International Journal of Coal Geology 51 (2002) 69 – 92

www.elsevier.com/locate/ijcoalgeo

High-pressure methane and carbon dioxide adsorption on dry

and moisture-equilibrated Pennsylvanian coals
B.M. Krooss a,*, F. van Bergen b, Y. Gensterblum a,
N. Siemons a, H.J.M. Pagnier b, P. David b
a
Aachen University of Technology, Aachen, Germany
b
Netherlands Institute of Applied Geoscience TNO—National Geological Survey, The Netherlands
Received 10 August 2001; accepted 15 March 2002

Abstract

In the context of research on the reduction of CO2 emissions and the production of coalbed methane (CBM), high pressure
adsorption measurements of CH4 and CO2 have been performed on dry and moisture-equilibrated Pennsylvanian coals of
different rank (0.72, 1.19 and 1.56% VRr). Adsorption isotherms of the two gases were measured up to pressures of 20 MPa
(200 bar), at 40, 60 and 80 jC using a volumetric method. Total excess sorption capacities for methane on dry coals ranged
between 11 and 14 Std. cm3/g coal. The 40 jC sorption isotherms showed a saturation behavior while the 60 and 80 jC
isotherms exhibited a monotonous increase over the entire experimental pressure range (up to 20 MPa). Methane sorption
capacities of moisture-equilibrated coals were lower by f 20 – 25% than those for dry coals and ranged between 7 and 11 Std.
cm3/g coal. No distinct maturity effect was discernible for methane adsorption on the three samples studied, neither in the dry
nor in the moist state. CO2 adsorption isotherms for dry and moist coals showed substantial differences. For dry coals the
highest CO2 excess sorption capacities were observed at 40 jC with maximum values of 70 Std. cm3/g within limited pressure
ranges. Carbon dioxide excess sorption for the moisture-equilibrated coals was usually lower than for the dry samples in the low
pressure range. All high-pressure CO2 adsorption isotherms for moist samples were bimodal with distinct minima and even
negative excess sorption values in the 8 – 10 MPa (80 – 100 bar) range. Beyond this range CO2 adsorption capacity increased
with increasing pressure. High-temperature (80 jC) sorption capacities for CO2 were very low ( < 5 Std. cm3/g) in the low-
pressure range but reached much higher levels (25 – 50 Std. cm3/g) above 12 MPa. The strong bimodal character of the CO2
excess isotherms on moist coals is interpreted as the result of a swelling effect caused by supercritical CO2 and enhanced by
water. Some extent of swelling was also inferred for dry coals. Absolute sorption isotherms for CO2 were calculated assuming a
sorbed-phase density of 1028 kg/m3 and compared with literature data. Like the excess isotherms, the absolute isotherms show a
distinct decline in the 8 – 10 MPa pressure interval. At higher pressures, however, they increase monotonously. D 2002 Elsevier
Science B.V. All rights reserved.

Keywords: High-pressure adsorption; Excess sorption capacity; Coalbed methane; Carbon dioxide; Pennsylvanian coals; CO2 storage

1. Introduction
* Corresponding author. Rheinisch-Westf älische Technische
Hochschule, Lehrstuhl für Geologie, Geochemie und Lagerstätten
des Erdöls und der Kohle, Lochnerstrasse 4-20, 52056 Aachen,
Reducing carbon dioxide (CO2) emissions in order
Germany. Fax: +49-241-80-95753. to control the overall levels of CO2 in the atmosphere
E-mail address: krooss@lek.rwth-aachen.de (B.M. Krooss). has become an international priority in the wake of the

