S, halogen compounds)

Fig. 1. Tar reduction concept by secondary methods.

Gasifier
+

Application

Tar free gas

Biomass

Gas cleanup

Tar Removal

Air/Steam/O2

Dust

N, S, halogen Compounds

Fig. 2. Tar reduction concept by primary method.

as follows

2.2. Primary methods

tar cracking downstream the gasi er either thermally or catalytically,


mechanical methods such as use of cyclone, baOe
lter, ceramic lter, fabric lter, rotating particle
separator, electrostatic lter and scrubber.

Primary methods can be de ned as all the measures taken in the gasi cation step itself to prevent
or convert tar formed in the gasi er. An ideal primary 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 gasi er performance has to be optimized. For an optimized
performance of the gasi er, the main attractive factors
are the design and the operation of the gasi er. Corella
et al. [9] mentioned that in-bed use of dolomite results
in a similar tar content as using it in downstream catalytic reactor. If the gasi er bed is well designed and
operated, the measures taken during the gasi cation
step can produce a very clean gas with respect to the
end user application, eliminating the use of downstream 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 gasi cation, and (c) a proper gasi er design.

Although, downstream gas cleaning methods are reported to be very e3ective in tar reduction, in some
cases they are not economically viable. In addition,
several researchers reported secondary methods to be
very e3ective 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 process. NarvPaez 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].

128

L. Devi et al. / Biomass and Bioenergy 24 (2003) 125 140

2.2.1. Gasi5cation conditions


The operating conditions play a very important
role during biomass gasi cation in all respects, such
as carbon conversion, product gas composition, tar
formation and tar reduction. The most important inIuencing 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 depends on the type of gasi er used. A homogeneous
bed temperature pro le and a well-functioning bed
Iuidization are of utmost importance to avoid disturbances in the operation of a Iuidized-bed gasi er.
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
gasi er is preferred. To produce a relatively clean
gas by increased temperature, several temperature
ranges are reported in the literature. The present paper cites only a few of these works. Temperature not
only a3ects the amount of tar formed, but also the
composition of tar by inIuencing the chemical reactions involved in the whole gasi cation network.
Kinoshita et al. [10] observed during sawdust gasication in a xed bed gasi er that the total number
of detectable tar species decreased with increasing
temperature. Oxygen-containing compounds such as
phenol, cresol and benzofuran exist in signi cant
quantities only at temperature below 800 C. They also
con rmed that higher temperature favour the formation of fewer aromatic tar species without substituent
groups such as benzene, naphthalene, phenanthrene,
etc. Destruction of these aromatic hydrocarbons occurs 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 e3ect 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 formation 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 gasi cation 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 l1 ) and in naphthalene
contents (from 2 to 8 mg l1 ), when the temperature was raised from 700 C to 900 C. By changing
the bed temperature of the bubbling Iuidized bed
from 700 C to 850 C, NarvPaez et al. [13] observed
an increase in H2 content from 5 to 10 vol%, CO
content from 12 to 18 vol%, slight decrease in CO2
content from 16 to 13 vol% and almost no change
in the amount of CH4 and C2 H2 . They observed a
drastic decrease in tar content (about 74% less); the
tar amounts being 19 g m3
at 700 C and 5 g m3
o
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 Iuidized-bed gasiers [13,14]. Besides tar, temperature also inIuences
the formation of NH3 and N2 . The level of these two
species in the product gas largely depend on the thermochemical reactions occurring in the gasi er and
these reactions are directly related with temperature.
Zhou et al. [15] reported almost 58% decrease in NH3
content when the temperature was raised from 700 C
to 900 C for sawdust gasi cation. Over the same
temperature range, NO and HCN were also detected,
but at a much lower level than NH3 . For leucaena
gasi cation, an 80% decrease in NH3 content is reported when the gasi er 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 NH3 [15].
However, there are several other factors that limit
the operating temperature. Hallagren [16] mentioned
a typical temperature range for di3erent feed materials with respect to various critical factors that largely
inIuences the entire gasi cation 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 gasi cation. Knight [17] investigated the effect of system pressure for biomass gasi cation. When
the pressure was increased to 21:4 bar, almost complete elimination of phenols was observed for wisconsin whole tree chips. Although the amount of total
tar decreased, the fraction of PAH increased with increasing pressure. Moilanen et al. [18] studied the

