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Catalytic reforming of tar during gasification.

Part II. Char as a catalyst or as a catalyst
support for tar reforming
Article in Fuel July 2011
DOI: 10.1016/j.fuel.2011.03.027

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Fuel 90 (2011) 25452552

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Catalytic reforming of tar during gasication. Part II. Char as a catalyst

or as a catalyst support for tar reforming
Zhenhua Min a,b, Piyachat Yimsiri b, Mohammad Asadullah a,b, Shu Zhang a,b, Chun-Zhu Li a,b,
a
b

Fuels and Energy Technology Institute, GPO Box U1987, Curtin University of Technology, Western Australia 6845, Australia
Department of Chemical Engineering, PO Box 36, Monash University, Victoria 3800, Australia

a r t i c l e

i n f o

Article history:
Received 6 February 2011
Received in revised form 17 March 2011
Accepted 17 March 2011
Available online 30 March 2011
Keywords:
Char-supported iron catalyst
Steam reforming
Tar reforming
Hot gas cleaning

a b s t r a c t
Char, char-supported catalysts and ilmenite were investigated for the steam reforming of biomass tar
derived from the pyrolysis of mallee wood in situ. Special attention was given to the reforming of
aromatic ring systems in tar. The results indicated that the char-supported iron/nickel catalysts exhibited
much higher activity for the reforming of tar than the char itself. Ilmenite and the char-supported iron
catalyst contained similar active phase but showed different tar reforming activities. Kinetic compensation effects demonstrated that the reaction pathways on the char-supported catalysts were similar but
were different from those on ilmenite. The proprieties of support could play important roles for the activities of the catalysts and the reaction pathways on the catalysts. Char would not only disperse the catalysts but also interact with the catalysts to enhance their activity for the steam reforming of tar.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Biomass gasication faces a number of technical challenges to
become a commercial renewable energy technology. The most
important one is the presence of tar in the gasication product
gas. Catalytic reforming is commonly accepted as the best option
that can convert tar into syngas efciently. Many types of catalysts
such as minerals [18] and Ni-based catalysts [915] have been
tried to reform tar. Iron-based catalysts [8,1619], having adequate
catalytic activities but less prone to coke formation and cheaper
than the Ni-based catalysts, show great promise for reforming tar
during biomass gasication.
The functions of support are important for the activity of the
catalyst. The support should be favourable for extending the life
of catalyst by inhibiting the agglomeration of the active phases
in the catalyst. Our recent review [20] has clearly indicated that
the chars from the pyrolysis and gasication of low-rank coal
and biomass could serve as support for a new class of cheap industrial catalysts with superior performance. Char itself also exhibits
some activity for tar reforming with its reforming activity being
inuenced by pore size, surface area and AAEM contents of char
[2123]. The coke deposited on the char can block the pores and
reduce the surface area to decrease its activity. However, the coke
can also be consumed by gasication/reforming agents and gas Corresponding author at: Fuels and Energy Technology Institute, GPO Box
U1987, Curtin University of Technology, Western Australia 6845, Australia. Tel.: +61
8 9266 1133; fax: +61 8 9266 1138.
E-mail address: chun-zhu.li@curtin.edu.au (C.-Z. Li).
0016-2361/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2011.03.027

eous products, such as steam, O2, and CO2, which would inhibit
its deactivation by producing new pores [22,23]. Furthermore, char
can act as a good support to disperse the active clusters at
nanoscale following pyrolysis or partial gasication [20,2426].
The char-supported catalysts would have low costs and be simply
burned/gasied to recover the energy of the char without the need
of often expensive regeneration after deactivation [20]. Hence, it is
worthy to understand the catalytic activities of the char-supported
catalysts on tar reforming and the functions of char during the catalytic steam reforming process.
In this study, char-supported iron/nickel and ilmenite catalysts
are used for the steam reforming of biomass tar derived from the
pyrolysis of mallee wood in situ. The performance of the catalysts
on the steam reforming of biomass tar was studied under a wide
range of operating conditions. The effects of support on the steam
reforming of tar were investigated. The kinetic parameters have
been calculated using a rst-order kinetic equation and are discussed in terms of changes in the reaction pathways.
2. Experimental
2.1. Preparation of catalysts
A Victorian brown coal was used to prepare the catalyst. The
main procedures for treating brown coal were acid washing and
ion-exchanging [2426]. Briey, Loy Yang brown coal (Victoria,
Australia) with a particle size range of 53150 lm (Table 1) was
washed with 0.2 M H2SO4 solution and de-ionised water to remove
inherent metallic species (mainly, Na, Mg, Ca, Fe, etc.). These

