Liquefaction studies of some Indonesian low rank coals

Y. Artanto
a,b
, W.R. Jackson
a,
*
, P.J. Redlich
a
, M. Marshall
a
a
Department of Chemistry, Monash University, Clayton, Victoria 3168, Australia
b
BPPT (Badan Pengkajian dan Penerapan Teknologi), J1. MH. Thamrin 8, Jakarta, Indonesia
Received 2 September 1999; received in revised form 16 November 1999; accepted 23 November 1999
Abstract
One sub-bituminous and ve brown coals from South Banko and Kalimantan, Indonesia have been evaluated under a range of liquefaction
conditions for the provision of liquid fuels. The coals were reacted with hydrogen using various catalysts in the presence and absence of a
donor solvent, both with and without added sulfur-containing compounds. In addition, the coals have been reacted with CO/H
2
O in the
presence and absence of an added alkali catalyst, sodium aluminate. The results conrm the effectiveness of Ni/Mo in the absence of added S,
and Mo in the presence of S, as catalysts for solvent-free hydrogenation of low rank coals. The most interesting nding for the CO/H
2
O
reactions was that Tanito Harum, a sub-bituminous coal, gave as high a conversion as any of the low rank coals. 2000 Elsevier Science Ltd.
All rights reserved.
Keywords: Liquefaction; Indonesian low-rank coals; No-solvent hydrogenation; Catalysts; CO/H
2
O/alkali
1. Introduction
Oil demand in Indonesia is increasing at 56% per annum
due to rapid industrialisation, whereas domestic oil produc-
tion is declining by 4% annually [1]. On the basis of these
gures, it is predicted that Indonesia will suffer an oil crisis
by the year 2006.
Therefore, energy diversication, which utilises alter-
native energy resources, is needed to postpone the oil crisis
and to facilitate further economic growth.
It has been estimated that around 45 billion tonnes of low
rank coal are accessible in the Indonesian islands [2].
However, these low-rank coals are not economically trans-
portable and are not marketed because of their high water
content ( 35 wt%) and tendency to spontaneously ignite
when dried. Therefore, the utilisation of these low-rank
coals for oil production is being evaluated by the Indonesian
Agency for the Assessment and Application of Technology
(BPPT).
In this study, two approaches to coal liquefaction have
been investigated, both of which have been shown to give
good conversions with other low rank coals. The rst of
these, the organic solvent free hydrogenation of coals
impregnated with catalysts, was pioneered by Weller and
Pelipetz [3], and further developed by groups led by Derby-
shire [4] and Schobert [5]. It has been shown to give high
yields of liquid products from some Australian low rank
coals [6] and good yields from some bituminous and sub-
bituminous coals [7]. Pilot plant operation has established
that high capital, maintenance and operational costs are
associated with the provision of recycle solvents of appro-
priate quality [8]. Thus enormous potential savings exist if
high conversions can be achieved for solventless reactions.
An efcient catalyst recovery is obviously essential for
commercial development to succeed.
The second method involved reaction of the coals with
carbon monoxide and water in the presence of a sodium
aluminate catalyst (CO/H
2
O/NaAlO
2
), based on the original
observations of Fischer and Schrader [9]. This method using
water as a medium does not require drying of coal, which
represents a signicant saving when working with low rank
coals. Reactions of low rank coals using a variety of alkaline
catalysts have been shown to give moderate to high conver-
sions combined with low asphaltene yields [1014].
2. Experimental
2.1. Coals
The elemental composition of the six Indonesian coals
and a comparison with a Victorian brown coal (Loy
Yang) are given in Table 1. The coals were ground to less
than 75 mm and stored under water. In order to evaluate the
Fuel 79 (2000) 13331340
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PII: S0016-2361(99)00275-6
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* Corresponding author. Tel.: 61-3-9905-4552; fax: 61-3-9905-4597.
E-mail address: w.r.jackson@sci.monash.ed.au (W.R. Jackson).
effects of the inorganic constituents on liquefaction, some
coals were washed with 0.1 M H
2
SO
4
solution (acid/coal
ratio 20:1). The coalacid solution mixture was held
under vacuum for 1 h, stirred for 24 h and then ltered,
with the pH of the ltrate being monitored. The coal was
then slurried with distilled water, stirred for 24 h and again
ltered. This slurryingstirringltration procedure was
repeated until the pH of the ltrate became constant. The
acidwashed coals were then representatively divided using
a V shaped splitter and stored under water until required
[15]. They were characterised by using the product analyses
and distribution from pyrolysis and liquefaction reactions
under standard conditions established in earlier work (see
below).