0166-5162/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 6 - 5 1 6 2 ( 0 2 ) 0 0 0 7 8 - 2
70 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92
Kyoto Protocol. In that protocol, the Netherlands
committed to reducing their CO2 emissions by 6%
from 2008 to 2012. Despite all past and ongoing
efforts put into the development of sustainable energy
supply, the world still depends heavily on fossil fuels
and will continue to do so for years to come. For this
reason, technology options are required that will allow
for the continued use of fossil fuels without substan-
tial emissions of CO2. Subsurface storage of CO2 in
geological systems is considered as one promising
perspective, which is currently being investigated
worldwide. This concept can be defended by the basic
principle of closed circles: emitted CO2 originates
from fossil fuel, taken from the subsurface, and should
therefore be returned to the subsurface. In general, the
research window for projects on subsurface CO2
storage is slowly but surely shifting from desk studies
to demonstrations. One of the options considered in
this context is the storage of CO2 in underground coal
seams.
The injection of CO2 into coal while simultane-
ously producing coalbed methane (CBM) combines
the production of a ‘‘clean’’, hydrogen-rich fossil fuel
(methane) with CO2 sequestration (see Hamelinck et
al., 2001). The advantages expected from injecting
CO2 into coalbeds are numerous: apart from the effect
of CO2 sequestration it may accelerate CBM produc-
tion and improve the recovery of CBM (therefore the
term Enhanced CBM production, or ECBM). Another
benefit of this technology is that coal seams that
cannot be profitably mined could still be exploited
for the in situ methane, making available substantial
amounts of fossil fuel that could otherwise not be used
for energy production. Finally, this new technology
could be used for the decentralised generation of
energy in remote areas close to coal-bearing basins,
minimising the costs of energy transportation. To date,
only a few experimental ECBM/CO2 field sites have
been realised worldwide. A micro-pilot field test was
set-up in Alberta (Canada) by the Alberta Research
Council (Gunter et al., 1997, 1998), while the world’s
first large-scale ECBM pilot using CO2 injection is
operated by Burlington Resources in the San Juan
Basin in New Mexico, USA (Schoeling and McGov-
ern, 2000; Reeves and Schoeling, 2000; Gunter et al.,
1998). In Europe, the first field experiment with
ECBM/CO2 is scheduled to start in 2003 in the Upper
Silesian Coal Basin in Poland. The ongoing tests
document the great potential of this process for both
CO2 sequestration and ECBM production.
Two main advantages must be emphasised that CO2
storage in coal has above other subsurface sequestra-
tion options. Firstly, injected CO2 replaces adsorbed
CH4 at the internal coal surface, adsorbing firmly to the
coal at a near-liquid density. Since the process of gas
adsorption has proven its stability through geological
time periods, the chances of future CO2 release from
non-mineable coal are considered minimal. Secondly,
both laboratory experiments and field tests suggest that
for two sequestered CO2 molecules, one CH4 molecule
is produced. Laboratory experiments showed that this
exchange ratio of 2:1 could be even larger at pressures
higher than 9.6 MPa, where the gaseous CO2 changes
to supercritical CO2 (Hall et al., 1994). This exchange
ratio could imply that, in areas rich in coal, energy
plants could be developed that would have an emission
of CO2 per energy unit that is much lower than that of
conventional energy plants or even approaches zero.
This would make the technology of ECBM with gas
(CO2) injection a clean source of energy.
The exchange ratio is of specific interest, since the
present European perspective for ECBM is on the CO2
sequestration potential rather than on the CH4 produc-
tion. To study this exchange ratio an experimental
programme has been set up for adsorption experiments
with CH4 and CO2 on coals. This experimental pro-
gram is unique because it involves experiments with
pressures of up to 20 MPa (200 bar; f 3000 psi).
The project work comprised the measurement, eval-
uation and interpretation of methane and CO2 adsorp-
tion isotherms on three representative Pennsylvanian
coal samples of different rank from the Netherlands.
The study aimed at the quantification and prediction of
gas storage capacity and expected displacement behav-
ior of methane by CO2 under subsurface conditions.
The experiments were carried out on dry and moisture-
equilibrated coals in order to assess the effect of natural
moisture content on the sorption of the two gases.
Adsorption isotherms were determined at 40, 60 and
80 jC.
2. Samples
The major part of the Dutch territory lies within the
Northwestern European Coal Basin. The most impor-
 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92 71

