Journal of Supercritical Fluids 18 (2000) 73 – 79

[Link]/locate/supflu

Physical properties of low rank coals dried with supercritical

carbon dioxide
Yoshio Iwai a,*, Tadaaki Murozono a, Yasutake Koujina a, Yasuhiko Arai a,
Kinya Sakanishi b
a
Department of Chemical Systems and Engineering, Graduate School of Engineering, Kyushu Uni6ersity, 6 -10 -1 Hakozaki,
Higashi-ku, Fukuoka 812 -8581, Japan
b
National Institute for Resources and En6ironment, 16 -3 Onogawa, Tsukuba, Ibaraki, 305 -8569, Japan

Received 19 September 1999; received in revised form 25 February 2000; accepted 18 April 2000

Abstract

Three coal samples from low rank coals (Berau and Taiheiyo) were prepared, such as raw coals, dried coals with
supercritical carbon dioxide, and thermally dried coals at 110°C. The physical properties of three samples were
analysed by a FT-IR spectroscopy, BET surface area measurement, and solvent swelling with pyridine and methanol.
The FT-IR spectra of Berau and Taiheiyo coals showed that the infrared absorption for the thermally dried coals was
slightly different from those of the raw coals and coals dried with supercritical carbon dioxide. The surface areas of
Berau and Taiheiyo coals dried with supercritical carbon dioxide were larger than thermally dried coals. The changes
of structures in the coals may be minimized by drying with supercritical carbon dioxide especially at higher pressures.
From the swelling experiments with pyridine, the swelling ratio of Berau coal dried with supercritical carbon dioxide
was the highest and that of the thermally dried coal was the lowest among the samples. The swelling results of
Taiheiyo coal showed almost the same tendency as those of Berau coal. This indicates that the swellability of low rank
coals is enhanced by drying with supercritical carbon dioxide. © 2000 Elsevier Science B.V. All rights reserved.

Keywords: Carbon dioxide; Coal; Lignite; Sub-bituminous coal; Supercritical fluid drying

1. Introduction tive drying has detrimental effect on the coal

conversion. For example, oxidation reaction to
Drying of coals plays an important role in coal form more oxygen functional groups and irre-
conversion processes. In pyrolysis of coals, water versible changes in the coal structures should be
reserved at various places inside the coals prevents caused by heating at temperatures than 100°C.
the heat transfer and the reactivity during the Recently, an advanced coal drying process able to
heating processes. However, the thermal or oxida- prevent the declination in reactivity of coals has
been given much attention, as one of the pretreat-
* Corresponding author. Tel./fax: +81-92-642-3496. ment techniques to improve the efficiency in the
E-mail address: iwai@[Link] (Y. Iwai). coal conversion processes [1–4].

0896-8446/00/$ - see front matter © 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 8 9 6 - 8 4 4 6 ( 0 0 ) 0 0 0 5 9 - 0
74 Y. Iwai et al. / J. of Supercritical Fluids 18 (2000) 73–79

