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Bioresource Technology 101 (2010) 71237130

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Gas cleaning, gas conditioning and tar abatement by means of a catalytic


lter candle in a biomass uidized-bed gasier
Sergio Rapagn a,*, Katia Gallucci b, Manuela Di Marcello a, Muriel Matt c, Manfred Nacken d,
Steffen Heidenreich d, Pier Ugo Foscolo b
a

Dipartimento di Scienze degli Alimenti, University of Teramo, 64023 Mosciano S. Angelo, Teramo, Italy
Dipartimento di Chimica, Ingegneria Chimica e Materiali, University of LAquila, Via Campo di Pile Ex Optimes, 67100 LAquila, Italy
LCME EA4164, University of Metz UFR SciFA, 1 Bd Arago, 57078 Metz Cedex 3, France
d
Pall Filtersystems GmbH, Werk Schumacher, D-74564 Crailsheim, Germany
b
c

a r t i c l e

i n f o

Article history:
Received 19 January 2010
Received in revised form 30 March 2010
Accepted 31 March 2010
Available online 21 April 2010
Keywords:
Biomass gasication
Ni catalyst
Ceramic lter candles
Fluidized-bed
Tar analysis

a b s t r a c t
A bench-scale uidized-bed biomass gasication plant, operating at atmospheric pressure and temperature within the range 800820 C, has been used to test an innovative gas cleaning device: a catalytic lter candle tted into the bed freeboard. This housing of the gas conditioning system within the gasier
itself results in a very compact unit and greatly reduced thermal losses. Long term (22 h) tests were performed on the gasier both with and without the catalytic candle lter, under otherwise identical conditions. Analysis of the product gas for the two cases showed the catalytic ltration to give rise to
notable improvements in both gas quality and gas yield: an increase in hydrogen yield of 130% and an
overall increase in gas yield of 69% with corresponding decreases in methane and tar content of 20%
and 79%, respectively. HPLC/UV analysis was used to characterize the tar compounds.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
The anticipated increase of fossil fuel prices and in particular
the perceived threat to the environment brought about by the
accumulation of greenhouse gases in the atmosphere has resulted
in a fundamental review of energy policies over the last decade.
The great potential of biomass as a renewable and CO2 neutral
feedstock for energy production is now universally recognized.
Gasication is a technically mature thermal conversion process
for the production of combustible gases from solid fuels. Syngas
obtained in this way, appropriately conditioned and upgraded,
may be used for electricity generation by means of internal combustion engines, gas turbines, and (in the near future) fuel cells,
and also for the production of synthetic bio-fuels. Industrial plant
simplication and intensication could play an important role in
biomass applications in general and in particular in increasing
the feasibility of gasication processes.
Biomass steam gasication as a source of hydrogen and other
valuable gases provides a convenient energy vector for a wide
range of applications. The use of steam as a gasication agent gives
rise to an increase in fuel gas product yield as a result of reductions
* Corresponding author. Tel.: +39 0861266893; fax: +39 0861266915.
E-mail address: srapagna@unite.it (S. Rapagn).
0960-8524/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.03.139

in both tar and char brought about by the steam reforming processes (Rapagn et al., 2000). Hydrogen and carbon monoxide
and a signicant amount of methane, carbon dioxide, steam and
nitrogen are always present in the producer gas, together with organic (tar) and inorganic (H2S, HCl, NH3, and alkali metals) impurities and particulates. The organic impurities comprise a range of
low to high molecular weight hydrocarbons which condense under
ambient conditions. They are known collectively as tar (Li and
Suzuki, 2009). Tar deposits can block gas coolers, engine suction
channels and also interfere with the performance of catalysts used
in the production of synthetic bio-fuels. In all cases, the presence of
tar means lower gas yields (Bangala et al., 1997). The product content of these undesirable contaminants can be reduced by careful
control of the operating conditions (temperature, biomass heating
rate, etc.), appropriate reactor design and suitable gas conditioning
systems (Van Paasen and Kiel, 2004). Characterization and quantication of tar produced during a gasication process enables an
assessment to be made of the relative ease or difculty of destroying it (Corella et al., 2002). Classication of tar under ve group
headings based on its solubility and condensability rather than
reactivity has been proposed by Devi et al. (2005).
Fixed bed gasiers have been traditionally employed for smallscale energy production. Operated under downdraft conditions
these can give rise to a relatively low tar content in the product