L. Devi et al. / Biomass and Bioenergy 24 (2003) 125 140


Higher

Higher

Lower

Lower

Char conversion

Higher

Sintering

700 O C

Decreasing risk

Gas heating value


Tar content

800 O C

Agro

RDF

fuels

129

Lower

Increasing risk

9 00 O C

1000 O C

Woody

Coal

Biomass

Fig. 3. Typical gasi cation temperature for various feedstock and inIuence of temperature change on some critical factors as reported by
Hallgren [16].

dependence of pressure on wood char gasi cation. The


pressure was raised from 1 to 15 bar of CO2 and H2 O
at temperatures of 750 C and 850 C. Increase in CO2
pressure slightly reduced char gasi cation whereas
this increased with increasing H2 O pressure. Pressurized gasi cation (5 20 bar) is also being investigated
in the Lund University [19,20]. Wang et al. [19] observed 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
gasi cation with 100% carbon conversion.
Di3erent gasifying agents such as air, steam,
steamoxygen and carbon dioxide have been reported
in the literature. Selectivity of the gasi cation reactions varies with di3erent gasifying media, thus
a3ecting 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. NarvPaez et al. [13] reported
a gas composition of 10% H2 , 14% CO, 15% CO2
(vol%) from a gasi er with gasi cation 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 m3
o . The ER strongly inIuences the type
of gasi cation 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 Iaming pyrolysis zone.
This e3ect of ER is more signi cant at higher tem-

perature. The ER is very crucial because its higher


value results in lower concentration of H2 , CO and
higher CO2 content in the product gas, thus decreasing 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. NarvPaez et al. [13] reported a similar trend
with increasing ER for gasi cation of pine sawdust
at 800 C. A tar content of about 27 g m3
o was reported 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 signi cantly inIuence the
concentration of nitrogenous products during biomass
gasi cation. A slight increase in NH3 (from 310 to
350 ppm) was observed when the ER was increased
from 0.25 to 0.37 at 800 C for sawdust gasi cation.
In view of lower heating value as well as poor gas
composition, several researchers used pure steam and
they observed a completely di3erent product gas distribution. The steam gasi cation product is more or
less free from N2 and more than 50% H2 in the product gas. Herguido et al. [21] reported steam gasi cation and the e3ect of steam/biomass ratio (SB) on the

130

L. Devi et al. / Biomass and Bioenergy 24 (2003) 125 140

gasi cation products. They observed an increase in


H2 (as high as 60%) and CO2 (from 10 to 30%) contents, a sharp decrease in CO (from 35 to 10%) content, a slight decrease in CH4 content and relatively
no change of C2 -fractions (C2 H2 ; C2 H4 ; C2 H6 ) 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. GarcPSa 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 H2 production during steam gasi cation
can be attributed by the following chemical reactions:
Cn Hx + nH2 O (n + x=2)H2 + nCO;

(1)

CH4 + H2 O  3H2 + CO;


0
TH298
= +205:81 kJ mol1 ;

(2)

C2 H4 + 2H2 O  4H2 + 2CO;


0
TH298
= +210:07 kJ mol1 ;

(3)

CO + H2 O  H2 + CO2 ;
0
TH298
= 41:16 kJ mol1 ;

(4)

C + H2 O  H2 + CO;
0
TH298
= +131:29 kJ mol1 :

(5)