2546

Z. Min et al. / Fuel 90 (2011) 25452552

Table 1
Proximate and ultimate analyses of coal and biomass.
Proximate analysis (wt.%)
a

Brown
coal
Mallee
wood
a
b
c

Ultimate analysis (wt.%)

Ash

Volatile
matterb

Fixed
carbonb

Cb

Hb

Nb

Sb

Clb

Ob,c

3.2

51.9

48.1

68.1

4.9

0.6

0.6

0.1

25.7

0.9

81.6

18.4

48.2

6.1

0.15

0.01

0.04

45.5

Dry basis.
Dry and ash-free basis.
By difference.

inherent metallic species are removed only for the purpose of fundamental investigation to ascertain the catalytic activities of each
species although these species themselves could also act as tar
reforming catalysts. The air-dried acid-washed coal that contains
a negligible amount of inorganic species is termed as the H-form
coal because all carboxylates (COOM) have been turned into acids
(COOH). The H-form coal was ion-exchanged with 0.2 M FeCl3 or
Ni(NO3)2 solutions to load iron or nickel into the H-form coal,
respectively. The treated coals are thus termed as the iron-loaded
coal or the nickel-loaded coal.
The catalysts were prepared by pyrolysing and subsequently
gasifying the H-form coal, the iron-loaded coal and the nickelloaded coal at 800 C in a one-stage uidised-bed/xed-bed quartz
reactor [27]. Silica sand, ranging from 212 to 300 lm, was used as
the bed material. The ow rates of feeding gas and uidizing gas
were each 1 L min1. The coal particles were fed into the reactor
at a rate of around 300 mg min1 through a water-cooled probe
when the reactor had reached the target temperature. After the
feeding process, the steam was injected into the reactor to start
gasication that lasted for 10 min. An HPLC pump (Alltech 426)
was used to supply water directly into the reactor at the required
ow rate to make the steam concentration as 15 vol.% of the total
gas fed into the reactor. Finally, the char samples were collected
and used as the catalysts for the steam reforming of biomass tar
in subsequent experiments. The iron content of the char-supported
iron catalyst and the nickel content of the char-supported nickel
catalyst, measured using ICP, were 2.34 wt.% and 0.88 wt.% on
dry basis, respectively.
In some experiments, prior to being used for the steam reforming experiments, the char-supported iron catalyst was reduced at
600 C in situ for 1 h using Ultra High Purity (>99.999%) hydrogen
controlled by a mass ow controller (0.3 L min1).
In order to investigate the functions of the active phase and the
support of the catalysts, ilmenite (TiWest Joint Venture, WA, 106
150 lm) and iron oxide (SigmaAldrich, Fe3O4, <5 lm) were also
employed as catalysts for the steam reforming of biomass tar.
The main components in the raw ilmenite were Fe2O3 and TiO2 [8].
2.2. Steam reforming of biomass tar
A two-stage uidised-bed/xed-bed quartz reactor with three
frits, modied from our earlier design [28], was used for the
in situ catalytic steam reforming of biomass tar (Fig. 1a). The middle frit separated the reactor into two stages. Biomass was pyrolysed in the bottom stage and the product volatiles (tar) were
reformed with steam and the catalysts in the top stage.
In the three-frit reactor (Fig. 1a), the gas ow rates used were so
high for the char-supported catalyst particles (i.e. in the transport
reactor region) that the particles were elutriated to form a thin bed
underneath the top frit. The majority of the top stage was actually
available for the complete mixing of steam and volatiles before
they came into contact with the catalyst particles. However, when
ilmenite and Fe3O4 were used as catalysts, their high density

Fig. 1. A schematic diagram of the experimental set-ups for the steam reforming
experiments. (a) Three-frit reactor [modied from Ref. [24]], (b) four-frit reactor
[modied from Ref. [8]]. (1) water-cooled probe; (2) thermocouples; (3) biomass
particles and argon; (4) steam; (5) argon; (6) gas outlet (to condenser).

