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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
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
Nomenclature
Daf
ER
FCC
GR
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 ]
Tar
Removal
Syn. gas
Biomass
127
Application
Gasifier
+ Tar
Gas
Cleanup
Air/Steam/O2
Downstream Cleaning
(Tar; Dust; N, S, halogen compounds)
Gasifier
+
Application
Biomass
Gas cleanup
Tar Removal
Air/Steam/O2
Dust
N, S, halogen Compounds
as follows
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
Higher
Lower
Lower
Char conversion
Higher
Sintering
700 O C
Decreasing risk
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].
130
(1)
(2)
(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)
(6)
(7)
(8)
CO2 + H2 CO + H2 O;
0
= +41:16 kJ mol1 ;
TH298
(9)
CO2 + C 2CO;
0
TH298
= +172:46 kJ mol1 :
(10)
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
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
133
134
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
Additive
Reference
Limestone
K2 CO3
Dolomite
FCC
Dolomite
Dolomite
NiAl
NiAl
Dolomite
Dolomite
FCC
Olivine
Dolomite
Silver sand
Olivine
Ni-based
135
Biomass Feed
Gasifier
Pyrolytic zone
Pyroly
(1 st stage)
Primary air
Reduction zone
nd stage)
(2nd
(2
stage)
Secondary air
136
Flue Flue
gas 2 gas 1
Char
Counter-current
Reduction zone
Remaining
Injector
(From
reduction
zone)
Char
Injected gas
Drying +
Pyrolysis zone
Gasifier
Air
Combustor
Flue gas
Recycle gas=
Volatile +
Injected gas
Co-current
Reduction zone
Product gas
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
Combustion
Zone
Heat
Gasification
Zone
Air
Biomass
Steam
Bed material
Gasifier
Fig. 7. Fast internally circulating Iuidized-bed gasi cation concept.
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
138
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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140