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S. Rapagn et al. / Bioresource Technology 101 (2010) 71237130

gas, but present operative limitations with regard to the biomass


feed size and moisture content as well as scale-up difculties
(Gao et al., 2009). For direct heating applications and capacities below about 10 MW, xed bed updraft gasiers are popular because
of their good thermal efciency and ability to handle high moisture
content feed streams without the need for pre-drying; tar production for this conguration is high however higher than for all
other gasier types (Beenackers, 1999). Fluidized-bed gasiers
are well known for their excellent mixing characteristics and consequential high gassolid reaction rates; in addition they may be
operated under solid circulation conditions, allowing for the inclusion of separate reduction and oxidation zones while using steam
and air as gasication agents; such a conguration can result in a
gas with a relatively high heating value (1013 MJ/Nm3 of dry
gas) (Hofbauer and Knoef, 2005).
Gas cleaning systems may be used to reduce drastically the tar
and particulate components of the product stream. This step is
usually carried out by ltration and scrubbing of the producer
gas, involving reduction of the gas temperature to near ambient,
with a resulting loss of thermal efciency for subsequent power
generation purposes. This factor penalizes signicantly the overall
economic performance for green electricity generation from biomass. This has had the result of focusing attention on hot gas
cleaning techniques. Recent advances in this eld have been made
by the inclusion of one or more monolith converters at the gasier
outlet. Satisfactory performances for this application have been obtained but problems of rapid catalyst deactivation due to temperature reduction have been encountered (Toledo et al., 2006; Ising
and Gil, 2001).
It is worth mentioning here that additions to the plant scheme
to obtain a tar-free product signicantly contribute to the overall
investment cost. This is particularly the case for small-to-medium
scale gasication plants, which are those that best match the
requirements of most regions for a number of reasons: one being
the relatively high transportation cost of biomass, it being a dilute
energy source in comparison with fossil fuels; another concerns
the economic advantages of combined heat and power generation
(co-generation) for strictly local distribution; yet another is in response to the scarce social acceptability of large thermal conversion plants. All this points to biomass power plants that are
small and compact thereby minimizing investment and operating
costs.
A previous study has considered the inclusion of a catalytic lter within the biomass gasication reactor vessel (Heidenreich
et al., 2008; Rapagn et al., 2009). The object in this case was to obtain a particle-free syngas with the tight specication required for
its use in fuel cells in a cost-effective manner, and with the high
overall thermal efciency that is a consequence of the absence of
a cooling step in the gas cleaning process. Although a number of
studies are reported in the literature which deal with hot gas catalytic ltration (Engelen et al., 2003; Ma and Baron, 2008; Ma et al.,
2005; Simeone et al., 2010) its coupling with a real biomass gasication process has never been tested before.
The experimental tests of biomass steam gasication described
in this paper were carried out using a segment of a full industrial
size lter candle with an integrated xed bed of nickel catalyst
grains. This innovative device was placed in the freeboard of a
bench-scale uidized-bed gasier and operated over an extended
period of time. The activity of the catalyst was determined as a
function of time in order to evaluate its performance under real
gasication conditions. The gas product composition was monitored during each run and tar samples collected at the end of a
run were analyzed as described in the sections below. The global
tar content of the producer gas was evaluated as Total Organic Carbon (TOC) of the total condensate. Additional qualitative and quantitative determinations were performed by HPLC/UV analysis of