The rst reaction represents tar reforming reaction


which contributes to increment in the content of H2
and CO gases.
Steam gasi cation is endothermic and hence sometimes 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
gasi cation and then the gasi er works as an autothermal reactor. In view of that, many researchers
used steamoxygen mixtures for biomass gasi cation.
Aznar et al. [24] reported more than 85% reduction in
total tar when they increased the (steam+O2 )/biomass
ratio termed as gasifying ratio (GR) from 0.7 to 1.2.
The researchers also reported that for low GR values in the gasi er produces light tars which can be
easily destroyed using catalyst [25]. Gil et al. [26]
recommended H2 O=O2 ratio of around 3.0 (mol/mol)

for steamO2 mixture for gasi cation. When the GR


was increased from 0.6 to 1.7, they observed the following changes in gas composition, decrease in H2
content from 29% to 13%, decrease in CO content
from 50% to 30%, increase in CO2 content from 14%
to 37%, slight decrease in CH4 content from 7% to
5% and a change in C2 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 m3
o at a GR of 1.2. The same
researchers also observed that the e3ect of gasi er
bed temperature on tar content is signi cant at lower
GR values ( 1:0). They recommended a gasi er
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 NarvPaez 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 steamO2 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 gasi ers used were di3erent in
design. Hofbauer et al. [28] and Fercher et al. [29]
reported use of a combination of steam and air in a
fast internally Iuidized bed biomass gasi er which
is explained in the following section of this paper.
Air combustion provided the heat required for steam
gasi cation.
The use of CO2 as gasifying medium is promising
because of its presence in the gasi cation atmosphere.
Tar reduction is also enhanced by dry reforming reactions of CO2 , which is a gasi cation product. According to Minkova et al. [30], a mixture of steamCO2
gives highest degree of carbonization for pyrolysis and
gasi cation of biomass in a horizontal rotating reactor.
They also mentioned that a steamCO2 mixture produced the highest activity char, which resulted in high
ash content. GarcPSa et al. [31] investigated CO2 gasi cation in the presence of Ni/Al coprecipitated catalyst
and compared the results with those of steam gasi cation [22,23]. CO2 gasi cation in the presence of a catalyst transformed tars and also causes a decrease of the
amounts of CH4 and C2 -fraction (C2 H2 ; C2 H4 ; C2 H6 )
as well as an increase in H2 and CO yields. Also, a

L. Devi et al. / Biomass and Bioenergy 24 (2003) 125 140

signi cant decrease in the CO2 content was observed


with a CO2 /biomass ratio of 1.16 indicating that CO2
itself converts to other products. Deposition of carbon
in the catalyst particles can be avoided to a certain
extent by feeding CO2 in excess. The main chemical
reactions with CO2 as gasifying medium are listed
below:
Cn Hx + nCO2 (x=2)H2 + 2nCO;

(6)

CH4 + CO2  2H2 + 2CO;


0
TH298
= +246:98 kJ mol1 ;

(7)

C2 H4 + 2CO2  2H2 + 4CO;


0
TH298
= +292:41 kJ mol1 ;

(8)

CO2 + H2  CO + H2 O;
0
= +41:16 kJ mol1 ;
TH298

(9)

CO2 + C  2CO;
0
TH298
= +172:46 kJ mol1 :

(10)

Reaction (6) represents dry reforming reaction of tar.


According to Kinoshita et al. [10] residence time
has little inIuence on the tar yield, but it signi cantly
inIuences the tar composition. The residence time
they reported was based on the super cial velocity
of the wet product gases in the gasi er. Amounts of
O2 -containing compounds tend to decrease with increasing residence time. Yields of 1- and 2-ring compounds (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 gasi cation with in-bed
use of dolomite. The space time was expressed as
(kg calcined dolomite (kg biomass daf h1 )1 ). The
tar amounted 2 g m3
at space time 1.0 which was
o
at
a
space
time
of 0.1.
6 g m3
o
In addition to the optimized operational conditions,
presence of some active materials in the gasi er can
largely improve the product gas distribution. The following section covers some of the reported literature
on use of bed additives.
2.2.2. Bed additives
Catalytic tar reduction has been extensively reported in the literature [32]. These catalysts include