In an earlier work [5], the authors performed hydrogen bonds assigned at high wavenumber
the extraction of water from the coals with super- such as OHether and OHp bonds are released
critical carbon dioxide, and showed that water by heat treatment, but strong hydrogen bonds
contained in the coals can be almost removed by assigned at low wavenumber such as OHN hy-
supercritical carbon dioxide at low temperature drogen bonds still remain. The released OH
(313.2 K). It is noted that coal drying near room groups again form weak hydrogen bonds such as
temperature may be accelerated by using super- OHp bond.
critical carbon dioxide. It seems that drying of Solvent swelling is usually performed using pyr-
coals with supercritical carbon dioxide will be idine, tetrahydrofuran and amine compounds, be-
much more costly than thermal drying. However, cause these solvents can easily break most of
drying with supercritical carbon dioxide at low noncovalent interactions and strong polar or hy-
temperature may prevent degradation of coals due drogen bonded sites in the coals. Especially, an
to thermal effects. In this work, the properties of electron donor solvent such as pyridine can easily
the coals dried with supercritical carbon dioxide break the noncovalent cross-linkings such as CO
were analyzed and compared with those of the bonds. Swellabilities of coals are dependent on the
thermally dried and raw coals in order to examine characteristics of solvents used and the physical
the effect of supercritical carbon dioxide drying and chemical changes in coal structures caused by
on the coal structures. FT-IR spectroscopy, BET drying. In this work, pyridine and methanol were
surface area measurement, and solvent swelling used as the solvents.
were adopted to analyze the physical properties of
the coals.
The changes of oxygen functionality in the low 2. Experimental section
rank coals can be identified by the information
obtained from FT-IR spectra [6 – 9]. The oxidized 2.1. Sample preparation
coals and the coals having large oxygen contents
show strong oxygen functionalities. In the present Berau coal as lignite from Indonesia and Tai-
work, the physical changes of coal structures heiyo coal as a sub-bituminous coal from Japan
caused by drying are examined. Some workers were adopted. Analysis of the coals are reported
have reported on the studies with respect to hy- in a previous paper [5]. These coals were ground
drogen bonds caused by drying. Painter et al. [6] and screened to prepare 18–30 mesh size particles
have shown that absorption bands of five hydro- (500–850 mm). The samples were placed in wide-
gen bonded OH groups exist in the spectrum mouth jars and stored in a desiccator at room
between 2800 and 3600 cm − 1, and hydrogen temperature. The initial weight percent of water in
bonding force is weak at high wavenumbers. Mi- Berau and Taiheiyo coals are about 23 and 6%,
ura et al. [7] have concluded that relatively weak respectively.
Berau and Taiheiyo coal samples were dried
Table 1 with supercritical carbon dioxide at 313.2 K and
Water contents in coal samples 9.8, 14.7 MPa according to the experimental pro-
cedure previously reported [5]. The weight of coal
Sample Berau coal Taiheiyo coal
samples, flow rate of carbon dioxide, and drying
(g-water/g-dried (g-water/g-dried
coal) coal) period were about 8 g, 1.5 mol h − 1, and 20 h,
respectively. Thermally dried coal samples were
Supercritical 0.0188 0.0100 prepared by heating at 110°C in air for about 25
drying h. Water contents in coal samples are presented in
(14.7 MPa)
Table 1. The values listed in Table 1 were ob-
Thermal drying 0.0153 0.0091
(110°C) tained from an arithmetic average of more than
Raw coal 0.2271 0.0622 three measurements at each condition, and experi-
mental errors were within 92%.
 Y. Iwai et al. / J. of Supercritical Fluids 18 (2000) 73–79 75

2.4. Sol6ent swelling experiments

The measurements of solvent swelling were per-

formed in scaled glass tubes of 6 mm inner diame-
ter and about 20 cm length. The coal samples
were ground to prepare under 100 mesh size
particles (150 mm) with the mortar and pestle. The
coal samples (0.4 g) were placed in the tubes, and
then tapped for 2 min to permit accurate measure-
ments of initial packed heights, H0, of the coals.
Solvents (5 ml) were added to the glass tubes, and
contents were vigorously stirred. Pyridine and
methanol were used as solvents. The glass tubes
were placed in a thermostat bath at 42°C. N2 gas
was passed in the tubes at low flow rate (1 ml
Fig. 1. FT-IR spectra of Berau coal. The used three samples
are the coal dried with supercritical carbon dioxide at 313.2 K
min − 1). After the settlement, the heights of the
and 14.7 MPa, the thermally dried coal at 110°C, and the raw swollen coals, Ht, were measured every 1 h. Be-
coal. fore the measurements of Ht, the glass tubes were
tapped for 1 min. After 24 h, the equilibrium was
2.2. FT-IR spectra analysis achieved. The swelling ratio is defined by Ht/H0.

