Bioresource Technology 96 (2005) 15701577

Volatilisation of alkali and alkaline earth metallic species during

the pyrolysis of biomass: dierences between sugar cane bagasse
and cane trash
Daniel M. Keown a, George Favas a, Jun-ichiro Hayashi b, Chun-Zhu Li a,*

a
Department of Chemical Engineering, Monash University, P.O. Box 36, Monash, Vict. 3800, Australia
b
Centre for Advanced Research of Energy Technology, Hokkaido University, N13-W8, Kita-ku, Sapporo 060 8628, Japan
Received 29 June 2004; received in revised form 14 December 2004; accepted 26 December 2004
Available online 22 February 2005

Abstract

Sugar cane bagasse and cane trash were pyrolysed in a novel quartz uidised-bed/xed-bed reactor. Quantication of the Na, K,
Mg and Ca in chars revealed that pyrolysis temperature, heating rate, valence and biomass type were important factors inuencing
the volatilisation of these alkali and alkaline earth metallic (AAEM) species. Pyrolysis at a slow heating rate ( 10 K min 1) led to
minimal (often <20%) volatilisation of AAEM species from these biomass samples. Fast heating rates (>1000 K s 1), encouraging
volatilechar interactions with the current reactor conguration, resulted in the volatilisation of around 80% of Na, K, Mg and Ca
from bagasse during pyrolysis at 900 C. Similar behaviour was observed for monovalent Na and K with cane trash, but the
volatilisation of Mg and Ca from cane trash was always restricted. The dierence in Cl content between bagasse and cane trash
was not sucient to fully explain the dierence in the volatilisation of Mg and Ca.
2005 Elsevier Ltd. All rights reserved.

Keywords: Biomass; Pyrolysis; Fluidised-bed; Volatilisation; Chlorine; Potassium

1. Introduction solar energy into the chemical energy of environmentally

Gasication/reforming of biomass represents a
potentially ecient way to use biomass as a renew-
able energy source. If coupled with CO2 sequestration,
gasication/reforming-based power generation using
biomass could lead to a net reduction of CO2 in the
atmosphere. In particular, the gasication/reforming of
biomass constitutes an attractive way of renewable pro-
duction of H2 (Asadullah et al., 2002; Demirbas, 2002;
Garcia et al., 2002) for ecient power generation using
fuel cells or gas turbine systems. As an endothermic pro-
cess, the gasication of biomass also has the potential of
acting as a chemical heat pump to convert the thermal
*
Corresponding author. Tel.: +61 3 9905 9623; fax: +61 3 9905 5686.
E-mail address: chun-zhu.li@eng.monash.edu.au (C.-Z. Li).
friendly and renewable fuels such as H2.
Most of the biomass gasication processes proposed
or demonstrated so far are largely based on experiences
from coal gasication. The special thermochemical
properties of biomass are often ignored in these gasica-
tion processes. Compared with most bituminous coals,
one of the important features of biomass materials is
the presence of signicant amounts of alkali and alkaline
earth metallic (AAEM) species (mainly K, Na, Mg and
Ca). The AAEM species tend to volatilise during pyroly-
sis (and gasication/combustion) and are an important
consideration in all aspects of biomass thermochemical
conversion processes such as gasication. While the vol-
atilisation of AAEM species may create slagging and/or
fouling problems for the operation of gas turbine blades
or in the conventional pulverised fuel combustion