the tar sampled in accord with technical specication CEN/TS


15439. Liquid chromatography was used to follow the evolution
of aromatic hydrocarbons in the various samples recovered.
HPLC/UV is capable of analyzing a wide range of components that
are thermally labile, exhibit high polarity or have a high molecular
mass (i.e. GC/MS undetectable tar). Because the concentrations of
the chemical species of interest amount to a few mg/l, more sensitive techniques, such as GC/MS, were not considered necessary
(Rapagn et al., 2010).
2. Methods
2.1. Experimental rig
A description of the gasication facility available in our laboratory has been provided in previous papers (Rapagn et al., 2009;
Rapagn et al., 2010). The following remarks relate to the specic
arrangement and procedures adopted for the work presented here.
The bench-scale equipment consists essentially of a bubbling
uidized-bed gasier with an internal diameter of 0.10 and
0.85 m high (from the gas distributor to the exit pipe), externally
heated by means of a 6 kW electric furnace and modied to house
the ceramic lter candle in the freeboard (Fig. 1A). Fig. 1B shows
the main dimensions of the catalytic ceramic lter, of which the
effective ltration length is 394 mm and the total length is
478 mm. For all experimental runs no particles were observed to
emerge downstream of this lter.
The biomass feedstock consists of crushed almond shells with
an average particle size of 1054 lm and of proximate and elemental composition as reported in Table 1. It is delivered from the top
of the reactor by means of a continuous biomass feeder. Fig. 1C
shows a schematic view of the entire experimental rig. Three condensers in series are used to separate condensable components:
the rst, of stainless steel, is cooled with tap water; the remaining
two, of glass, are cooled with refrigerated diethylene glycol. Online gas analyzers (UV, IR and TCD) provide volume composition
measurements of H2, CO, CO2, CH4, NH3 and H2S. Temperatures
in various plant locations are measured by means of thermocouples, and measurement devices for the continuous monitoring of
ow rates and pressure drops are also provided. Steam is generated
from liquid water fed by means of a peristaltic dosing pump to a
cylindrical stainless steel evaporator housed in an electric furnace.
The uidized-bed consists of 3 kg of olivine particles (d = 306 lm,
q = 2500 kg/m3) provided by Magnolithe GmbH. When this is uidized by a mixture of steam and nitrogen at 810 C, the predicted
minimum uidizing velocity is about 0.05 m/s (Rapagn et al.,
1994); the values of the supercial gas velocity in the gasication
tests range from 0.10 to 0.19 m/s, well in the bubbling regime. The
bed height in these conditions is just above that at minimum uidization conditions (with Geldart Group B particles the only difference being the bubble holdup), i.e. about 0.3 m. The reliability of
these estimates has been conrmed by direct measurements at
ambient temperature.
2.2. Preparation of the ceramic lter with integrated catalytic xed bed
A commercial hot gas lter candle of the type DIA-SCHUMALITH with a particle separation efciency of 99.999% was further
developed to a catalytic lter candle by Pall Filtersystems GmbH
Werk Schumacher. This involves a porous inner tube allowing
the integration of catalyst grains as xed bed inside the ceramic lter candle. The advantage of such catalyst integration is the higher
exibility it provides for potential applications. Several tests previously performed on this type of lter element, using synthetic gas
mixtures, resulted in complete conversion of naphthalene at 800 C

S. Rapagn et al. / Bioresource Technology 101 (2010) 71237130

7125

Fig. 1. Scheme of the uidized-bed gasier with a catalytic lter candle in its freeboard (A). Main constituent parts and dimensions of the catalytic ceramic lter (B).
Schematic view of the whole experimental rig (C).