meant that these catalyst particles were only uidised. There was
concern that the volatiles and steam might not have well mixed
before contacting with the catalyst particles in the lower part of
the top stage. In order to ensure that steam and volatiles are well
mixed before entering the catalyst bed, the three-frit reactor was
modied into a four-frit two-stage uidised-bed/xed-bed quartz
reactor [8] (Fig. 1b). The distance between the catalyst bed and
the steam injection position of two reactors was the same
(30 mm) and the heights of the static catalyst bed were similar
(1.01.5 mm). These conditions ensured that the gas residence
time in the two reactors was comparable, allowing the direct comparison of the data obtained in these two reactors.
Mallee wood (WA, Australia, Table 1) with a particle size range
of 90180 lm was dried at 105 C for overnight prior to use. Silica
sand (212300 lm) was chosen as the uidised-bed material in the
bottom stage.
The catalysts were pre-loaded into the top stage before the
reactor was heated up. The temperature of the top frit and the temperature distribution of the bottom stage were measured using
two thermocouples for each reactor conguration (Fig. 1). The
feeding gas ow rate was 1 L min1. The uidising gas ow rate
was varied in the range of 0.721.50 L min1 to guarantee the same
residence time at different reforming temperatures. The steam
(15 vol.% of the total gas ow rate) was generated by feeding water
directly into the reactor with a HPLC pump (Alltech 426). The biomass particles were fed into the reactor (at approximately
100 mg min1) through a water-cooled probe after the reactor
had reached and stabilised at the target temperature. After the required amount of biomass had been fed into the reactor, the reactor was lifted out of the furnace immediately.
2.3. Sampling and analysis of tar
The details have been given in Part I of this series [8]. Briey, a
mixture of HPLC grade methanol and chloroform (1:4, vol) was

2547

Z. Min et al. / Fuel 90 (2011) 25452552

2.4. Characterisation of catalysts

X-ray diffraction (XRD) patterns of the fresh and spent catalysts
were acquired with a Philips PW1140/90 diffractometer with Cu
Ka radiation (25 mA and 40 kV) at a scan rate of 2 min1 and a
step size of 0.02.
3. Results and discussion
3.1. Tar reforming using char-supported catalysts
3.1.1. Reduction of tar yields
Fig. 2 shows the tar yields after the steam reforming of volatiles
from mallee wood with/without char-supported catalysts at different temperatures. The tar yields always decreased with increasing
temperature due to the enhanced thermal cracking and reforming.
However, the tar yields after pyrolysis were similar to those after
the steam reforming without catalyst at lower temperatures. In
agreement with literature [8,31], the external steam has weak
inuences on the thermal cracking and reforming of tar in the
gas phase due to its low reactivity at low temperature.
The tar yields after the steam reforming with all char-supported
catalysts (H-char, Fe-char and Ni-char, in Fig. 2, prepared
from H-form coal, Fe-loaded coal and Ni-loaded coal) dropped
compared with those after the steam reforming without catalyst,
especially at higher temperatures. Even the H-form char catalyst
showed some activity for decreasing the tar yield at high temperature. According to our previous studies [20,2426], the iron/nickel
clusters exist as nanoparticles highly dispersed in the char, giving
their high activities. Although the effects of the char-supported
iron catalyst on the tar yields were inconspicuous at low temperature, its catalytic activity became very prominent at high temperature (P800 C). Taking the tar yields after pyrolysis as the basis
for comparison, the use of the char-supported iron catalyst brought
about 84% and 96% reduction in the tar yield at 800 C and 850 C,
respectively. Furthermore, the tar yields after the steam reforming

35

Tar yield (wt% of biomass,db)