The inorganic constituents of the coal were examined by
analysis of the ash using a borate fusion/ICP method based
on the Australian standard AS 1038.14.1. The material
extracted from the coal by 0.003 M H
2
SO
4
was analysed
by ICP of the resulting solution. The results are summarised
in Table 2. Two of the coals, Gegas River (GR) and North
Suban Jeriji (NSJ), had relatively high S contents; the distri-
bution of iron and sulfur types was estimated for all of the
coals and is summarised in Table 3.
2.2. Catalyst addition
Ni
II
and Co
II
acetates (0.2 wt% db Ni or Co), ammonium
heptamolybdate (0.6 wt% db Mo) and sodium aluminate
(NaAlO
2
, 1.2 wt% db Na) were added as aqueous solutions
to the coals. 10 g of coal db was slurried with distilled water
under vacuum for about 20 min to ensure complete wetting
prior to catalyst addition. Catalysts were dissolved in 50 ml
distilled water (Ni: 0.2 wt% db coal, Mo: 0.6 wt% db coal,
Co: 0.2 wt% db coal, NaAlO
2
: 4.1 wt% db coal) and then the
solution was ultrasonicated for 2 min and added to the coal
water slurry. The coalcatalyst mixture was then stirred for
another 20 min. Afterwards, the liquid water was removed
under vacuum (0.1 kPa) at ca. 30C [16].
Sulded forms of the catalysts were obtained by the
addition of 0.03 ml of carbon disulde to the reaction
mixture as recommended by Derbyshire et al. [4].
2.3. Hydrogenation and pyrolysis reactions
Reactions were performed in 35 ml, 316 stainless steel
tubular reactors loaded with 1.0 g of dry, catalyst-impreg-
nated coal. The sealed reactor was ushed with H
2
and
Y. Artanto et al. / Fuel 79 (2000) 13331340 1334
Table 1
Ultimate analysis and ash yield
Coal Elemental Composition (wt% daf coal) Ash
(wt% db)
H/C C H N S O
a
Loy Yang ROM (LY ROM)
b
0.83 70.7 4.9 0.6 0.5 23.2 0.5
South Banko:
Lengi River (LR) 0.86 73.7 5.3 1.4 0.5 19.1 2.5
Gegas River (GR) 0.97 68.2 5.5 1.2 4.1 21.0 3.5
Selingsing River (SR) 0.92 70.5 5.4 1.1 0.4 22.7 5.5
North Suban Jeriji (NSJ) 0.87 70.1 5.1 1.5 3.2 20.1 5.4
AsamAsam (AA) 0.90 70.6 5.3 1.0 0.2 22.9 4.4
Tanito Harum (TH) 0.91 75.5 5.6 1.8 0.5 16.6 8.3
c
a
Oxygen calculated by difference.
b
Acid-washed coal, from La Trobe Valley, Victoria, Australia.
c
6.1% for acid-washed coal.
Table 2
The inorganic constituents of the coals (na: not available)
Coal Inorganic content of the coals (mmol/kg db) Inorganics extractable with 0.003 M H
2
SO
4
(mmol/kg db)
Si Al Fe Ti K Mg Na Ca Al Fe
NP
a
Ca Mg Na Cl
LY ROM na na 8 na na na na na na na na na na na
South Banko:
LR 60 90 43 2 3 12 9 92 60 38 90 12 4 6
GR 18 60 321 0.4 2 4 4 25 50 251 23 4 4 9
SR 180 230 68 9 5 60 17 260 60 63 200 60 9 6
NSJ 290 245 240 8 3 12 9 20 60 176 13 0.0 4 9
AA 280 130 152 5 7 40 9 52 60 147 50 40 4 3
TH 600 390 79 9 33 60 39 130 100 52 102 50 40 6
a
NP: not pyritic.
pressurised with 6 MPa (cold) H
2
. The reactor was rapidly
heated to 400C by immersing in a uidised sand bath set at
450C. Isothermal conditions were achieved within 2 min
with a maximum temperature overshoot of 23C unless
otherwise stated and the reactor was held at temperature
for 30 min. After the reaction, the reactor was rapidly cooled
in water and the gases vented. The solid/liquid products
were then thoroughly scraped and washed from the reactor
with dichloromethane (CH
2
Cl
2
) into a 250 ml round bottom
ask. Water was removed by Lundin azeotropic distillation.