0960-8524/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2004.12.014
 157 D.M.
D.M.Keown
Keown
et et
al. al.
/ Bioresource
/ Bioresource
1 1
systems using biomass (Nielsen et al., 2000), the AAEM
species retained in char during pyrolysis are impor-
tant catalysts for the gasication/combustion of char
(Raveendran and Ganesh, 1998; Zolin et al., 2001), help-
ing to reduce the gasication temperature and thus
increasing the overall gasication process eciency and
process economy. The volatilised AAEM species may
also act as catalysts for the steam reforming of volatiles
in the gas phase (Hosokai et al., 2004). Clearly, the devel-
opment of a biomass gasication process would require a
good understanding of the volatilisation of AAEM spe-
cies during the pyrolysis of biomass in order to take
advantage of the special thermochemical properties of
biomass.
Annual biomasses often contain much higher concen-
trations of Cl than coal. Because the Cl and high pro-
portions of AAEM species (particularly K) in biomass
are water soluble, simple leaching/washing can remove
large fractions of both alkali metals (in most cases
>80% of K and Na) and Cl (>90%) from biomass (or
char) and therefore has been considered as a means of
mitigating the problems caused by the volatilisation of
AAEM (particularly K) (Davidsson et al., 2002; Dayton
et al., 1999; Gabra et al., 2001; Jenkins et al., 1996;
Jensen et al., 2000, 2001; Mojtahedi and Backman,
1989; Olsson et al., 1997; Turn et al., 1998, 2003).
While it is often agreed that K contained in biomass
is released into the gas phase mainly as KCl during
pyrolysis and gasication of biomass (Dayton et al.,
1995; Olsson et al., 1997), the detailed mechanisms re-
main unclear, often contradicting with results such as
volatilisation of a portion of Cl preferential to K (Jensen
et al., 2000) and volatilisation of Cl mainly as HCl
(Bjo rkman and Stromberg, 1997). The ratio of K
and Cl in biomass appears to aect the volatilisation
of K and Cl (Gabra et al., 2001; Jensen et al., 2000,
2001; Mojtahedi and Backman, 1989; Olsson et al.,
1997). In agreement with Olsson et al. (1997), Jensen
et al. (2000) showed two steps in the volatilisation
of Cl:
200400 C and 700900 C. Signicant amounts of K
were only released above 700 C. Previous results (Quyn
et al., 2002a) on the pyrolysis of a NaCl-containing Vic-
torian brown coal also showed that the release of Na
and Cl took place independently and not as NaCl mole-
cules during pyrolysis. As Cl and K may volatilise from
solid fuels [biomass (Jensen et al., 2000; Olsson et al.,
Table 1
Proximate and ultimate analyses of the biomass samples used in this study
Biomass type Particle size range (lm) Ash yield (wt% db) [0.1]
Bagasse 125210 6.9
Cane trash 125210 7.6
a
Oxygen calculated by dierence.
Technology
Technology
9696
(2005)
(2005)
15701577
15701577 157
1997) and brown coal (Quyn et al., 2002a)] indepen-
dently during pyrolysis, this poses a question as to
whether Cl in biomass would indeed facilitate the
volatilisation of K or other AAEM species during
pyrolysis.
With the preferential release of Cl during the pyroly-
sis of biomass (Jensen et al., 2000; Olsson et al., 1997),
K must have been bonded to the char matrix. In fact,
as will be shown in this study, there is often not enough
Cl to account for the AAEM species, or even just K, in
biomass. In other words, a signicant proportion of
AAEM species exist in biomass in forms other than
chlorides. Furthermore, signicant amounts of Ca and
Mg also exist in biomass as the essential nutrients for
the growth of the biomass. Very little is known about
the volatilisation of these non-chloride AAEM species
during pyrolysis.
The purpose of this study is to investigate the volatil-
isation of AAEM species during the pyrolysis of bio-
mass. Two biomass samples were chosen in this study:
a sugar cane bagasse sample and a cane trash sample.
Both bagasse and cane trash are considered as impor-
tant potential renewable energy sources. A novel
uidised-bed/xed-bed reactor was used to study the
pyrolysis of these biomass samples, providing insights
into the mechanisms of the volatilisation of AAEM
species during the pyrolysis of biomass.
2. Experimental
2.1. Biomass samples
Sugar cane bagasse and cane trash samples were pro-
vided by the Sugar Research Institute. The properties of
these biomass samples are shown below in Tables 1 and
2. The chlorine contents shown in Table 2 were deter-
mined using a slightly modied Eschka method (Chak-
rabarti, 1978; Quyn et al., 2002a). The sugar cane was
grown in Queensland, Australia. The sugar cane bagasse
has been washed/leached with water at an elevated tem-
perature during the extraction of its sugar. In contrast,
the cane trash sample has high contents of AAEM spe-
cies and Cl. The bagasse and cane trash samples were
air-dried and pulverised using a Bauer rener and sieved
repeatedly to a particle size range of 125250 lm.
Ultimate analysis (wt% daf)
C [0.3] H [0.1] N [0.05] S [0.03] Oa
49.7 6.1 0.31 0.04 43.8
49.5 6.1 0.31 0.08 44.0
Table 2
Contents of AAEM species and Cl in the biomass samples used in this study
Biomass type AAEM content (wt%, db) Cl content (wt%, db) [0.005] K:Cl atomic ratio [0.1]
Na [0.005] K [0.005] Mg [0.005] Ca [0.005]
Bagasse 0.057 0.174 0.104 0.095 0.027 5.9
Cane trash 0.043 0.525 0.185 0.368 0.176 2.7