used to capture the tar in three tar traps tted with thimbles and
placed in an ice-water bath and a dry ice bath, respectively. The
solvents improved heat transfer and dissolved the tar immediately,
avoiding the blockage of the thimble lters. Steam in the gas was
condensed in the rst trap with 50 ml solvent that was placed in
an ice-water bath (0 C), which avoided the blockage by ice of
the thimble lter in the second trap setting in a dry ice bath
(78 C). The second trap captured the tar efciently in experiments because negligible amounts of heavy tar (i.e. no colour)
were found in the third trap placed in a dry ice bath (78 C). After
experiments, the tar condensed at the exit of the reactor was
washed with the solution in the third trap. The recovered tar solutions from all three traps were mixed well and weighed accurately.
The tar yield was determined by evaporating the solvents and
water at 35 C for 4 h. The tar is hereby dened experimentally
as the material soluble in the mixture solvents (methanol and chloroform, 1:4) but would not evaporate (with the solvents) at 35 C
within 4 h. The residues in the solvents themselves (i.e. blank)
and the moisture content of biomass were considered in the calculation of the tar yields. The estimated reproducibility of tar yield
measurement is about 0.3 wt.%.
The aromatic ring systems in tar were characterised using a PerkinElmer LS50B luminescence spectrometer with a 1 cm light
path length. The slit widths were 2.5 nm and the scan speed was
200 nm min1. The synchronous spectra were recorded with a constant energy difference of 2800 cm1. The uorescence intensity
was multiplied by the tar yield to be displayed on the basis of per
gram of biomass (db) [29,30].

Pyrolysis
Reforming no catalyst
Reforming with H-char
Reforming with Fe-char
Reforming with Ni-char

30
25
20
15
10
5
0
400

500

600

700

800

900

Temperature ( C)
Fig. 2. The yields of tar after the reforming of mallee wood volatiles with steam
using char and char-supported catalysts as a function of reforming temperature.
Pyrolysis refers to the thermal decomposition of volatiles in the absence of
externally added steam or catalyst.

with the char-supported nickel catalyst were even lower than

those after the steam reforming with the char-supported iron catalyst, especially at low temperature. Nickel clearly has higher
activity for tar reforming than iron even at temperature as low as
500 C.
3.1.2. Reduction of the yields of aromatic ring systems
Tar is a very complex mixture of compounds having aromatic,
aliphatic and oxygen-containing structures. The presence of aromatic structures in tar is the major concern in terms of gasication
product gas quality. The tar yields may not always reect the
changes in aromatic ring systems during the steam reforming process. Therefore, in addition to the measurement of tar yields, UVuorescence spectroscopy was used to characterise the aromatic
structural features of tar so as to understand the performance of
the catalysts in the steam reforming of the aromatic ring systems.
2 ppm and 4 ppm (wt) solutions were examined under the same
conditions to conrm the minimal self-absorption of uorescence
by the tar solution. The intensities of 4 ppm (Fig. 3) tar solutions
were about double of those of 2 ppm tar solutions, demonstrating
that 4 ppm was low enough to minimise the self-absorption effects
and the observed UV-uorescence intensity thus semi-quantitatively reects the concentrations of the aromatic ring systems in
the tar solution.
It was noticed that the shapes of spectra were similar for tars
after reforming at the same temperature (Fig. 4), indicating that
the types of aromatic ring systems were similar in the tars produced under different steam reforming conditions. At low temperature, the intensities of the tar after pyrolysis and the steam
reforming without any catalyst were similar. In agreement with
the overall tar yields explained above, these data in Fig. 4 imply
that the aromatic ring systems cannot be further broken down
by the externally added steam without catalysts at low temperature (600 C or lower) due to the low activity of steam and the high
thermal stability of the aromatic ring systems at low temperatures
(Figs. 4a and b). With increasing temperature to 700 C, the intensity of the tar after the steam reforming without the catalyst became slightly lower than that after pyrolysis (Figs. 4ce). Some
aromatic ring systems would have been further reformed by the
externally added steam when the temperature was higher than
700 C.
The UV-uorescence intensities, on the basis of per gram of
biomass (i.e. multiplied by the tar yield), changed drastically when
the catalyst was used (Fig. 4). The yields of the small aromatic ring

Z. Min et al. / Fuel 90 (2011) 25452552

2000

60

1. 4 ppm
2. 2 ppm

1600

Intensity (a.u., per g of

biomass (db)

Intensity (a.u., per g of

biomass (db)

2548

1200
2

800
400
0
260

300

340

380

420

460

1. 4 ppm
2. 2 ppm

45
30

15
0
260

500

300

340

380

420

460

500

Wavelength (nm)

Wavelength (nm)

(b)

(a)

Fig. 3. Constant energy (2800 cm1) synchronous spectra of mallee wood tar solution. (a) The tar was produced from the pyrolysis of mallee wood at 500 C, (b) the tar was
produced from the steam reforming of mallee wood volatiles at 850 C with the char-supported iron catalyst.