Reaction products were extracted by ultrasonication and
fractionated into residues (CH
2
Cl
2
insoluble), asphaltenes
(CH
2
Cl
2
soluble, hexane insoluble) and oils (hexane solu-
bles). Duplicate reactions were carried out for Co/Mo and
Ni/Mo reactions and in some cases for coals which had been
treated with a single metal. Results were repeatable to ^2%
and the average values are given.
A standard set of reactions was carried out to calibrate
the reactivity of the coals relative to a series of Australian
[15] and International coals [17]. Reaction conditions were
as follows:
(1) 3 g of dry coal and 9 g of tetralin at 405C under
6 MPa hydrogen (cold) for 1 h;
(2) 6 g of dry coal and 12 g of decalin at 320/350C under
6 MPa nitrogen (cold) for 1 h;
(3) 9 g of dry coal without added solvent at 320/350C
under 6 MPa nitrogen (cold) for 1 h.
The conversions are shown in Fig. 1. Oils from reactions
(3) and asphaltenes from reactions (1) were analysed by
1
H
NMR. Spectra were recorded at 200 MHz for deutero-
chloroform solutions (CDCl
3
) with tetramethylsilane
(TMS) as an internal reference, using a Bruker AC-200
spectrometer. Selected spectra were recorded with D
2
O
exchange so as to suppress the OH proton signals of phenols
and alcohols and allow analysis of other underlying signals
of protons associated with carbons. The spectra were
separated into four regions: H
ar
, 9.06.0 ppm due to
aromatic and ArOH protons; H
a
, 4.51.96 ppm due to
protons on carbons adjacent to aromatic rings together
with protons on carbons joined directly to oxygen atoms,
H
b
, 1.961.0 ppm due to protons attached to carbons at least
one carbon away from an aromatic ring; H
g
, 1.00.5 ppm
due to methyl hydrogens at least two carbons distant from an
aromatic ring.
Gas liquid chromatography (GLC) was carried out using
a gas chromatograph with a 25 m BP-X5 capillary column
and a ame ionisation detector. Oven temperature was
raised from 30 to 320C at 4C/min, with a total run time
of 90 min.
2.4. CO/H
2
O/NaAlO
2
reactions
These reactions were carried out for 30 min in 35 ml
autoclaves loaded with 1.0 g of dry, catalyst-
impregnated coal and 2.5 ml H
2
O at 365 and 400C
with an initial CO pressure of 3 MPa. The workup
was identical to that of the hydrogenation reactions
except that the residues were rinsed with 2 M HCl 2
150 ml and then with distilled water 4 200 ml to
remove salts.
Y. Artanto et al. / Fuel 79 (2000) 13331340 1335
Table 3
The distribution of pyritic/non-pyritic iron and sulfur in the coal
Coal Concentration (mmol/kg db)
S total Fe Pyr Fe NP
a
S Pyr S NP
a
LR 150 5 40 10 140
GR 1230 70 250 140 1090
SR 120 5 60 10 110
NSJ 930 60 180 120 810
AA 50 5 150 10 40
TH 150 30 50 50 100
a
NP: not pyritic.
Fig. 1. Total conversion (3:1 tetralin/dry coal, 6 MPa initial H
2
pressure, 405C, 1 h reaction time) vs. atomic H/C ratio.
3. Results and discussion
3.1. Coal reactions under standard conditions
The reactivity of the Indonesian coals generally followed
the correlation between total conversion and atomic H/C
ratio established for a wide range of Australian and Inter-
national coals (Fig. 1) [15,17]. The only anomaly was TH
coal that gave a lower conversion than expected, but after
acid-washing the conversion rose to the expected value.
Conversions usually decrease when Victorian brown coals
are acid-washed [18] in contrast to American sub-bitum-
inous and brown coals, which often show increased conver-
sion after acid-washing [19]. The good t to the correlation
was somewhat surprising as the correlation was established
for acid-washed coals in order to minimise the catalytic
effects of inherent metals. Some of the Indonesian coals
(NSJ and GR) have high iron contents (250300 mmol/kg
db), which could have been expected to lead to the increased
reactivity [18].