2.2. Pyrolysis
Pyrolysis of the biomass samples was carried out
using a quartz uidised-bed/xed-bed reactor (Fig. 1)
heated with an external furnace. This reactor system
was originally developed to examine the volatilisation
of AAEM species during the pyrolysis of Victorian
brown coal (Quyn et al., 2002a). A 160 g bed of acid-
washed zircon sand (150180 lm) was uidised with
ultra high purity (>99.999%) argon. The reactor could
be operated in either fast or slow heating modes. In
the fast heating rate mode, biomass particles were en-
trained in a feeder and fed at a nominal rate of
1
75 mg min via a water-cooled injection probe directly
into the hot sand bed which was maintained at the de-
sired experimental temperature. Biomass particles were
3 4 1
heated at a rate in excess of 10 10 K s , based on
the estimation by Tyler (1979) for a similar reactor.
Due to the brous nature and elongated shape of the
biomass particles, the 1/8 in. diameter of the water injec-
tion probe (Quyn et al., 2002a) was increased to 1/4 in.
diameter to avoid biomass blockages during feeding.
The reactor design in this study (Fig. 1) diered from
a normal uidised-bed reactor in that a quartz frit was
Fluidising gas
Biomass
particles
ption
To absor
Water-
bottles
cooled
probe
Char
particles
Vol atiles
Quartz frits
installed in the freeboard. The frit prevented char elutri-
ation during pyrolysis so that the volatilised AAEM spe-
cies and the parent char were separated at the reaction
temperature. The elutriation of char out of the reactor
would have led to the re-condensation of the volatilised
AAEM species on the char surface at temperatures
lower than the pyrolysis temperature, causing major
errors in the quantication of the true volatilisation of
AAEM species. The presence of the frit in the freeboard
also allowed the elutriated char particles to be held
underneath the frit, subsequently forming a thin xed
char bed. Therefore, the reactor had features of a ui-
dised-bed reactor (e.g. fast heating rates) and of a
xed-bed reactor.
When the reactor was operated at the fast heating
rate mode, after about 2 g of biomass had been fed into
the reactor (actual mass of the fed biomass was accu-
rately determined later), the reactor was lifted out of
the furnace and brought to room temperature by natural
cooling. The argon gas continuously owed through the
reactor to prevent any char oxidation during quenching.
The ow rates of the uidising and feeding argon gas
were controlled by mass ow controllers. The total ow
1
rate was constant at 4.31 l min (at room temperature)
for all experiments.
The light tars and condensable gases that were pres-
ent in the volatiles were absorbed using two absorption
bottles (containing 0.1 M NaOH) connected in series to
the exit of the reactor. This arrangement was sucient
for the collection of all Cl (likely as HCl) and light carb-
oxylates/carboxylic acids in the volatiles (Quyn et al.,
2002a,b).
In contrast, in the slow heating rate mode, the bio-
mass particles were fed into the reactor (with sand) at
room temperature and the reactor was heated slowly
1
(nominally 10 K min ) to the desired temperature,
which was maintained for 15 min before cooling.
In all experiments, the char yield was determined by
weighing the reactor and biomass/char before and after
the experiment.