2500

2000

4
3

1500

1
2

1000

Intensity (a.u., per g of

biomass (db))

Intensity (a.u., per g of

biomass (db))

2500
(a), 500C

500

(b), 600C
2000

1500

4
1
2

1000
5

500
0

0
260

300

340

380

420

460

260

500

300

Wavelength (nm)
Intensity (a.u., per g of
biomass (db))

Intensity (a.u., per g of

biomass (db))

2500
(c), 700C
2000
1
1500

2
3

1000

500
5
0
260

300

340

380

340

380

420

460

500

Wavelength (nm)

420

460

2500
(d), 800C
2000
1500

1000

2
3

500

0
260

500

300

5
340

380

420

460

500

Wavelength (nm)

Wavelength (nm)

Intensity (a.u., per g of

biomass (db))

2500
(e), 850C
2000
1500
1000
1

500

0
260

300

340

380

420

460

500

Wavelength (nm)
Fig. 4. Constant energy (2800 cm1) synchronous spectra of mallee wood tar solution (4 ppm) after the steam reforming of its volatiles with/without the char-supported
catalysts at the temperatures (1, pyrolysis; 2, reforming without catalyst; 3, reforming with H-char; 4, reforming with Fe-char; 5, reforming with Ni-char).

systems (mainly 23 rings, 280 nm < wavelength < 360 nm) after
the reforming with H-char or Fe-char were higher than those after
pyrolysis or non-catalytic reforming while the yields of the larger
aromatic ring systems (wavelength >360 nm) were similar at

500 C and 600 C (Figs. 4a and 4b). The increases in the yields of
smaller aromatic ring systems took place when the corresponding
changes in tar yields due to catalyst were small at this temperature
level. There are three possible reactions due to the catalysts. Firstly,

2549

Z. Min et al. / Fuel 90 (2011) 25452552

3.2. Active phases in char-supported iron catalyst

The fresh and spent char-supported iron catalysts were characterised using X-ray diffraction (Fig. 5). In the iron-loaded coal
(Fig. 5a), the only clear peak observed is due to quartz present in
the raw coal as its mineral matter. The iron would exist in coal
in the form of FeOOH or be associated with certain functional
groups (COOH, OH) in coal [20,2426]. Both forms of iron were
well dispersed in the coal matrix and cannot be detected by XRD.
As are shown in Fig. 5, the XRD patterns of the char-supported iron
catalysts indicated the presence of magnetite (Fe3O4) coexisting
with the reduced irons (a-Fe and c-Fe). According to the FeC equilibrium phase diagram, a-Fe is a stable species when the temperature is lower than 700 C and c-Fe become a stable species when
the temperature is higher than 900 C. The iron phases present in
the char depend on the cooling rate of the sample [24]. c-Fe (C)
would be kept rather than transformed into a-Fe/Fe3C when cooling rapidly [24].
The crystal sizes of the iron-containing species were calculated
using Scherrer equation (Table 2). The crystal size of SiO2 was calculated as a standard to verify the Scherrer equation. The crystal
size of Fe3O4 in the catalyst remained almost unchanged (or, if anything, showed small decreases with increasing temperature), indicating that the char has effectively inhibited sintering and
agglomeration of the iron-containing species during the steam
reforming process. This is at least partly due to the fact that magnetite was not at the optimum status for sintering when it is continuously involved in partial reduction and oxidation as a part of

(g)

300
0
300

M M

M M

M M

0
300

Intensity (a.u.)