The reactions of the low rank coals at 320C in decalin
gave conversions between 17 wt% for NSJ (H/C, 0.87) and
34% for GR (H/C, 0.97) generally increasing with atomic
H/C ratio and following a trend similar to that established
for the Victorian and New Zealand brown coals [15,17]. The
sub-bituminous TH coal gave, as expected, a lower conver-
sion (10 wt%).
3.2. Coal structure
Information concerning coal structure can be derived
from reactions under standard conditions [17]. The oils
from pyrolysis at 320C in the absence of solvent were
examined by
1
H NMR and GLC.
1
H NMR data are
summarised in Table 4.
The high H
b
values for all of the oils from the Indonesian
Y. Artanto et al. / Fuel 79 (2000) 13331340 1336
Table 4
Hydrogen distribution from
1
H NMR spectra of oils
Coal sample
1
H NMR distribution of oils
a
H
ar
H
a
H
b
H
g
TH 0.11 0.21 0.50 0.18
South Banko:
LR 0.09 0.16 0.60 0.14
GR 0.10 0.23 0.54 0.13
SR 0.10 0.17 0.56 0.15
NSJ 0.13 0.18 0.57 0.12
AA 0.11 0.18 0.56 0.15
LY ROM 0.12 0.23 0.49 0.16
a
Oils produced form pyrolysis at 320C except from TH coal which was
pyrolysed at 350C.
Fig. 2. Product yields from hydrogenation of Co/Mo-treated coals. (OGW oil gas water).
coals reect the high wax content of the coals and are
consistent with their high atomic H/C ratios. The GLC
analysis was consistent with the
1
H NMR data, showing
the presence of signicant amounts of n-alkanes. The
aromatic portions of the chromatograms were very similar
to those reported for some Victorian brown coals [20], with
phenol and naphthalene substituted with short alkyl chains.
1
H NMR spectra of asphaltenes produced from reactions
of the Indonesian brown coals with 6 MPa H
2
(cold) in
tetralin at 405C for one hour showed
1
H distributions in
the range H
ar
, 0.270.30; H
a
, 0.350.40; H
b
, 0.260.29; and
H
g
0.060.08, very similar to those reported for the Victor-
ian brown coals with similar atomic H/C ratios [21].
This evidence strongly suggests that the Indonesian coals
share many structural features with their Victorian counter-
parts. This is consistent with their similar age [22,23], but
perhaps surprising in view of the very different climatic
conditions and vegetation in the two regions in the Oligo-
cene/Miocene.
3.3. Metal-catalysed hydrogenations in the absence of
added organic solvent
3.3.1. Reactions without added catalysts
The raw coals were reacted with H
2
at 400C for 30 min.
GR coal with a high atomic H/C ratio (0.97) gave a good
conversion (69 wt%), presumably due to the presence of
iron and sulfur in this coal (see Tables 2 and 3). The NSJ
coal, also with high iron and sulfur contents, gave a modest
conversion (33 wt%), which increased signicantly (to
48 wt%) on addition of sulfur. All the other coals gave
modest conversions (2534 wt%), which were not signi-
cantly increased by the addition of sulfur as CS
2
(26
36 wt%). The higher rank TH coal gave slightly lower
conversions (ca. 22 wt%).
3.3.2. Catalysis by Co/Mo
The coals were impregnated with Co (0.2 wt% db) and
Mo (0.6 wt% db), which is the ratio of Co/Mo found in
many commercial catalysts. The results of reactions under
the standard conditions and with added CS
2
are shown in
Fig. 2.
In the absence of added sulfur, only GR gave a high and
NSJ a moderate conversion, again probably because of the
high sulfur content of these coals. On addition of sulfur, the
low conversions (ca. 40 wt%) of the other coals and the
moderate conversion (57 wt%) of NSJ were all increased
to 8287 wt%, except that of TH, the subbituminous coal,
which was 74 wt%. The results for the low rank, low-sulfur
Indonesian coals are comparable to those found for a typical
Victorian coal, LY ROM (see Fig. 2).
3.3.3. Catalysis by Ni/Mo
Results for hydrogenations of Ni/Mo-treated coals are
shown in Fig. 3. Conversions for reactions without added
sulfur were much higher than for the Co/Mo-catalysed
Y. Artanto et al. / Fuel 79 (2000) 13331340 1337
Fig. 3. Product yields from hydrogenation of Ni/Mo-treated coals. (OGW oil gas water).
reactions. Addition of sulfur generally led to small but
signicant increases such that the conversions for several
of the coals (SR, GR and AA) were over 90 wt%, in some
cases 510% higher than the values obtained using the Co/
Mo/S-catalyst system.