2.3. Characterisation of products

Sand The AAEM species in biomass and char were quanti-
bed ed using a previously established procedure (Li et al.,
2000). Briey, the biomass/char sample was ashed in a
TGA in air. The ash was digested with 1 ml of concen-
Fig. 1. A schematic diagram of the uidised-bed/xed-bed reactor trated hot HF:HNO3 (1:1) for at least 16 h. The acid
(modied from Quyn, 2002).
mixture was then evaporated on a hotplate and the
residue re-dissolved in 20 mM CH3SO3H (MSA). The
resulting MSA solutions were analysed using a Dionex
DX-500 ion chromatograph (IC) equipped with a
CS12A column and a CSRS cation suppressor to quan-
tify the concentrations of Na, K, Mg and Ca in each solu-
tion. The eluent used for the IC was also 20 mM MSA.
The sample size used in the TGA was limited by the need
to avoid ignition (Quyn, 2002; Sathe, 2001) and this may
have led to non-homogeneous samples being analysed.
To minimise the eect of non-homogenous samples, each
char was analysed in at least two separate ashings.
The same Dionex DX-500 IC equipped with an AS10
column and an ASRS suppressor was also used to ana-
lyse the solutions for anions such as Cl , formate, ace-
tate, oxalate and benzoate, following the procedures
described elsewhere (Quyn et al., 2002a). The eluent
used for the IC was 0.1 M NaOH.
3. Results and discussion
3.1. Char yields
Fig. 2 shows the char yields from the pyrolysis of
cane trash and bagasse samples as a function of temper-
ature and heating rate. The majority of sample weight
loss occurred at temperatures below 400 C for both
the bagasse and cane trash samples (Fig. 2) at both
heating rates. Increasing the temperature from 400 to
600 C only resulted in slight decreases in the char yield.
Further increases in temperature to 950 C at the slow
Char yield [wt%, db] Char yield [wt%, db]
heating rate resulted in less than 3 wt% (db) additional
weight loss for both biomass samples.
100
80
60
40
20
0 the fast heating rate. Soot formation could occur as
80
60
40
20
0 around 400600 C. However, at high temperatures
300 400 500 600 700 800 9001000
Pyrolysis Temperature [C]
Fig. 2. Char yields from the pyrolysis of (A) cane trash and (B)
bagasse as a function of temperature and heating rate in the uidised-
bed/xed-bed reactor.
For both bagasse and cane trash, the fast heating rate
experiments at temperatures below 400 C gave higher
char yields than the slow heating rate experiments.
These dierences are likely attributed to the relatively
short holding time in the fast heating experiments (i.e.
the reactor was lifted out of the furnace as soon as feed-
ing was completed, so some particles had only a few sec-
onds at temperature). At temperatures above 700 C, the
fast heating rate experiments gave noticeably lower char
yields than the corresponding slow heating rate experi-
ments (Fig. 2). A number of factors may have contrib-
uted to the observation of the eects of heating rate
on char yields shown in Fig. 2. Firstly, for many solid
fuels, a fast heating rate tends to give lower char yields
than a slow heating rate, due to the fact that the recom-
bination reactions inside a pyrolysing particle are less
favoured by high heating rates. Secondly, in a reactor
such as used in this study that encourages the interac-
tions between volatiles and char, the self-gasication
of nascent char by reactive components in the volatiles
is favoured at the fast heating rate mode. When the bio-
mass particles were pyrolysed at the fast heating rate
mode, volatiles generated from the particles fed into
the reactor would have to pass through the bed of char
underneath the frit in the freeboard (Fig. 1) that was
formed from the biomass particles fed at an earlier
stage. The reactive components in the volatiles such as
H2O and CO2, produced from the thermal cracking of
the light hydrocarbons and tar at elevated temperatures,
would react with the nascent char to result in the gasi-
cation of the nascent char. Moreover, to avoid changes
in biomass structure due to complete drying, the bio-
mass samples in this study were only air-dried prior to
pyrolysis: the biomass samples had moisture contents
in equilibrium with ambient atmosphere (the moisture
contents were determined and considered in the char
yield determination). This moisture inherently present
in the biomass samples would have been driven out of
(4A) Cane trash the biomass as steam, gasifying the nascent char.
Slow heating rate Indeed, the observed char yields at the fast heating rate
Fast heating rate decreased with increasing temperature due to the inten-
sication of these self-gasication reactions.
Thirdly, soot formation and destruction could also
have aected the observed char yields, particularly at
(B) Bagasse the volatiles passed through the thin char bed held
Slow heating rate
Fast heating rate underneath the frit in the freeboard. It is believed that
the possible soot formation may have partially oset
the eect of heating rate on the char yield, leading
to the insensitivity in char yield with heating rate at
(>600 C), the thermal cracking of soot would intensify
and the in situ reforming of volatiles (Hosokai et al.,
2004) by steam would have minimised the soot forma-
tion on char particles. The reforming reactions are likely
to be catalysed by the AAEM species volatilised into the
 gas phase (see later) or retained on char surface. Data on 100
Victorian brown coal (Li et al., 2004), which produces 80
volatiles that are more aromatic and thus of higher soot-
60
ing propensity than the volatiles from biomass, did show