Table 1
Biomass proximate and ultimate analysis.
Proximate analysis
% wt./wt. (as received)
Dry matter
Ash
Volatile matter
Fixed carbon

Elemental composition
% wt./wt. (dried at 105 C)
92.3
1.1
71.7
19.5

C
H
N
O
Cl
S

48.9
6.2
0.18
43.5
0.029
0.026

even in presence of 100 ppmv of H2S, suggesting that this contaminant does not cause irreversible deactivation of the catalyst in the
lter candle (Nacken et al., 2009).
The Ni catalyst used in the present application was lled into
the hollow-cylindrical space of a 398 mm long thermo-shock resistant silicon carbide (SiC) based hot gas lter element of 60 mm
outer diameter and 40 mm inner diameter and a porous inner tube
of 20 mm outer diameter closed with a perforated ceramic cup at
the bottom of the lter element (Fig. 1B). The perforated ceramic
cup itself is sticked onto a dense cylinder as bottom end of the lter
element. After catalyst lling the upper end of the lter element
was closed with a second perforated ceramic cup. Additionally, a
standard hot gas lter candle head was sticked onto the upper

ceramic cup to be able to hang in the as-prepared catalytic lter


candle into a tube sheet and to x and seal it using hot gas gaskets.
The Ni catalyst was manufactured by incipient wetness impregnation of MgO grains of the size range 0.10.3 mm by using a nickel
nitrate hexahydrate solution to adjust a NiO loading of 6 wt.%
(Nacken et al., 2007).
2.3. Gasication conditions and method
For each experimental trial, the bed was rst uidized with air
and heated to the chosen operating temperature; the uidizing gas
was then switched to a nitrogen/steam mixture and after the system had stabilized (12 min) the biomass feed was started. Nitrogen was supplied to assist the smooth feeding of biomass particles,
to stabilize the ow and to adjust the face ltration velocity to
close to its nominal value (of about 2 cm/s). The overall gasication
conditions for the tests are reported in Table 2.
The biomass feed rate was kept constant throughout the test to
maintain a constant rate of gas production and to avoid pressure
uctuations that would disturb the system.
At the end of each test the carbonaceous residue formed in the
gasier was burnt in an air stream thereby enabling the quantity of
char produced during the gasication process to be determined by
analysis of the CO2 and CO in the exit gas all the while ensuring
that the reactor temperature during the char combustion process

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S. Rapagn et al. / Bioresource Technology 101 (2010) 71237130

Table 2
Gasication operating conditions.
Gasication test number

II

III

IV

VI

VII

VIII

IX

Duration of test (min)


Biomass ow rate (g/min)
Nitrogen ow rate (l/min)
Steam feeding rate (g/min)
Catalytic ltration candle