The FT-IR spectra of the coal samples were

measured using a Fourier transform infrared spec- 3. Results and discussion
trophotometer (JEOL; JIR – 5500) at a resolution
of 4 cm − 1. The samples were prepared as KBr 3.1. FT-IR spectra
pellets. The dried and raw coals were ground to
under 100 mesh particle sizes (150 mm) with mor- Fig. 1 shows the FT-IR spectra of three sam-
tar and pestle. The coal samples (1.5 mg) were ples of Berau coals; the coal dried with supercriti-
mixed with KBr powder (150 mg), and were cal carbon dioxide at 313.2 K and 14.7 MPa, the
ground again. The KBr pellets were predried at thermally dried coal at 110°C, and the raw coal.
40°C for 24 h in a vacuum oven to remove The spectra of the OH stretching vibrations re-
moisture until water contribution was negligible lated to hydrogen bonding appear in the region
( B 0.05%). The FT-IR spectra of the coal samples between 3000 and 3600 cm − 1. From this figure, it
were obtained by subtracting the reference spectra is observed that the intensity of hydrogen bonding
of pure KBr from the sample spectra. for the thermally dried coal in the region between
3400 and 3600 cm − 1 is slightly stronger than that
2.3. BET surface area measurements of the other two samples. On the other hand, the
OH stretching band of the coal dried with super-
The BET surface areas and pore volumes of the critical carbon dioxide almost overlaps with that
coals were measured by a standard N2 gas adsorp- of the raw coal. The difference among the spectra
tion analysis using a commercial instrument of coal samples is too small to identify the func-
(FISONS Instrument Co. Ltd.; Sorptmatic 1990). tional group of hydrogen bondings induced by
The coal samples (about 0.4 g) were pretreated drying. But the change due to the drying methods
prior to the BET surface area measurements. The appeared.
coal sample was placed in a sealed glass tube, and Fig. 2 shows the FT-IR spectra of the two
degassed at 50°C for 1.5 h. After the pretreat- samples of Taiheiyo coals; the coal dried with
ment, the glass tube was set in the instrument, and supercritical carbon dioxide at 313.2 K and 14.7
the measurements were carried out. MPa, and the thermally dried coal at 110°C. It is
76 Y. Iwai et al. / J. of Supercritical Fluids 18 (2000) 73–79

found that change due to the drying method 3.2. Surface areas and pore 6olumes
appeared. However, the spectra difference between
samples of Taiheiyo coals is weaker than those of Table 2 shows the surface areas and pore vol-
the dried Berau coal, because the Taiheiyo coal is umes of the three samples for Berau and Taiheiyo
of a higher rank coal and has lower oxygen coals. The values listed in Table 2 were obtained
content than Berau coal. The changes in the coal from an arithmetic average of two measurements
structure caused by drying with supercritical car- at each condition, the experimental error being
bon dioxide have the similar tendency as in the within 9 5%. During degassing at 50°C, it is likely
case of Berau coals. that structural changes may be caused by removal
of water from all the samples. However, samples
dried with supercritical carbon dioxide and ther-
mally dried, which contain the same amount of
water, may suffer the structural change caused by
degassing to a similar extent. So it is reasonable to
compare these two samples. The surface areas and
pore volumes of Berau and Taiheiyo coals dried
thermally are the smallest among the samples. It is
well known that shrinkage of coals and collapse of
pores are caused by drying even at room tempera-
ture, as well as heat-treatment, and that if the
drying condition of low rank coals such as lignites
is severe their pores will collapse more [10–14]. As
a result, their surface areas decrease. The surface
areas of Berau and Taiheiyo coals dried with
supercritical carbon dioxide at 14.7 MPa are larger
than coals dried thermally and almost the same as
that of the raw coals. Furthermore, it is noted that
Fig. 2. FT-IR spectra of Taiheiyo coal. The used two samples Berau coal dried with supercritical carbon dioxide
are the coal dried with supercritical carbon dioxide at 313.2 K at higher pressure has a much larger surface area
and 14.7 MPa, and the thermally dried coal at 110°C. and pore volume than when dried at lower pres-
sure. It is suggested, that the changes of structure
Table 2 in the coals may be minimized by drying with
BET surface areas and pore volumes of coals
supercritical carbon dioxide especially at higher
Sample Surface area Pore volume×102 pressure, because supercritical carbon dioxide is
(m2 g−1) (cm3 g−1) sufficiently immersed and more effectively diffused
into the pores to extract water.
Berau coal
Supercritical drying
9.8 MPa 68.7 8.66
3.3. Sol6ent swellings
14.7 MPa 77.3 9.43
Thermal drying 66.2 6.95 In the present work, pyridine and methanol
(110°C) were used for the solvent swellings. Pyridine can
Raw coal 77.7 8.31 disrupt the noncovalent interactions as an electron
Taiheiyo coal donor. Methanol has an electron affinity for OH
Supercritical drying groups, and can break only weak noncovalent
14.7 MPa 63.1 5.77
interactions such as weak hydrogen bonds.
Thermal drying 58.2 5.04
(110°C) The swelling results of Berau and Taiheiyo coals
Raw coal 61.8 5.31 with pyridine are shown in Figs. 3 and 4 and the
equilibrium swelling ratios of the coals with
 Y. Iwai et al. / J. of Supercritical Fluids 18 (2000) 73–79 77