tant coal-bearing deposits in The Netherlands are the
Upper Carboniferous (Pennsylvanian) Westphalian A
to Upper Westphalian C sequences, which are present
throughout the major part of The Netherlands at
various depths with a total thickness of up to 3000
m. The coal content of the Westphalian strata varies
between 1.5% and 5%, with thickness of individual
layers up to a maximum of 3.5 m. Within the West-
phalian A and B sequences coal horizons occur with
an average spacing of 10 m (Pagnier et al., 1987).
From a geological point of view the Dutch coal basins
are comparable to the CBM production fields of the
Black Warrior Basin in Alabama (US), which were
deposited in a similar depositional setting.
All coal deposits in the Netherlands are presently
at considerable depth, and only accessible by subsur-
face mining and by wells. Since active coal mining
in the Netherlands ceased in late 1974, the most
recent coal samples from cores are from coal explo-
ration wells that were drilled in the mid-1980s. Coal
samples from these cores were taken at that time and
stored in sealed glass containers. The three selected
samples (Table 1) are from the Achterhoek area (Fig.
1). A correlation exists between coal seam IV of
Joppe-1 and coal seam VI of Hengevelde-1, indicat-
ing that these seams belong to the same coal layer
(Krans et al., 1986). The third sample with a higher
maturity was taken from a deeper coal seam in well
Joppe-1. The three coal samples have approximately
the same vitrinite contents (about 70%; Table 1).
While liptinite contents are in the same range (11.6%
and 14%) for the Hengevelde-1 VI and the Joppe-1
IV coals, the Joppe-1 IX coal has a very low liptinite
content (1%) and a substantially higher percentage of
inertinite (30%).
Due to the long storage time the coal samples may
be affected by oxidation. According to Mavor and
Pratt (1993) oxidation can reduce sorption capacities
of coals by as much as 11%. Comparison of the
analytical results from 1987 with those of 2000 (Table
1) shows a slight increase in the Rock-Eval Oxygen
Index and a slight decrease in the Rock-Eval Hydro-
gen Index, indicating a marginal oxidation of the
samples. It must be noted, however, that the results
were acquired by different analytical apparatus (Rock-
Eval II and Rock-Eval VI, respectively), which may
also be a cause of differences in the absolute values
(see for example the increase in the TOC value of