60
8.0
11.2
8.50
No

90
9.0
12.0
8.44
Yes

56
9.0
12.0
8.96
Yes

120
6.0
11.2
6.60
Yes

120
6.0
12.0
6.33
Yes

160
4.5
9.0
3.82
Yes

120
5.5
6.0
6.20
Yes

180
6.0
5.0
6.18
Yes

240
6.0
5.0
5.99
Yes

230
6.0
5.4
5.96
Yes

was kept below 800 C by diluting the air with nitrogen where necessary. Periodic thermal regeneration by coke combustion of the
catalytic lter candle is only applied in this validation test rig.
For the large-scale application, efcient back-pulsing is foreseen
for dust cake removal.
2.4. Determination of tar content by Total Organic Carbon analysis
The condensate fraction recovered in the Erlenmeyer asks at
the end of each gasication run was weighted and the tar content
estimated by measurement of the Total Organic Carbon (TOC),
using naphthalene as the key component. This was done on a representative sample that was rst ltered, using a 0.45 lm pore
sizes lter, and then diluted with high purity distilled water. The
TOC content was measured by injecting the sample in a Shimadzu
TOC-VCPN Total Organic Carbon analyzer, operating the complete
catalytic oxidation at 680 C.
2.5. Characterization and quantitative analysis of tars by HPLC/UV
The samples recovered in accord with technical specication
CEN/TS 15439 were used to characterize the aromatic tar components. About 1 ml of the tar samples were diluted 10 times with
2-propanol HPLC gradient grade (Fisher Scientic, Loughborough,
Leicestershire, UK) and centrifuged for 10 min at 2000 rpm. The
20 ll of the samples were then injected in a HPLC apparatus (Hitachi Elite LaChrom L-2130). The system was equipped with an
UV-detector (Hitachi UV-detector L2400) set at 254 nm. The column used to permit the chromatographic separation of the tar fraction was a reversed phase C18, 150  4.6 mm (Alltech Apollo C18
5 lm), protected with a guard column.
A gradient elution was carried out using methanol (Fisher Scientic, Loughborough, Leicestershire, UK) and water as mobile
phase, at a ow rate of 1 ml/min; pure standard compounds were
used in order to characterize the tar aromatic prole (Rapagn
et al., 2010).
3. Results and discussion
3.1. Gasication tests
The results of ten gasication runs are reported. Measurements
with (tests IIX) and without (test I) the catalytically active lter
candle in the gasier were performed; tests with the lter candle
were carried out consecutively in order to evaluate the catalyst
performance as a function of time. Altogether, the catalytic lter
candle was subjected to the gasication conditions for a total of
22 h. No damage to the candle and its ttings were found to have
occurred at the end of the trials.
The signicant parameters for each test, such as temperature,
gas yield, water conversion, composition of the puried syngas,
are given in Table 3. In all experiments, the steam:biomass mass
ratio was kept constant, and close to 1. The carbon mass balance
was checked for each test: in most catalytic gasication runs, the
ratio (C inC C out  100) is in the range of 2  3% (except tests IV and
in

V, where this value reached 8%). In test I (without lter candle),


the overall mass balance closes quite well (to within 7%), while
the average carbon balance shows that carbon measured in the
products (char, tar and gas) is 14% less than that in the feedstock:
it should be noticed here that when no lter candle is present in
the reactor freeboard, ne char particles may be elutriated from
the gasier thereby contributing to a reduction of the carbon quantities measured.
In Fig. 2A and B, the product gas composition, expressed as the
percentage by volume of H2, CO, CO2 and CH4, is reported as a function of gasication time. A comparison of data obtained using the
catalytic lter candle (Fig. 2B) with those obtained without it (test
I, Fig. 2A), reveals a substantial improvement of all the representative gasication criteria. This observation is valid for the entire test
campaign. Small uctuations in performance however were observed among tests and during each test. During the rst 90 min
of gasication in the presence of the catalytic candle test II
there is a strong reduction in methane and tar content (measured
by TOC analysis) in comparison with test I, these values decreasing
by 49% and 75%, respectively. This clearly results in an increase in
gas yield and hydrogen content (Table 3). As shown in Fig. 2B there
is a progressive increase in H2 concentration during the rst 5 h,
stabilizing in time to reach about 53% on a N2 free basis (tests
VIIIX): this represents an average enhancement of 36% over the
test I results.
The largest concentration of H2 was observed for tests IV and V,
with a percentage by volume of around 55% and with a consequential low concentration of methane. In comparison with test I, the
CH4 content decreases from 10.3% to 3.8%. The experimental tests
also show an interesting evolution in gas yield and the tar content.
For test V for example the gas yield obtained, 1.62 Nm3 dry/kg daf,
is mainly caused by increased reforming of tar brought about by
the catalyst, which shows a maximum in its activity. Tar content
in fact decreases from 0.79 to 0.55 g/Nm3. Increasing the gasication time beyond 6 h (tests VIX) shows a growing trend followed
by stabilization with regard to both the methane and tar content in
the product gas when compared with the previous results. Especially for methane, it is possible to observe how its concentration
increases and stabilizes at around 5%, suggesting that a minor decrease of the number of active sites has occurred resulting in a
slightly lower but stable activity. At the same time the gas yield increases due to an increased char conversion: evidently, there
seems to be a strong correlation between decreasing the face
velocity, and water as well as carbon conversion.
It is worth mentioning that in the blank test (test I) only 56% of
the hydrogen content of the biomass (62 g/kg daf) is found in the
producer gas as H2, while in each test with the catalytic candle
(tests IIX) this value greatly exceeds 100% as a result of enhanced
hydrocarbon reforming reactions with steam that in this way contributes additional H2 moles to the produced gas. A clear indication
of the outstanding reforming activity of the catalytic candle in the
gasier environment is obtained by comparing the experimental
values of steam conversion in each test with its theoretical maximum consumption at the conditions of the test calculated with
the assumption that methane, tar and char are completely absent
in the fuel gas and that thermodynamic equilibrium is attained