131

Ni-based catalysts, calcined dolomites and magnesites, zeolites, olivine and iron catalysts. Among all
these only few have been tried as active bed additive
inside the gasi er itself during gasi cation. 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 gasi er. The presence of additives not only inIuences the gas composition, but also the heating value
of the product gas. The use of catalytically active materials during biomass gasi cation promotes the char
gasi cation, 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
gasi er to improve the gasi cation. Walawender et al.
[33,34] performed series of experiments using limestone as bed additive in a Iuidized bed gasi er. They
used a mixture of 25 wt% limestone and 75 wt% silica
sand as a bed material for steam gasi cation of alpha
cellulose with an intention of predicting the behaviour
of the gasi er with increase in temperature [33]. The
researchers also applied the same mixture of bed material for steam gasi cation 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 inIuenced 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 agglomeration 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 demonstration of biomass IGCC process (VEGA Gasi cation with combined cycle) which involved dolomite
as bed material. The tar content observed was about
12 g m3
o of light tars (excluding benzene) and 100
300 mg m3
a et al. [36] also
o of heavy tars. RapagnV
mentioned the use of calcined dolomite directly in
the gasi er and observed improvements in the gas
yield. Corella et al. [37] reported that the use of calcined dolomite inside the gasi er could decrease the
tar amount from 6.5 (without dolomite) to 1:3 wt%.

132

L. Devi et al. / Biomass and Bioenergy 24 (2003) 125 140

The two research groups in Spain (University of Complutense and University of Saragossa) have done several experiments with in-bed use of dolomite. NarvPaez
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% calcined dolomite to biomass feed. A 10 wt% of calcined
dolomite is reported to be suKcient by Olivares et al.
[38] for signi cant 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 di3erence in
the lower heating value of the gas produced by using in-bed dolomite and that of downstream use of
dolomite. The increase in H2 production compensated
the CO decrease; also there was hardly any variation
in the CH4 and C2 Hn amounts in the product gas. The
tar content in the product gas with the use of in-bed
dolomite was signi cantly reduced and this reduction 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 section of this paper. An amount of 20 30 wt% dolomite
(rest being silica sand) in the gasi er was reported to
reduce the tar content as low as 1 g m3
at an ER
o
of 0.3 [14]. The authors also studied the inIuence 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 signi cantly
enhance production of a clean gas. Although dolomite
has been proven to be a very e3ective 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 production of nes. So, there is a great problem of carry over
of solids from the bed.
An alternative of dolomite can be naturally occurring particles of olivine, which is a mineral containing
magnesium, iron oxide and silica. Olivine is advantageous in terms of its attrition resistance over that of
dolomite. RapagnVa et al. [39] investigated the catalytic
activity of olivine and observed that it has a good performance 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
3
amounted 2:4 g m3
o compared to 43 g m 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 combined action of the materials was very promising; a
gas with around 0:3 g m3
o of tar was produced [40].
RosPen et al. [41] reported the use of olivine as a bed
material for pressurized gasi cation (0.4 1:0 MPa) of
birch.
Mudge et al. [42] studied the catalytic steam
gasi cation of biomass using alkali carbonate and
Ni-based catalyst at the Paci c Northwest Laboratory
(PNL). Supported Ni catalysts were found to be very
e3ective in producing high yields of synthesis gas
[42,43]. Baker et al. [44] studied a number of catalysts (Ni=Al2 O3 ; K2 O3 ; NiCuMo=SiO2 Al2 O3 ) for
pressurized steam gasi cation of bagasse and wood
to produce synthesis gas for methanol and ammonia
production in a laboratory-scale gasi er. The catalytic
gasi cation resulted in increase in the gas yield at
the expense of tar and char. They also carried out
gasi cation tests in a 1-t d 1 Iuidized-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
V2 O5 , Cr 2 O3 ; Mn2 O3 ; Fe2 O3 , CoO, NiO, CuO, MoO3
on Al2 O3 were tested by Yoshinori et al. [45] for
wood gasi cation 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. MoO3 , CoO and V2 O5
produced higher amount of CO2 , whereas NiO, Cr 2 O3
and Fe2 O3 produced relatively low amounts of CO2 .
The most suggested favourable gasi cation catalyst
was NiO=Al2 O3 , which could produce a gas with a
H2 =CO ratio close to 2.0, also observed to produce
only traces of total ole ns. 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. Several 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 considerable decrease in the methane content. The same