pyridine and methanol are shown in Table 3. The

values listed in Table 3 were obtained from an
arithmetic average of two measurements at each
condition, the experimental error being within
9 5%. Figs. 3 and 4 show that the coal samples
swell rapidly at the initial stage. After 6 or 7 h,
the equilibrium conditions of swollen coals are
gradually achieved. The swelling ratios of all the
samples for Berau coals with pyridine are larger
than those for Taiheiyo coals, because lower rank
coals have many noncovalent interactions such as
hydrogen bonds and noncovalent cross-linkings
Fig. 3. Solvent swelling ratios with pyridine for Berau coal. involving oxygen functional groups.
The used three samples are the coal dried with supercritical
The swelling rates of Berau and Taiheiyo coals
carbon dioxide at 313.2 K and 14.7 MPa ( ), the thermally
dired coal at 110°C ( ), and the raw coal (). dried with supercritical carbon dioxide and raw
coals have almost the same tendency at the initial
stage of swelling with pyridine, and those of the
thermally dried Berau and Taiheiyo coals are the
slowest among all the samples. This indicates that
the diffusional transport rates of pyridine in the
thermally dried coals are affected by the structural
changes as is observed from the results that the
surface areas and pore volumes of thermally dried
Berau and Taiheiyo coals are the smallest among
their samples. Berau and Taiheiyo coals dried
with supercritical carbon dioxide, of which sur-
face areas and pore volumes are larger than the
thermally dried coals, can uptake solvent rapidly
into the structures inside the coals. And, the equi-
Fig. 4. Solvent swelling ratios with pyridine for Taiheiyo coal. librium swelling ratios of Berau and Taiheiyo
The used three samples are the coal dried with supercritical coals dried with supercritical carbon dioxide are
carbon dioxide at 313.2 K and 14.7 MPa ( ), the thermally
dried coal at 110°C ( ), and the raw coal ().
the largest among their samples. Furthermore, on
the effects of water on the swelling of coals,
Suuberg et al. [15,16] have noted that the swelling
Table 3 rates of wet lignite and wet high-volatile bitumi-
Equilibrium swelling ratios of coals nous coals in pyridine increase rapidly compared
with dried coals, because water enhances the rate
Sample Solvent
of solvent uptake to a significant degree. The
Pyridine Methanol swelling of raw coals is also governed by the
moisture content in the coal.
Berau coal As seen from Table 3, the swelling ratios of
Supercritical drying (14.7 MPa) 3.40 1.69 Taiheiyo coal with methanol have the same ten-
Thermal drying (110°C) 3.00 1.77
Raw coal 3.10 1.43
dency as that of Taiheiyo coal with pyridine. But
in the case of Berau coals, the swelling ratio of the
Taiheiyo coal
thermally dried coal is the largest among all the
Supercritical drying (14.7 MPa) 2.72 1.55
Thermal drying (110°C) 2.62 1.47 samples. The solvent swelling of coals by
Raw coal 2.61 1.51 methanol affects only the weak noncovalent bond
interactions. The authors assume that methanol
78 Y. Iwai et al. / J. of Supercritical Fluids 18 (2000) 73–79

can disrupt only the weak cross-linking interac- Acknowledgements

tions such as additional weak hydrogen bonds
formed in Berau coal by thermal drying at 110°C. The authors gratefully acknowledge the finan-
Coal structure is released, and solvent uptake by cial support in part provided by Research for the
the coal may increase more rapidly than the coal Future Program (96P00401), the Japan Society
dried with supercritical carbon dioxide and raw for the Promotion of Science (JSPS).
coal.