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S. Rapagn et al. / Bioresource Technology 101 (2010) 71237130

Table 3
Results of steam gasication tests with olivine bed inventory, without any lter element housed in the gasier (test I) or in presence of a catalytic lter candle (tests IIX).
Gasication test number

II

III

IV

VI

VII

VIII

IX

Reactor outlet temperature (C)


Gasier bed temperature (C)
Steam:biomass mass ratio
Water conversion (%)
Gas yield (Nm3 dry/kg daf)
Tar content (g/Nm3 dry)
Char residue (g/kg daf)
Carbon conversion (%)
H2 (vol.% dry gas, N2 free)
CO2 (vol.% dry gas, N2 free)
CO (vol.% dry gas, N2 free)
CH4 (vol.% dry gas, N2 free)
Filtration velocity (cm/s)

738
808
1.06
16.15
1.00
3.67
93.66
80.14
39.17
26.24
24.32
10.27
2.36

816
815
0.94
33.56
1.65
0.91
67.68
85.87
50.33
23.09
21.38
5.20
2.84

816
808
1.00
24.26
1.54
0.95
106.60
77.92
51.62
23.14
21.69
3.55
2.65

825
814
1.10
20.94
1.49
0.79
70.05
85.45
54.50
21.96
19.66
3.88
2.24

815
813
1.06
35.27
1.62
0.55
68.53
85.82
55.61
21.46
19.12
3.81
2.19

818
814
0.85
39.78
1.60
0.71
77.67
83.90
52.45
19.54
22.75
5.26
1.76

822
813
1.13
35.61
1.68
0.75
66.45
86.17
54.12
21.67
19.19
5.02
1.70

812
813
1.03
37.30
1.77
0.81
47.72
89.97
53.24
20.16
21.58
5.02
1.72

809
811
1.00
40.82
1.77
0.85
35.79
92.39
53.25
19.90
21.71
5.15
1.69

819
808
0.99
42.01
1.79
0.75
40.52
91.46
53.23
19.62
22.09
5.07
1.72

100

90
80

vol %, N2 free

70
60
H2

50
40
30

CO2

20

CO

10
CH4
0
0

500

1000

1500

2000
time (min)

2500

3000

3500

4000

100

B
90
II

III

IV

VI

VII

VIII

IX

80

vol %, N2 free

70
60
H2
50
40
30

CO

20
CO2
10
CH4
0
0

10

12
time (h)

14

16

18

20

22

24

Fig. 2. Product gas composition in % by volume (N2 free basis) as a function of gasication time, without any lter candle in the gasier (test I) (A), and with the catalytic lter
candle in the gasier freeboard (tests IIX) (B).

for watergas shift reaction. As shown in Table 4, the water conversion obtained experimentally is quite close to this limiting reference value in almost all tests with the catalytic candle. This is a
noteworthy result as low water conversion is often considered a
drawback for steam gasication.

Because methane reforming is a strongly endothermic process


there is a danger of signicant temperature reduction in the reactor freeboard. However, it has been checked that when this reaction takes place on the catalyst integrated in the lter candle, the
operating conditions are such that the adiabatic temperature

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Table 4
Water conversion achieved experimentally compared with the corresponding theoretical value.
Gasication test number

II

III

IV

VI

VII

VIII

IX

Theoretical value
Experimental value

43.19
16.15

46.10
33.56

44.74
24.26

42.31
20.94

43.29
35.27

45.72
39.22

43.78
35.98

43.89
37.30

44.63
40.82

44.80
42.01

Table 5
Percentage variation of the main gasication indicators, with respect to the blank test.