Table 1
Origin and properties of coal samples used in this study, for details cf. Krans et al. (1986)
Location Hengevelde-1 Joppe-1 Joppe-1
Coal seam VI IV IX
Depth (top) [m] 1106 1164 1484
Thickness of layer [cm] 72 97 57
Pure coal [cm] 57 96 57
Year of measurement 1987 2000 1987 2000 1987 2000
Liptinite (%) 11.6 16.8 14.0 15.0 1.0 4.3
Vitrinite (%) 73.6 73.3 67.5 71.2 68.4 68.6
Inertinite (%) 14.8 9.9 20.4 13.8 30.6 27.1
Moisture content (%) 4.87 3.00 1.27 0.50 n.a. 0.40
Ash content (%) 12.0 10.1 5.54 5.70 n.a. 4.40
Vitrinite reflectance (%) (50 readings) 0.72 0.73 1.19 1.18 1.56 1.53
Volatile matter (d.a.f.) 41.18 n.a. 27.25 n.a. n.a. n.a.
Fixed carbon (d.a.f.) 58.82 n.a. 72.75 n.a. n.a. n.a.
Rock-Eval Tmax 429 428 461 461 476 476
Rock-Eval S1 [mg HC/g] 2.65 3.19 3.10 2.15 3.03 4.89
Rock-Eval S2 [mg HC/g] 151.27 125.12 126.30 133.90 96.24 99.34
Rock-Eval S3 [mg CO2/g TOC] 4.25 6 1.40 2.48 2.01 3.26
Rock-Eval TOC (%) 75.68 69.71 70.16 84.20 90.44 74.18
Rock-Eval Hydrogen Index [mg HC/g TOC] 199 179 180 159 106 133
Rock-Eval Oxygen Index [mg CO2/g TOC] 5 9 1 3 2 4
Rock-Eval measurements were performed with a Rock-Eval II instrument in 1987 and with a Rock-Eval VI instrument in 2000.
 72
B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92
Fig. 1. Location of the coal-bearing Achterhoek area in the Northwestern European coal basin. Indicated are the distribution of Pennsylvanian (Westphalian) deposits and coalfields in
Northwestern Europe. The inset shows the depth of the top of the Pennsylvanian deposits (in meters) and the location of the wells Joppe-1 (JPE-1) and Hengevelde-1 (HGV-1) and the
location of other coal, oil and gas exploration wells in the area (squares).
 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92
sample Joppe-1 IV). Oxidation effects thus cannot be
excluded but in our opinion this will not dramatically
affect the experimental results.
3. Experimental
3.1. Sample preparation
The crushed samples were divided and aliquots
were ground to pass a sieve size of 0.2 mm. The
moisture content of the samples as received was
determined according to DIN 51718. Between 0.9
and 1 g of coal was weighed to the nearest 0.0001 g
and then dried for 90 min in an insulated air cabinet.
The sample was then placed in a desiccator over silica
gel to cool down and weighed again. For adsorption
measurements on dry coals, the samples were vac-
uum-dried in the adsorption apparatus for 1.5 h at a
temperature of 105 jC.
Fig. 2. Schematic diagram of the experimental set-up for gas adsorption on coals (A) and definitions for the volumetric method for gas sorption
measurements (B).
73
Moisture equilibration of the samples was carried
out according to the ‘‘Standard Test Method for
Equilibrium Moisture of Coal at 96 to 97 Percent
Relative Humidity and 30 jC’’ (ASTM D 1412-93).
This modified ASTM procedure is the recommended
method to reproduce the moisture content under
reservoir conditions (Mavor et al., 1990). A quantity
of 25 g of sample was suspended in water and stirred
for 3 h at a temperature of 30 jC. After this wetting
period, the excess water was removed and portions of
5 g were transferred into a small vacuum-type desic-
cator and equilibrated over a saturated solution of
potassium sulfate at 30 jC. Instead of an equilibration
time of 48 h required by the ASTM procedure the
samples were moisture-equilibrated for 60 h in this
study. The progress of the moisturizing procedure was
not monitored by intermittent weighing of the sam-
ples, but the final moisture content was found to be in
the range of values reported for coals of similar rank
and composition by the German mining industry.
74 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92
After moisturizing, the sample material was trans-
ferred immediately to the adsorption cell. An ali-
quot was used for determination of the moisture
content.
3.2. Experimental set-up
Fig. 2A shows a schematic diagram of the exper-
imental set-up consisting of a stainless-steel sample
cell, a set of actuator-driven valves and a high-
precision pressure transducer (max. pressure 25
MPa, with a precision of 0.05% of the full scale
value). The volume between valves V2 and V3,
including the dead volume of the pressure transducer,
is used as reference volume (see below) and deter-
mined by helium expansion in a calibration procedure.
The powdered coal samples are placed into the
calibrated sample cell. A 2-Am in-line filter is used
to prevent coal or mineral particles from entering the
valves. The sample cell is kept in a thermostate oven
(GC-furnace) the temperature of which is constant to
F 0.1 jC of the setpoint. Due to temperature limita-
tions ( < 60 jC) the pressure transducer and the valves
(V1-V3) are kept in a separate thermo-regulated
compartment at a different temperature (45 jC) than
the sample cell. This temperature difference between
the two sections of the set-up is taken into account in
the evaluation. The temperature gradient in the (low-
volume) tubing connecting the sample cell with the
switching valve V3 is neglected. For the high-pressure
CO2 adsorption experiments the measuring gas is
stored in a 150-ml pressure vessel at 45 jC in its
supercritical state.
3.2.1. Volumetric method for gas sorption measure-
ments on coal
The theoretical background and experimental pro-
cedures for the volumetric measurement of gas sorp-
tion isotherms on coals are discussed in Mavor et al.
(1990). The process of adsorption removes sorbate
gas molecules from the free gas phase and thus results
in a decrease of the gas pressure within the exper-
imental system. The most fundamental operational
procedure to quantify gas adsorption is the Gibbs