3.3.4. Catalysis by single metals, Mo, Ni or Co
The contribution of the individual metals to the above
catalytic systems was investigated by impregnating the
coals with the individual metals, Ni and Co (0.2 wt% db)
and Mo (0.6 wt% db), the same amounts as were used in the
mixed catalysts. Detailed results for reactions involving Mo
are shown in Fig. 4.
Low conversions were obtained for reactions of all coals
in the absence of added sulfur except for the high S-contain-
ing coals, GR and NSJ. A comparison of Fig. 4 with Fig. 2
shows that the Co in Co/Mo had an effect of less than 5 wt%
in all cases except for AA coal (7 wt%). Addition of S as
CS
2
raised the conversions for Mo-treated coals to 79
88 wt%, except for the subbituminous TH coal (71 wt%).
Comparison with Fig. 2 also shows that the Co had little
effect even in the presence of CS
2
. The conversions for Mo/
CS
2
were comparable to those for Ni/Mo and Ni/Mo/CS
2
,
though generally slightly lower than for the latter.
The conversions for Ni-impregnated coals were the same,
or higher (by 20 wt% for TH) than for Mo-treated coals.
Addition of CS
2
, however, did not lead to such large
increases in conversions as for Mo, and the increases were
in the form of the less desirable asphaltene rather than oil.
The conversions for Co-impregnated coals were little higher
than for uncatalysed reactions of the same coals and
addition of CS
2
had little effect except for the sub-
bituminous TH coal. The reaction results were broadly simi-
lar to those for a typical Victorian brown coal such as LY
ROM.
3.4. CO/H
2
O/NaAlO
2
reactions
An alternative process to hydrogenation for the liquefac-
tion of the low rank coals involves their reaction with CO/
H
2
O in the presence of an alkaline catalyst [9]. Sodium
aluminate has been shown to be very effective alkaline cata-
lyst [13,14]. The Indonesian coals were thus reacted with
CO/H
2
O/NaAlO
2
. Reactions at 365C showed an increase in
the order of 20% relative to reactions without added NaAlO
2
except for NSJ coal. The results for the catalysed reactions
at both 365 and 400C are shown in Fig. 5.
The conversions at both 365 and 400C for the Indonesian
coals are similar to that for the LY ROM Victorian coal
[24]. In addition, conversion results for a suite of
Y. Artanto et al. / Fuel 79 (2000) 13331340 1338
Fig. 4. Product yields from hydrogenation of Mo-treated coals. (OGW oil gas water).
International coals at 365C gave very comparable conver-
sions [14].
The effect of the mineral and inorganic matter on these
reactions was briey examined by carrying out reactions of
acid-washed TH and GR coals at 365 and 400C. The
conversions for the GR coal increased by 13 and 14% for
reactions at the two temperatures, whereas no increase was
observed for the TH coal. Increase in conversion for a CO/
H
2
O/NaAlO
2
reaction of ca. 8% has previously been
observed on acid-washing a Wyoming subbituminous coal
[25] and shows that the effect of mineral and inorganic
matter on these reactions cannot be ignored.
All of the reactions gave products which contained only
small amounts (10 wt%) of asphaltenes, except for the
product from the subbituminous TH coal.
4. Conclusions
The Indonesian coals show results similar to those
obtained for other low rank coals in the two liquefaction
systems studied. The use of catalysts containing Mo/S to
give high yields of liquid products in the absence of added
organic solvents has been demonstrated, conrming obser-
vations made earlier by Derbyshire and his co-workers [4].
However, the use of a Ni/Mo catalyst gives comparable, and
even slightly better results in some cases, without the addi-
tion of sulfur.
Reactions with CO/H
2
O/NaAlO
2
gave products with low
asphaltene yields except for the subbituminous TH coal (ca.
15 wt% asphaltene). However, it should be noted that a
conversion of ca. 70 wt% was obtained from 30 min reac-
tion at 400C of this coal, similar to that for a Ni/Mo/S
catalysed reaction with H
2
under similar conditions.
Acknowledgements
One of us (YA) thanks AusAid for a scholarship and we
thank BPPT and PTBA (Indonesia) for provision of coal
samples.
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