Gas yield (%)


Tar content in the produced gas (%)
Tar content per kg biomass daf (%)
H2 yield (%)
CH4 yield (%)
Total C in permanent gas phase (%)

Maximum value

Average value

+79
85
76
+143
47
+38

+69
79
64
+130
20
+30

decrease per unit time becomes negligible (about 1 C/min), even


for complete reforming of the methane: this is due to the signicant heat capacity of the ceramic candle that assures temperature
stability in the reactor freeboard.
In Table 5, the main results of the experimental program are
presented as percentage variations with the catalytic candle lter
in place over those obtained with the blank test. This shows the
catalytic lter to have given rise to an average increase in gas yield
of 69%, of hydrogen yield by 130% and of carbon atoms in the
permanent gas phase by 30%. Correspondingly, methane and tar

60

A
Pressure drop through the candle (cmH 2O)

50

40

30

20

10

0
0

2
Filtration velocity (cm/s)

60

B
Pressure drop through the candle (cmH 2O)

50

40

P at 2.2 cm/s, 800C, empty reactor

30

P at 1.7 cm/s, 800C, empty reactor

20

10

0
0

50

100

150

200

250

time (min)
Fig. 3. (A) Pressure drop across the catalytic lter candle with the reactor empty of particles; temperature levels: (d) 20 C, (h) 300 C, () 450 C, (s) 600 C, (N) 800 C. (B)
Pressure drop across the catalytic lter candle, as a function of time on test; average ltration velocity: (s) 2.25 cm/s test IV, (D) 2.19 cm/s test V, (d) 1.75 cm/s test VI,
(h) 1.72 cm/s test X.

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S. Rapagn et al. / Bioresource Technology 101 (2010) 71237130

conditions both on the empty system (with no powder in it) and,


as a function of time, during some of the gasication runs. These
results are reported in Fig. 3A and B respectively. From Fig. 3A it
is evident that the behavior of the catalytic lter candle containing
a xed bed of catalyst particles is similar to that reported for catalytic layer design (Rapagn et al., 2009); this is due to the presence
in both lters of a very thin outer mullite membrane where most of
the resistance to gas ow is located.
On removing the candle from the reactor at the end of a run
patches of a ne particle layer (particle diameter less than
45 lm) were found adhering to the outer ltration surface. It
should be recalled here that after each gasication run the char
accumulated in the bed is burnt in a current of air. This presumably
leads to the breaking up of the sticky particle layer built up during
the previous gasication step. Fig. 3B shows that for each gasication run the initial pressure drop is comparable to that measured,
under similar temperature and face velocity conditions, with the
system empty of powder (Fig. 3A). As time progresses, the pressure
drop increases almost linearly with time, with a gradient reecting
the growing thickness of the particle layer. The growing fraction of
nes in the bed as time progresses does not lead to a substantial
change in the pressure drop trend, indicating that the nes fraction
always remain below reasonable limits, and towards the end of the
nal test (test X) it appears that a pressure drop plateau is being
approached. These results agree with those of a parallel uid dynamic study carried out at room temperature to gather experimental evidence on fouling of a candle surface in a uidized-bed
freeboard (Di Carlo et al., 2009). Fig. 4 shows the catalytic ceramic
lter before and after the full 22 h of gasication trials.

Fig. 4. Catalytic ceramic candle before and after the whole gasication test (22 h).

content in the gas are seen to have been reduced by 20% and 79%,
respectively, and tar production by 64%. In addition, the ammonia
concentration in the producer gas was found to have been reduced
by an order of magnitude, from 500 ppmv in the blank test to an
average value of 50 ppmv with the catalytic candle providing further conrmation of the activity of the reforming catalyst. The
presence of H2S in the product gas was also monitored. In all the
biomass gasication experiments its concentration remained below that found to be of negligible signicance in the preliminary
activity studies of the catalytic lter (100 ppmv).