aliphatic hydrocarbon structures could combine together to form

new aromatic ring systems through polymerisation [32]. However,
this type of polymerisation seems unlikely here because it would
only occur at very high temperatures (>1000 C) under the current
experimental conditions [32] and the catalyst is unlikely to make
the polymerisation to take place at such a low temperature level.
Secondly, the decomposition (via the breakdown of weak bonds
connecting aromatic ring systems) of a large molecule may result
in the detachment of small aromatic ring systems from the larger
ones originally connected in the big molecule. Due to the intramolecular energy transfer from small to large aromatic ring systems in a big tarry molecule [33], this type of breakdown would
have little effect on the observed synchronous uorescence intensity from the larger aromatic ring systems whilst the observed synchronous intensity for the smaller aromatic rings would increase
[33]. Thirdly and importantly, the dehydration and dehydrogenation of aliphatics and/or O-functional groups, especially sugar compounds derived from the pyrolysis of cellulose and hemicelluloses,
could have taken place. Sugar compounds containing larger
amounts of OH groups could be dehydrated and dehydrogenated
easily to form new heterocyclic and/or substituted aromatic ring
systems on the surface of the catalyst. It is believed that the dehydration and dehydrogenation of aliphatics and/or O-functional
groups would be a predominant factor for generating additional
aromatic ring systems at low temperatures.
At high temperatures (>700 C, Figs. 4ce), the yields of the aromatic ring systems after the catalytic reforming were signicantly
lower than those after pyrolysis or non-catalytic reforming. The
char-supported iron catalyst showed higher activity for the
reforming of the aromatic ring systems than the H-form char catalyst at high temperature. The activities of Fe-char and Ni-char
proliferated dramatically with increasing temperature, which were
in agreement with the tar yield (Fig. 2). Furthermore, the data in
Fig. 4c also indicated that the char-supported nickel catalyst had
much higher activity than the char-supported iron catalyst in
reforming the aromatic ring systems at 700 C. However, their
activities became comparable at 800 and 850 C.

(f)

Q
M
M

0
300

Q
M

0
300

Q
M
M

0
300

Q
M M

0
300

M M
(e)

M M M

(d)

MM

(c)

M M M
(b)

M M

(a)

0
10

20

30

40
50
2 (degree)

60

70

80

Fig. 5. XRD spectra of fresh and spent char-supported iron catalysts after the steam
reforming of mallee wood tar. (a) Raw Fe-loaded coal, (b) fresh char-supported iron
catalyst prepared at 800 C, (c) spent catalyst after reforming at 500 C, (d) spent
catalyst after reforming at 600 C, (e) spent catalyst after reforming at 700 C, (f)
spent catalyst after reforming at 800 C, and (g) spent catalyst after reforming at
850 C. (M: magnetite (Fe3O4); a: a-Fe; c: c-Fe; Q: quartz).

Table 2
Crystal sizes of iron-containing species in fresh and spent char-supported iron
catalysts calculated using the Scherrer equation.

Fresh catalyst
After being used
After being used
After being used
After being used
After being used

at
at
at
at
at

500 C
600 C
700 C
800 C
850 C

SiO2 (nm)

Fe3O4 (nm)

34.1
33.4
33.9
33.8
34.6
34.6

16.2
17.9
18.7
21.5
15.4
15.3

the redox reaction mechanism [1618] during the steam reforming

process.
Further experiments were carried out using magnetite, prereduced char-supported iron catalyst and the mixture of magnetite
and H-form char as catalysts for the steam reforming of volatiles
from mallee wood. The amounts of catalysts used during these
experiments were 1 g, except the experiments with Fe3O4 in which
the amount of Fe3O4 was 5 g (due to its high density) to keep the
same height of the static catalyst bed. In the mixture of Fe3O4
and char, the content of Fe3O4 is 10%. The peak areas of UV-uorescence spectra of tar produced with different catalysts at 800 C are
shown in Fig. 6. All catalysts showed activity for reforming the aromatic ring systems. Compared with the mixture of magnetite and
the H-form char (Fe3O4 content, 10%), magnetite or the H-form
char alone exhibited lower activity for breaking down aromatic
ring systems. The H-form char in the mixture would improve the
dispersion of magnetite. More importantly, the H-form char (carbon) would interact with magnetite to produce new forms of iron
(i.e. metallic iron and/or other reduced forms of iron) which would
have high activity. However, the activity of the mixture of magnetite and H-form char was lower than that of the char-supported
iron catalyst, indicating that the physical mixing cannot disperse

Z. Min et al. / Fuel 90 (2011) 25452552

12.0

H-char

80000
60000

ln[-ln(1-X tar)/]

Small aromatic ring systems

Large aromatic ring systems

40000
20000

Fe-char

Ni-char

Ilmenite

8.0

4.0

r
Fe
-c

ha

ha
r
-c

0.8

0.9

1.0

1.2

1.3

1.4

(a)

R
ed

1.1

1000/T (1/K)

10

Fe
3O

0.0

uc
ed

Fe

Fe

-c
h

3O

ar

ha
r

H
-c

ta
ly

st

0
ca

Peak area (per g of biomass,db)

2550

18
Fig. 6. Peak areas of constant energy (2800 cm1) synchronous spectra of mallee
wood tar solution (4 ppm) after the steam reforming with different catalysts at
800 C.