L. Devi et al. / Biomass and Bioenergy 24 (2003) 125 140

Ni/Al coprecipitated catalyst was also observed to be


very e3ective for CO2 gasi cation of biomass [23] The
ratio of catalyst weight and biomass Iow rate signi cantly inIuences 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 H2 S. These problems 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 option. 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 gasi er. Placing the NiCuMo on SiAl2 O3 and Ni
on -alumina catalysts in a secondary Iuidized-bed
reactor downstream the gasi er, they observed no deactivation for 30 40 h tests.
Ni-based catalysts are also very e3ective for NH3
reduction. Wang et al. [47] reported that NH3 can
be decomposed e3ectively with an Ni-based catalyst
above 800 C. Wang and his coworkers [50] reported
95% conversion of NH3 along with 89% conversion
of light hydrocarbons, which they de ned as C2 H6 ,
C6 H6 ; C7 H8 and C9 H8 , 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 e3ect on NH3 decomposition. Mojtahedi et
al. [51] investigated Ni/alumina and Ru/alumina catalyst for NH3 decomposition in a synthesis gas mixture. The same catalysts were studied for ammonia
and tar decomposition in an actual biomass gasi cation system [6]. These catalysts are less e3ective in
terms of NH3 reduction in the presence of tars. Simell
et al. [7] also observed that Ni/alumina catalyst is effective for NH3 as well as tar reduction. The authors
observed that NH3 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 NH3 decomposition were carried
out in external reactors as secondary treatment of the
hot gas from the gasi er.
Douglas et al. [52] used 8 wt% potassium carbonate as bed additive impregnated on wood for steam
gasi cation in a Iuidized bed gasi er 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,

133

especially potassium, act as a promoter in unzipping


the cellulose chains during the thermal decomposition
of woody biomass, thus e3ecting the product gas
distribution.
Corella et al. [37] also reported the use of
in-equilibrium FCC catalyst as bed additive for steam
gasi cation of pine sawdust. This catalyst contained
zeolite in a silicaalumina matrix, and was once used
from oil re neries. The experiment was done by feeding the catalyst to biomass feed (biomass=FCC = 10)
and 20% reduction in tar content was reported. However, 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
(800 820 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 gasi er itself. Char
has been reported to be used in secondary tar cracking
reactors by several researchers [53,54]. Chembukulam et al. [55] reported that cracking over a char bed
at a temperature of 950 C resulted in almost complete decomposition of tar and pyroligneceous liquor
into gases of low calori c value. It should be noted
that char itself gets converted during the gasi cation
process, and hence there may be need of external
continuous supply of char into the gasi er. Several
researchers reported use of char in two-stage gasier which is explained in the next section of this
paper.
Based on the reported literature, the following general observations can be made with the addition of
active bed material during gasi cation
1.
2.
3.
4.

a change in product gas distribution,


a decrease in tar amount,
an increase in hydrogen production,
a slight decrease in the amount of CO and increase
in the amount of CO2 ,
5. an almost no variation in the amount of CH4 ,
6. problems regarding catalyst deactivation and
carryover of nes were severe,

134

L. Devi et al. / Biomass and Bioenergy 24 (2003) 125 140

Table 1
In-bed additives used by researchers under di3erent operating conditions

Feed

Feed properties

Operating conditions

Moisture (%)

Size (mm)

Gasif. agent

Temp ( C)

Time (s)