References
4. Conclusions
[1] A. Ohki, X.F. Xie, T. Nakajima, S. Maeda, Coal proper-
The properties of Berau and Taiheiyo coals ties of upgraded low-rank coals by hot water drying
dried with supercritical carbon dioxide at 313.2 K method, in: Proc. ICCS, 1997, p. 487.
were analyzed by FT-IR spectra, BET surface [2] G.D. Bongers, F. Woskoboenko, W.R. Jackson, A.F.
Patti, R.J. Redlich, The properties of the coal and steam
area measurement and solvent swelling with pyri-
condensate from pressurised steam drying, Coal Sci. 1
dine and methanol. Their properties were com- (1995) 901.
pared with those of the thermally dried coals at [3] G.D. Bongers, W.R. Jackson, F. Woskoboenko, The use
110°C and raw coals. of a structural model to explain the behavior of brown
The change in coal structures caused by drying coal during pressurised steam drying, in: Proc. ICCS,
with supercritical carbon dioxide were different 1997, p. 483.
[4] T. Deguchi, T. Shigehisa, S. Katsushima, R. Nakanishi,
from those of thermally dried coals. The surface T. Shimizu, O. Okuma, Devolopment of UBC process, in:
areas of Berau and Taiheiyo coals dried with Proc. 7th Australian Coal Sci. Conf. 1996, p. 479.
supercritical carbon dioxide at 14.7 MPa are [5] Y. Iwai, M. Amiya, T. Murozono, Y. Arai, K. Sakanishi,
larger than those dried thermally. From this re- Drying of coals by using supercritical carbon dioxide,
sult, shrinkage and collapse of pore structures in Ind. Eng. Chem. Res. 37 (1998) 2893.
[6] P.C. Painter, M. Sobkowiak, J. Youtcheff, FT-ir study of
coal, observed in thermally dried coal, may be hydrogen bonding in coal, Fuel 66 (1987) 973.
minimized by drying with supercritical carbon [7] K. Miura, K. Mae, F. Morozumi, A new method to
dioxide. estimate hydrogen bondings in coal by utilizing FTIR and
Moreover, very interesting results are obtained DSC, Am. Chem. Soc., Div. Fuel Chem. 42 (1) (1997)
from the swelling experiment of the coals with 209.
[8] P.R. Solomon, R.M. Carangelo, FTIR analysis of coal. I.
pyridine and methanol. Diffusional transport Techniques and determination of hydroxyl concentra-
rates of pyridine in coals decreased by thermal tions, Fuel 61 (1982) 663.
drying. The diffusion rates of solvents in the coals [9] C. Chen, J. Gao, Y. Yan, Observation of the type of
dried with supercritical carbon dioxide are almost hydrogen bonds in coal by FTIR, Energy Fuels 12 (1998)
446.
the same as of raw coals. In the case with
[10] C. Song, A.K. Saini, H.H. Schobert, Effects of drying and
methanol, the effect of thermal drying for Berau oxidation of wyodak subbituminous coal on its thermal
coal is more emphasized than that of drying with and catalytic liquefaction. Spectroscopic characterization
supercritical carbon dioxide. Except for this case, and products distribution, Energy Fuels 8 (1994) 301.
the swelling ratios of coals dried with supercritical [11] F.P. Miknis, D.A. Netzel, T.F. Turner, J.C. Wallace,
C.H. Butcher, Effect of different drying methods on coal
carbon dioxide are always the largest among all
structure and reactivity toward liquefaction, Energy Fuels
samples. This indicates that the swellability of 10 (1996) 631.
coals can be enhanced by drying with supercritical [12] D.G. Evans, The Brown-coal/water system: Part 4.
carbon dioxide. Based on the present research, Shrinkage on drying, Fuel 52 (1973) 186.
supercritical carbon dioxide extraction of water [13] S.C. Deevi, E.M. Suuberg, Physical changes accompany-
ing drying of western US lignites, Fuel 66 (1987) 454.
from low rank coals is expected to be one of the
[14] K.S. Vorres, R. Kolman, T. Griswold, Kinetics of vac-
effective drying methods for the preparation of uum drying and rehydration of ILLINOIS c6 coal
activated or non-deteriorated coals in the combus- samples. Implications for pore structure, Am. Chem. Soc.,
tion and liquefaction process. Div. Fuel Chem. 33 (2) (1988) 333.
 Y. Iwai et al. / J. of Supercritical Fluids 18 (2000) 73–79 79

[15] E.M. Suuberg, Y. Otake, S.C. Deevi, Solvent swelling as [16] E.M. Suuberg, Y. Otake, Y. Yun, S.C. Deevi, Role of
a measure of the breakdown of the macromolecular struc- moisture in coal structure and the effects of drying upon
ture of coal, Am. Chem. Soc., Div. Fuel Chem. 36 (3) the accessibility of coal structure, Energy Fuels 7 (1993)
(1991) 258. 384.