16

the iron-containing species in the char as effectively as ionexchanging.

It is interesting to note that the results (Fig. 6) of the pre-reduced char-supported iron catalyst were similar to those of the
char-supported iron catalyst, implying that syngas product and
the char in the catalyst were enough to reduce the iron-containing
species at the initial stage of the steam reforming process These
further prove that the highly dispersed iron-containing species in
the catalyst were the predominate factor for its high activity for
tar reforming.

According to the tar yields, the kinetic parameters were calculated using a simple rst-order kinetic equation (Eqs. (1) and (2))
for the overall tar reforming reactions [3438].

dX tar
Eapp
kapp exp
1  X tar
dt
RT

ln1  X tar
Eapp
 ln kapp 
s
RT

where Xtar is the tar conversion after the steam reforming, on the
basis of tar yield after pyrolysis at 500 C, kapp is the apparent
pre-exponential factor, m3/(kg h), Eapp is the apparent activation energy, kJ/mol, s is the spacetime of gas the in the catalytic bed,
(kg h)/m3.
The spacetime for the catalytic bed is dened in Eq. (3).

kg of catalyst in the bed

m3 =hexit wet gas flow rate; reactor temperature

H-char

14
Ilmenite

12

10
40

50

60

70

80

90

100

Eapp (kJ/mol)

(b)
Fig. 7. (a) Arrhenius plots and (b) CremerConstable relationship for the catalytic
steam reforming of mallee wood tar.

3.3. Kinetic aspects of catalytic steam reforming

ln

lnk app

Fe-char
Ni-char

It should be noted that the steam supply was in excess and the
concentration of steam remained unchanged in all experiments.
Therefore, the term relating to the concentration of steam has been
lumped into the apparent pre-exponential factor kapp.
The Arrhenius plots and CremerConstable diagram of the catalytic steam reforming (500850 C) are shown in Fig. 7. The slopes
and intercepts of these lines were calculated by linear regression to
give the apparent activation energies and pre-exponential factors
(Table 3) for reforming with the H-form char catalyst, the charsupported iron catalyst, the char-supported nickel catalyst and
ilmenite.
As expected from their relative tar reforming activities, the
apparent activation energy and pre-exponential factor of the

Table 3
Apparent activation energies and pre-exponential factors for the overall tar removal.

H-form char catalyst

Char-supported iron catalyst
Char-supported nickel catalyst
Ilmenite

Eapp (kJ/mol)

kapp (m3/(kg h))

82.1
60.8
57.3
72.6

5.39  106
2.11  106
1.32  106
5.29  105

H-form char was higher than those of the char-supported catalysts.

The apparent activation energy of ilmenite was higher and the
pre-exponential factor of ilmenite was lower than those of
char-supported iron catalyst, in agreement with the observation
(Figs. 2 and 4) that the char-supported iron catalyst had higher
activity for the reforming of tar.

3.4. Some further discussion on the importance of support on tar

reforming
The kinetic parameters of all char-supported catalysts exhibited
a genuine kinetic compensation effect, closely following the
CremerConstable relationship (Fig. 7b); but the kinetic parameters of ilmenite were out of the relationship. Therefore, it could
be concluded that the reaction mechanisms or pathways of the
steam reforming process on the char-supported catalysts are similar, but the steam reforming reactions on ilmenite follow different
pathways. Because both ilmenite and the char-supported iron
catalyst have the same key catalytically active species (Fe species
forming a redox cycle), it then becomes clear that the support

Z. Min et al. / Fuel 90 (2011) 25452552

160000

Total peak area (per g of

biomass,db)

No catalyst
Fe-char
120000
Ilmenite
80000

40000

0
500

600
700
800
Temperature (oC)

850

Fig. 8. Peak area of constant energy (2800 cm1) synchronous spectra of mallee
wood tar solution (4 ppm) after the steam reforming with/without catalysts at
different temperatures.