Cellulose
Wood
Pine sawdust

8.5

1.0 2.0

1.0

Steam
Steam
Steam

600 800
750
750

1.26 1.54

Pine
Pine
Pine
Pine
Pine
Pine

10 25
10 12
10
10

10 15

4.0 0.8
5.0 1.0

Air
Steam=O2
Steam
CO2
Air;steam/O2
Air

800
795 835
700
700
800 850
800 845

0.6

0:4

Almond shell

7.9

1.1

Steam

770 820

Birch

6 8

1.0 3.0

O2 N2

700 900

Pine/bagasse

Steam

750

30

sawdust
chips
sawdust
sawdust
chips
chips

7. catalytic tar reduction depends on gasi cation


conditions.
A summary of some of the research work done using
bed additives is given in Table 1.
2.2.3. Gasi5er design modi5cation
Reactor design is very crucial for gasi cation in
terms of eKciency, heating value of the product gas
and also for tar formation. Modi cation of the gasi er
design can be very e3ective 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 gasi er results in a
signi cant tar reduction. A higher temperature could
be attained due to the secondary air injection in the
gasi er. Pan et al. [56] injected secondary air just
above the biomass feeding point in the Iuidized bed.
They reported that an optimal secondary to primary
air ratio of about 20% is suKcient to reduce 88:7 wt%
of the total tar for a gasi cation temperature range of
840 880 C. NarvPaez et al. [13] performed few experiments with secondary air injection in the freeboard
of Iuidized-bed gasi er. They observed a temperature rise of about 70 C and a tar reduction from 28 to
16 g m3
o . They expected that with longer size gasi-

Additive

Reference

Limestone
K2 CO3
Dolomite
FCC
Dolomite
Dolomite
NiAl
NiAl
Dolomite
Dolomite
FCC
Olivine
Dolomite
Silver sand
Olivine
Ni-based

Walawender et al. [33]


Douglas et al. [52]
Corella et al. [37]
NarvPaez et al. [13]
Olivares et al. [38]
Bilbao et al. [46]
GarcPSa et al. [23]
Corella et al. [9]
Gil et al. [14]
RapagnVa et al. [39]
RosPen et al. [41]
Baker et al. [44]

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 gasi er design has been reported to
be very e3ective in producing clean gas. The basic
concept of this design is to separate the pyrolysis
zone from the reduction zone. A two-stage gasi er is
equivalent to two single-stage gasi ers. Tars formed
during the pyrolysis ( rst stage) are decomposed in
the reduction zone (second stage). A two-stage gasier has been studied in the Asian Institute of Technology (AIT), Thailand, and it resulted in a gas of tar
content about 50 mg m3
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 represents the two-stage gasi cation 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 gasi er with a bed of char just above the
primary air inlet. The gasi er was loaded with char
before ignition. It was reported that char lling almost totally eliminates tar formation during start-up
in the reactor. Further modi cation was done by

L. Devi et al. / Biomass and Bioenergy 24 (2003) 125 140

135

Biomass Feed

Gasifier

Pyrolytic zone
Pyroly
(1 st stage)

Primary air

Pyrolysis gas ,Tar


Pyrolysis gas ,Tar

Reduction zone
nd stage)
(2nd
(2
stage)

Secondary air

Tar free gas

Fig. 4. Two-stage gasi cation concept (Asian Institute of Technology, Thailand).

Bhattacharya et al. [57] in such a way that char was


produced inside the gasi er itself, thus avoiding input
of external charcoal for subsequent experiments. For
this purpose, an extra primary air inlet above the original air supply was added. The researchers coupled the
char gasi er with the original two-stage gasi er and
reported that this design could produce considerably
low tar content (19 mg m3
o ) producer gas.
Successful operation of this type of gasi er 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 Iame
propagation. If the wood particles move faster than
the Iame propagation, the pyrolysis zone reaches the
second air intake thus making the whole system to act
like single-stage gasi er. If Iame propagation upward
exceeded wood consumption, both stages remained in
stable operation. The Iame propagation control was
done by adjustments of the airIow by changing the
width of the second air inlet.
Another two-stage gasi er designed at the Technical 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 gasi er (Technical University of Denmark).

et al. [58] reported the successful demonstration of


this type of gasi er (50 kW) for straw gasi cation.
Brandt et al. [59] also mention the same reactor design
(100 kW) for gasi cation of wood chips. The char
and the volatile pyrolysis products from the pyrolysis
unit entered the top of the gasi cation unit where the
gases were mixed with the preheated steam and air
starting partial combustion. The char is transported to
the char gasi cation unit. Allowing the gases to pass
through the bed of char, signi cant tar reduction in
the total tar content (15 mg m3
o ) has been reported.
Lower amounts of tar are attributed to the partial
combustion of the pyrolytic gases as well as the catalytic e3ect of the charcoal bed. The char conversion
was measured to be 70 90%.
Susanto et al. [60] developed a cocurrent moving
bed gasi er with internal recycle and separate combustion zone of pyrolysis gas. Their aim was to produce a design suitable for scaling up a downdraft gasier 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 m3
o . This gasi er 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 precombustion chamber. The Iue gas from this chamber then acts as the gasifying medium for the gasi er.