3.3. Tar analysis by HPLC/UV and comparison with TOC


At the end of each gasication run, tar sampled in 2-propanol
was analyzed as described earlier in order to characterize the aromatic molecules produced during the gasication process, and so
to better evaluate the catalytic action. The majority of peaks detected in the samples have now been identied and quantied
by external calibration. The results are reported in Fig. 5. The main
compounds are toluene and naphthalene. These light aromatics are
present in high concentration in test I (no catalytic candle); as observed, they drastically decrease when the catalytic lter candle is
used, due to the good tar reforming activity promoted by the nickel

3.2. Pressure drop through the catalytic lter candle


Pressure drop measurements through the lter candle in the
reactor freeboard were performed under various temperature

Aromatic hydrocarbons in the syngas, mg/Nm3 dry

1200

OH

Tol

Naph

Bph

Dpe

Fl

Phe

Anth

Flt

Pyr

800

400

II

IV

VII

VIII

IX

Fig. 5. Qualitative and quantitative analysis of tar produced during the gasication tests: phenol (uOH), toluene (Tol), naphthalene (Naph), byphenyl (Bph), diphenylether
(Dpe), uorene (Fl), phenanthrene (Phe), anthracene (Ant), uoranthene (Flt) and pyrene (Pyr).

7130

S. Rapagn et al. / Bioresource Technology 101 (2010) 71237130

stable, though with a slight reduction in methane and tar conversion. The tar content in the product gas has been evaluated using
two different and independent methods, TOC and HPLC/UV, showing good agreement and consistent results. The latter technique is
also proposed for tar characterization.

Tar content in the syngas, g/Nm dry

Acknowledgements

The authors acknowledge the nancial support of European


Contract Unique 211517. Manuela Di Marcello also acknowledges
the French-Italian University for her PhD grant.

References

0
I

II

IV

VII

VIII

IX

Fig. 6. Tar content values obtained using TOC (s) and HPLC/UV (d) analysis.

catalyst. The same behavior is observed for the heavier aromatics


(those with more than three aromatic rings). In tests IV and V it
was not possible to quantify these components due to their low
concentration.
The results of the HPLC/UV analytical determinations conrm
completely the evidence of catalyst activity arising from the gas
composition and TOC measurements discussed above. With regard
to the entire tar production trend throughout the 22 h on test, a
strong decrease of the aromatics concentration is observed during
the rst 6.5 h (tests IIV). In test V more than 90% of toluene and
naphthalene are reformed. For greater total gasication times
(tests VIX) a larger concentration of aromatics is observed: for
test IX, toluene and naphthalene decrease by 68% and 60% respectively from the values obtained in the blank test I (with no catalytic
candle). Gas yield and water conversion data, reported in Tables 3
and 4, suggest that in the later tests the experimental conditions
may have given rise to a somewhat lower availability of steam
thereby preventing further tar reforming. The total tar content nevertheless still remains very low. This conrms the constant performance of the catalyst during time.
Fig. 6, reports the tar content in the syngas downstream of the
lter candle. Data obtained by measurement of TOC in the water
condensate fraction are compared with the tar content obtained
by HPLC/UV (data on tests III and VI are not available). As shown,
tar concentrations obtained by both analytical methods follow
the same trend with the HPLC results normally somewhat lower
as these relate just to the identied compounds.
In blank test I the tar content is clearly higher than that exhibited when hot gas conditioning is performed (tests IIX). With an
increase in gasication time the amount of the reformed tar compounds remains fairly constant in a range of about 6070%. These
data obtained by HPLC/UV agree quite well with the overall tar
conversion brought about by the catalytic candle (79%) measured
by TOC analysis as reported above.
4. Conclusions
The innovative concept of integrating a catalytic hot gas lter in
the freeboard of a uidized-bed gasier has been tested. This
promising technology results in greatly increased gas and hydrogen yields, at the same time giving rise to signicant power plant
simplication and intensication. After a total gasication time
of 22 h, the catalytic performance of the lter element remains

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