Retention of species in char [%]

that in situ soot destruction was enough to eliminate the 40
(A) Na
char yield increases due to soot formation. The data in 20
Fig. 2 indicate that the combined eects of heating rate 0
and H2O/CO2 gasication of char was greater than any 100
possible eects of soot formation on the observed char 80
yields at temperatures higher than 600 C. 60
In contrast, for slow heating rate experiments, most
40
H2O and CO2 would have been released by the time
20 (B)
the reactor reached 450 C during pyrolysis (Wojtowicz
0
et al., 2003), and the majority of volatiles would have
100
been released at temperatures lower than 500 C and
carried out of the reactor (Fig. 2). Therefore, the self- 80
gasication reactions would have taken place to a min- 60
imal extent. With the same reasoning, soot formation 40
(C) Mg
would have also been eliminated at the slow heating rate 20
mode. The char yields at the slow heating rate remained 0
almost unchanged with increasing temperature above 100
about 600 C (Fig. 2); any small decreases in char yield 80
would have been due to the intensied thermal cracking 60
of char with increasing temperature. 40
20 (D)
3.2. AAEM retentions in char 0
500 600 700 800 900
Temperature [C]
The retentions of Na, K, Mg and Ca in the chars after
pyrolysis of the biomass samples are shown in Figs. 3 Slow heating rate Fast heating rate
and 4. Immediately clear are the signicant amounts Fig. 3. Retention of (A) Na, (B) K, (C) Mg and (D) Ca in char during
of AAEM species that were volatilised at temperatures the pyrolysis of bagasse as a function of temperature and heating rate
as low as 500 C for both biomass samples at both heat- in the uidised-bed/xed-bed reactor.
ing rates. The volatilisation of AAEM species was also
observed by Olsson et al. (1997) during the pyrolysis reaction temperature resulted in decreasing yields of
of biomass at temperatures as low as 180 C. As is both acetate and formate [0.5 wt% (db) and 0.01 wt%
shown in Table 2, there was insucient Cl in the bio- (db) at 900 C for acetate and formate respectively].
mass samples to account for the AAEM species: K/Cl Diminished yields of acetate and formate with increas-
atomic ratios were 2.70 and 5.85 for cane trash and ing temperature are possibly due to the thermal cracking
bagasse respectively. Some AAEM species must exist of carboxylates in the gas phase. These data indicate
in these biomass samples in forms other than chlorides, that structures containing COOH or COOX (X = K,
such as carboxylates. Quyn et al. (2002b) showed that Na, Mg or Ca) in biomass can be stable enough to be
some carboxylate structures in coal might be detached released as structures containing COOH and COOX.
and volatilised as light carboxylates, becoming an In other words, the thermal decomposition of carboxy-
important route of the volatilisation of AAEM species lates to release CO2 is not the only fate of the carboxy-
at temperatures as low as 300 C. Similarly, the thermal lates. This is at least partially related to the fact that the
breakdown of carboxylates in the biomass from large release of volatiles from biomass takes place at relatively