136

L. Devi et al. / Biomass and Bioenergy 24 (2003) 125 140


Biomass
Recycle
gas

Flue Flue
gas 2 gas 1

Char

Counter-current
Reduction zone
Remaining

Injector

(From
reduction
zone)

Char

Injected gas

Drying +
Pyrolysis zone

Gasifier

to gasify the remaining char in the second reduction


zone, thus providing more complete gasi cation. The
main cause reported by the researchers for tar reduction in such design is due to the fact that the tar Iow
is premixed with air prior to combustion and all tars
must pass through hot Iame. Also they mentioned that
any tar that might have escaped from the hot combustion chamber is subsequently converted over the char
in the combustion zone. A recycle ratio of 0.6 0.9 is
suggested to be optimal with regard to clean gas production as well as good gasi cation eKciency.
Several attempts have been made to develop new
Iuidized gasi cation techniques in view of better
eKciency as well as quality fuel gas. A two-stage
Iuidized gasi er which is a fast internally circulating Iuidized-bed gasi er (FICFB), was reported and
observed to produce a gas with higher calori c value
and nearly free of N2 [28,29,61]. This gasi er concept
is shown in Fig. 7. The Iuidized-bed gasi er was divided into two zones, a gasi cation zone with steam
as the Iuidizing 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 gasi cation zone. The
biomass is fed into the gasi cation zone and the bed
material together with char produced circulates to the
combustion zone. In the combustion zone the charcoal

Air

Combustor

Flue gas
Recycle gas=
Volatile +
Injected gas

Co-current
Reduction zone
Product gas

Fig. 6. Moving-bed gasi er with internal recycle.

The Iue gas is divided into two parts, one part being fed to rst reduction zone. This recycle gas Iows
countercurrently with the solid feed and char, thus enabling a more complete pyrolysis of the solids upon
entering the reduction zone. The second part is sent

Flue gas

Product gas

Bed material, char

Combustion
Zone

Heat

Gasification
Zone

Air

Biomass

Steam

Bed material

Gasifier
Fig. 7. Fast internally circulating Iuidized-bed gasi cation concept.

L. Devi et al. / Biomass and Bioenergy 24 (2003) 125 140

Biomass

Tar free

Gasification
+
Primary
Methods

Pre
Treatments

Secondary
Method

gas

137

Clean

Gas
Cleanup

Application
gas

Optional

Milling
Drying

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

Fig. 8. Tar removal approach in biomass gasi cation.

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 m3
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 e3ect of olivine particles in the same gasi er. The addition of olivine decreases the tar content of the product gas, but also it
depends on the gasi cation temperature. A total tar
amount of about 0:5 g m3
was observed for wood
o
gasi cation with olivine at a temperature of 800 C.
3. Remarks and conclusion
An optimized gasi cation 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 gasi er 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 (specially temperature, gasifying medium, ER and residence time) can simplify the entire gasi cation chain.
2. Addition of some active bed materials has been
proven to be e3ective. But there are a number of factors 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 modi cations made in the gasi er design
must be easily implementable. Most of the attempts
made to modify the gasi er design claimed to produce
a clean gas. Moreover, few factors should be kept
in mind while designing the entire gasi cation 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 gasi cation chain highly depends on the
end-use applications. The rst step for process selection for biomass gasi cation 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 importance for the gasi cation chain as a whole, but they
cannot solve the purpose of tar reduction without effecting the useful gas composition and heating value.
Combination of proper primary measures with downstream methods is observed to be very e3ective in all
respect. More research is required for developing an
eKcient primary technique (combination of optimal
operational parameters, bed additives and reactor design) which would be suKcient to produce a clean

138

L. Devi et al. / Biomass and Bioenergy 24 (2003) 125 140

gas and eliminating the need of downstream tar removal techniques. Also, more attention must be paid
to reduce other contaminants such as NH3 , HCN, HCl,
H2 S, etc. in combination with tar reduction.

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