Coke yield (wt% of biomass,db)

proprieties must have played important roles on the reaction pathways on the catalysts. In other words, the support would not only
disperse the iron-containing species but also interact with the
iron-containing species to become involved in the catalytic reactions during tar reforming.
In order to further understand the importance of support in
iron-based catalysts for the steam reforming of tar, the peak areas
of UV-uorescence spectra of aromatic ring systems in tar produced with ilmenite and the char-supported iron catalyst are compared in Fig. 8. These data conrm the drastic difference between
char-supported catalyst and ilmenite. At low temperatures
(<600 C), the aromatic ring systems increased after the steam
reforming with the char-supported iron catalyst, whereas they decreased after the steam reforming with ilmenite. As was mentioned above, the char-supported iron catalyst appears to be
particularly suitable for the dehydration and dehydrogenation
reactions to form additional aromatic ring systems.
In contrast, the char-supported iron catalyst showed higher
activity for reforming aromatic ring systems than ilmenite at high
temperature. Coke formation was still signicant on ilmenite at
high temperature (Fig. 9) [8], leading to slow deactivation of the
catalyst. However, in the case of char-supported catalysts, there

16

Reforming with H-char

Reforming with Fe-char
Reforming with Ni-char
Reforming with ilmenite

12
8
4
0

2551

was a net gasication of char in the char-supported catalyst

(Fig. 9). The iron (or nickel) nano clusters were never covered by
coke, allowing their catalytic activities to be maintained during
reforming.
Furthermore, at higher temperatures (P800 C), the data in
Figs. 2 and 4 show that the char support itself (i.e. H-char) also
has signicant catalytic activities for the reforming of tar/volatiles.
Therefore, the char support is not at all inert. In fact, it is fair to believe that the char and iron (nickel) must have acted together during reforming. For example, the tar/volatile molecules could easily
adsorb and dissociate on the char surface. The iron (or nickel) may
have acted to speed up the dissociation of steam to produce reactive intermediates (radicals) on the iron (nickel) surface. These
intermediates (radicals) could subsequently spill over easily to
the sites on char to react with the chemically adsorbed tar fragments on the char surface to result in the complete reforming of
tar/volatiles. Alternatively or concurrently, the fragments (radicals)
formed from the dissociation of tar/volatile molecules on the char
surface could easily migrate onto the iron/nickel cluster for the
ultimate reforming on the iron surface. Our data so far do not allow
for a clear evaluation of the relative importance of each route of
radical migration (spill over) between the char and ion/nickel clusters. The observation that H-char and char-supported iron/nickel
catalyst lie on the same straight line in Fig. 7b would indicate that
the reaction pathways, especially the key rate-limiting steps,
would be similar with char itself as a catalyst or with char-supported catalysts. Because TiO2 in ilmenite is relatively inert, this
type of radical migration is much less important for the observed
reforming kinetics.
4. Conclusions
The char-supported catalysts have shown high activities for the
reforming of biomass tar/volatiles. The char-supported iron/nickel
catalysts have much higher activity for the reforming of tar than
the H-form char catalyst. The difference in the catalytic activity between the char-supported iron catalyst and the char-supported
nickel catalyst decreases with increasing temperature. The
economic consideration would probably means that the charsupported iron catalyst may nd better practical application for
tar reforming than the char-supported nickel catalyst.
Comparison of ilmenite and the char-supported iron catalyst,
both having Fe as their key catalysts, indicates that the catalyst
support could interact with the catalyst signicantly to inuence
the activities of the catalysts and the reaction pathways on the catalysts. The kinetic analysis of our experimental data shows that all
char-supported catalysts may follow similar reforming reaction
pathways, which are different from those using the ilmenite catalyst. Migration of reactive intermediates (radicals) between the active sites on char and the iron (or nickel) clusters is believed to be
an important mechanism of support-catalyst interactions.
Acknowledgement

-4

This project received funding from the Australian Government

as part of the Asia-Pacic Partnership on Clean Development and
Climate.

-8
-12
400

500

600

700

800

900

Temperature (oC)
Fig. 9. The yields of coke after the reforming of mallee wood volatiles with steam
using char and char-supported catalysts as a function of reforming temperature.
(The data of ilmenite were re-plotted from Ref. [8]. The total gas ow rates of argon
were 2.50 L min1 at 500 C, 2.21 L min1 at 600 C, 1.98 L min1 at 700 C,
1.80 L min1 at 800 C and 1.72 L min1 at 850 C, respectively. The concentration
of steam was always maintained at 15 vol.% in the gas stream.)

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