molecular mass structures and the subsequent release low temperature (Fig. 2) and is a relatively rapid process
of light carboxylates might also be an important mech- favouring the survival of COOH and COOX struc-
anism for the release of AAEM species from the pyroly- tures in the volatiles.
sis of biomass at low temperatures (e.g. 500 C in Figs. 3 The experimental procedure applied in this study
and 4). does not allow for a clear distinction between carboxylic
The yields of acetate and formate from the pyrolysis acids and carboxylates when released from the biomass.
of cane trash were determined for fast heating rate It is likely that the majority of acetate and formate de-
experiments. At 500 C, approximately 25 wt% (db) of tected may have been released as acetic acid and formic
the cane trash fed to the reactor was released as acetate acid from the biomass. However, it is highly probable
and 1 wt% (db) as formate. Subsequent increases in that at least some were in the carboxylate salt form,
 100 bonds between AAEM species and char matrix are ther-
80 mally stable regardless of the original forms (chlorides
or carboxylates) of AAEM species in the biomass
60
substrates.
Retention of species in char [%]

40 In contrast, when temperature was increased from

20 (A) Na 500 to 900 C for the fast heating rate experiments, the
0 eects of increasing temperature strongly depended on
100
the biomass substrate. For the pyrolysis of bagasse,
80 increasing temperature from 500 to 900 C led to signi-
cant reductions in the retention of all AAEM species
60
(Na, K, Mg and Ca): less than 40% of these AAEM spe-
40
cies present in the bagasse were retained in the char at
20 (B) K
900 C (Fig. 3). This behaviour is contrastingly dierent
0
to the slow heating rate experiments (Fig. 3). Signicant
100
dierences in the retentions of AAEM species between
80 the fast and the slow heating rate experiments were
60 found at 700 C with more notable dierences with
40 increasing temperature. This temperature region also
(C) Mg
20 corresponds to the signicant dierences in the char
0 yield found between the fast and slow heating experi-
100
80 ments
cies at (Fig.
higher2).temperatures
Clearly, the large
at therelease of AAEM
fast heating rate spe-
were
60 at least partly due to the interactions of volatiles and
40 char. It is expected that the tar and light hydrocarbons
20 (D) Ca produced during the pyrolysis of biomass would be very
0 aliphatic in nature and prone to thermal cracking at ele-
500 600 700 800 900
vated temperatures, leading to the production of signi-
Temperature [C]
cant amounts of free radicals (especially H radicals).
Slow heating rate Fast heating rate
Free radicals interacting with char in the xed-bed
Fig. 4. Retention of (A) Na, (B) K, (C) Mg and (D) Ca in char during would take part in substitution reactions allowing the
the pyrolysis of cane trash as a function of temperature and heating volatilisation of AAEM species (Wu et al., 2002), which
rate in the uidised-bed/xed-bed reactor. may be represented symbolically with the following
reaction:

particularly considering that COOX (X = K, Na, Mg R CM X ! CM R X

or Ca) structures tend to be thermally more stable than
COOH structures. Furthermore, some carboxylates,
even of relatively low vapour pressure, may have been
released from the biomass particles, e.g. due to the
entrainment with the volatiles being released. Alterna-
tively, the carboxylates were released as part of high
molecular mass volatiles that may further decompose
outside the particles to give rise to the light carboxylates.
In any case, the release of carboxylate structures would
mean the volatilisation of AAEM species, providing a
plausible explanation for the release of AAEM species
at temperatures as low as 500 C (Figs. 3 and 4) or even
lower (Li et al., 2000; Olsson et al., 1997).
The data in Figs. 3 and 4 show that the eects of
increasing temperature on the volatilisation of AAEM
species depend on the type of biomass substrate, heating
rate and valence of the AAEM species. Increasing tem-
perature from 500 to 900 C at the slow heating rate
caused little changes in the volatilisation of all AAEM
species investigated (Na, K, Mg and Ca) for both
bagasse and cane trash. These results indicate that the
1
where CM denotes the char matrix, X represents the
AAEM species and R represents free radicals (including
H radicals). These data indicate that, while the bonding
between AAEM species and char may be thermally sta-
ble in the absence of radicals (as is the case of slow heat-
ing rate experiments explained above), the (H) radicals
present due to the volatilechar interactions would be
energetic enough to activate and break down the bonds
between AAEM species and char to result in the volatil-
isation of AAEM species.
Another possible reason for the decreasing retention
with increasing reaction temperature for fast heating
rate experiments is the reactions of volatile precursors
inside particles. During primary pyrolysis, concentra-
tions of hydrogen and other radicals would be much
higher than those from the gas phase (from volatiles).
Higher uidised-bed temperature will result in a higher
heating rate and therefore accelerated progress of the
primary pyrolysis. This will lead to enhancement of
reaction (1) during the radical/volatile-precursor forma-
tion inside the particle.
 Volatilechar interactions seem to explain the in-
creased volatilisation of K and Na with increasing tem-
perature during the pyrolysis of cane trash at the fast
heating rate (Fig. 4). However, the volatilechar interac-
tions were apparently not strong enough to activate and
break down the AAEMchar bonds in the cane trash
char for the release of Mg and Ca: the retentions of
Mg and Ca in the cane trash char were not aected by
the heating rate (Fig. 4). The retention behaviour of
Mg and Ca in cane trash is similar to that of Mg and
Ca in a Victorian brown coal (Li et al., 2004; Wu
et al., 2002).
The higher retentions of Ca and Mg in cane trash
char than those in the bagasse char are surprising con-
sidering the higher Cl content in cane trash (0.176 wt%
db) than in bagasse (0.027 wt% db) (see Table 2). In
other words, the higher Cl content in cane trash com-
pared to bagasse did not lead to more extensive volatil-
isation of Mg and Ca (or K and Na) compared with
those in bagasse (Figs. 3 and 4), contrary to the common
belief that Cl in biomass is likely to lead to higher vola-
tilisation of AAEM species (Dayton et al., 1999; Jensen
et al., 2000; Olsson et al., 1997). In fact, it is likely that
Cl would inhibit the release of Ca and Mg, probably
through the formation of MgCl2 and CaCl2, which are
of high lattice energies.
The extent of Cl volatilisation from cane trash was
determined for fast heating rate experiments. Results
indicate that approximately 1% of Cl originally present
in raw cane trash was retained in the char after a
500 C fast heating rate experiment. The extensive vola-
tilisation of Cl observed at this low temperature is in
qualitative agreement with the Cl release reported in
literature for biomass (Bjo rkman and Stromberg,
1997) and coal (Quyn et al., 2002a). With increasing
reaction temperature, the retention of Cl increased:
about 80% of Cl was retained in char at 900 C. This is a
direct result of interactions between Cl-containing
volatiles and char held underneath the frit in the
freeboard (see Fig. 1). While Cl may be bonded into
the char organic matrix, it may also react with Mg
and Ca to form refractory MgCl2 or CaCl2. In any
case, the data in Figs. 3 and 4 as well as the release of
Cl at low temperature indicate that a higher content of
Cl in biomass does not mean a high volatilisation level
of AAEM species. In fact, as was pointed above, there
is not sucient Cl in bagasse or in cane trash to
account for their AAEM species.
Two other possible explanations may be proposed for
the high retention of Mg and Ca in cane trash char com-
pared with that in the bagasse char. The rst one is the
structures of bagasse and cane trash may be very dier-
ent in terms of the forms and dispersion of Mg and Ca.
For example, the Mg and Ca species in cane trash may
be in close vicinity with SiO2 in the cane trash. On heat-
ing, Ca and Mg react with SiO2 to form silicates to inhi-
bit the volatilisation of Mg and Ca. The second
possibility may be due to the dierence in the micro-
structure of bagasse and cane trash. During the process
that precedes bagasse production, sugar cane is mechan-
ically crushed in roll mills with hot water (6590 C)
so as to squeeze sugar-containing juice from it. This pro-
cess may destroy the original cell wall structure. Cane
trash undergoes no such process, implying that its cell
structure is intact at least prior to pyrolysis. Similar to
bagasse, cane trash showed little evidence of melting
during pyrolysis: its particles did not stick to the sand
particles in the uidised-bed. It is then likely that its cell
structure was largely retained during pyrolysis. It may
be imagined that Mg and Ca in cane trash were tightly
bound inside the cell wall and organelles and struggle
to be released: the cell structure may have had a caging
eect for the rather large Ca and Mg species and inhib-
ited their volatilisation. In contrast, the open cell
structure of bagasse would have had little resistance
for the volatilisation of AAEM species.
4. Conclusions
A sugar cane bagasse sample and a cane trash sample
have been pyrolysed in a novel uidised-bed/xed-bed
reactor. The volatilisation of AAEM species (Na, K,
Mg and Ca) during pyrolysis has been quantied. Our
results show that the volatilisation of AAEM species
depends on many factors such as biomass properties,
valence of AAEM species, heating rate and temperature.
Even for the bagasse and cane trash grown in the same
area (Queensland, Australia), the volatilisation of
AAEM species during pyrolysis showed distinct charac-
teristics. The dierence in their chlorine contents is not
sucient to account for the dierence in the volatilisa-
tion of AAEM species between them. In fact, Cl is volat-
ilised independently from K or other AAEM species and
does not show any ability to facilitate the volatilisation
of AAEM species. Pyrolysis at a slow heating rate with
minimised volatilechar interactions would lead to min-
imal (often <20%) volatilisation of AAEM species from
these biomass samples. Under uidised-bed conditions
encouraging fast particle heating rates and volatilechar
interactions, over 80% of Na, K, Mg and Ca may be
volatilised from bagasse during pyrolysis at 900 C.
While the volatilisation of monovalent Na and K species
from cane trash was similar to that from bagasse, the
volatilisation of Mg and Ca from cane trash was always
limited. In addition to possible dierences in the form
and dispersion of Mg and Ca in cane trash and in ba-
gasse, the dierence in the cell structure between cane
trash and bagasse may be partly responsible for their
dierence in the volatilisation of Ca and Mg: the open
cell structure of bagasse may favour the volatilisation
of Mg and Ca compared with the intact cell structures
in cane trash.
Acknowledgement
The authors gratefully acknowledge the nancial sup-
port of this study by New Energy and Industrial Tech-
nology Development Organisation (NEDO) in Japan.
The authors also thank Drs. T.F. Dixon and P. Hobson
at Sugar Research Institute (SRI) in Australia for sup-
plying sugar cane bagasse and cane trash.
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