approach. Here the amount of adsorbed gas (nadsorbed)
is defined as the difference between the total amount
of gas (ntotal) present in the system and the amount
occupying the void volume (Vvoid), i.e. the volume not
occupied by the solid sample. This latter quantity is
calculated from the molar concentration (cgas) in the
gas phase which is obtained from an equation of state
(EOS) of the gas for the corresponding pressure and
temperature conditions:
nsorbed ¼ ntotal  cgas Vvoid
¼ ntotal  cgas ðVsample cell  Vsample Þ: ð1Þ
This approach assumes that the concentration of
the gas is uniform up to a mathematical surface (the
Gibbs dividing surface) separating the homogeneous
solid and gas phases (cf. Specovius and Findenegg,
1978). The volumes relevant for the measurement and
evaluation of the excess (Gibbs) adsorption are shown
in Fig. 2B. The total amount of gas introduced into the
system is computed from the amounts of gas trans-
ferred successively through the reference volume Vref
into the sample cell. The value of nsorbed depends on
the precise assessment of the volume Vsample which is
determined by helium expansion measurements prior
to the adsorption experiment.
The Gibbs excess sorption method assumes a
constant ratio of condensed phase volume and void
volume throughout the experiment and requires no
further assumptions. Sorption will, however, result in
non-uniform concentrations in the vicinity of the solid
surface and the formation of a sorbed phase. At low
pressures the gas phase has a much lower specific
density than the adsorbed phase so that the volume of
the latter can be neglected with respect to the void
volume of the sample cell. In high-pressure adsorp-
tion experiments the amount of sorbed phase
increases while at the same time the density differ-
ence between the free gas and the adsorbed gas
decreases.
In order to assess the ‘‘absolute sorption’’ of a
substance, the volume of the sorbed phase has to be
taken into account explicitly. The volume of the
sample cell is thus subdivided into the solid sample
(sorbent) volume, the volume of the sorbed phase and
the void volume:
Vsample cell ¼ Vsample þ Vvoid þ Vsorbed phase ð2Þ
As the density of the adsorbed phase cannot be
readily determined this evaluation has to rely on
estimates.
 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92
Like the Gibbs evaluation scheme the computa-
tion of ‘‘absolute sorption’’ assumes that the volume
of the solid sorbent remains constant during the
measurement, i.e. no swelling or volume decrease
occurs.
3.3. Equations of state (EOS)
The volumetric method for gas adsorption meas-
urements requires a precise knowledge of the specific
density of the free gas phase under the experimental
pressure and temperature conditions.
For methane a variety of equations of state (EOS)
are available describing the volumetric behavior of
this gas with good precision. The most commonly
applied EOS are the Peng –Robinson and Redlich–
Kwong equations which were also used in the initial
phase of this work. More recently, high-precision EOS
have been reported for methane (Setzmann and Wag-
ner, 1991) and carbon dioxide (Span and Wagner,
1996). In the further course of the study a program
package based on these EOS was used (courtesy Prof.
Wagner, University of Bochum).
4. Results
4.1. High-pressure methane adsorption on dry and
moisture-equilibrated coals
The isotherms of the high-pressure methane sorp-
tion experiments performed on the dry and moisture-
equilibrated coal samples are shown in Figs. 3 – 5.
Usually three experiments at different temperatures
were carried out on the same moisture-equilibrated
sample. It is evident from these figures that, while the
40 jC isotherms for the dry and moist coals exhibit a
saturation behavior at high pressures, and in some
instances even a slight decrease with pressure (i.e. a
maximum), the 60 and 80 jC isotherms increase
monotonously over the entire experimental pressure
range. This results in an intersection of isotherms
which is consistently observed for both dry and moist
samples, i.e. at high pressures the high-temperature
excess sorption capacities exceed the corresponding
low-temperature sorption capacities.
The occurrence of a maximum in the 40 jC
methane excess sorption isotherms on the dry coals
75
is in line with results of high-pressure methane
adsorption experiments on microporous adsorbents
(activated carbon). This phenomenon which is
observed when the bulk density of the gas phase starts
to rise faster than the adsorbed phase density as a
function of pressure was studied by Bénard and
Chahine (1997). These authors use a model based
on the Lennard –Jones interaction of methane mole-
cules adsorbed on a bidimensional hexagonal lattice
of graphite planes. High repulsive forces between
nearest-neighboring adsorption sites resist a full occu-
pation of the lattice and a corresponding increase of
the adsorbed phase density.
4.2. Low-pressure CO2 adsorption on dry coals
Four low-pressure adsorption tests were performed
with CO2 on dry Joppe-1 IV coal at 40 and 80 jC.
These test experiments reached maximum CO2 pres-
sures of f 5.5 MPa (55 bar). Fig. 6 shows the low-
pressure CO2 excess sorption isotherms measured at
40 jC. At the final pressures of the two experiments
the excess sorption of the CO2 amounts to f 20 –22
cm3 STP/g coal. For comparison this graph also
shows the methane sorption isotherm measured under
the same conditions. At the final pressure of the CO2
isotherms the excess sorption for methane ranges
around 13 cm3 STP/g and approaches a value of
16.3 cm3 STP/g between 160 and 180 bar. Plotted
in Fig. 7 are the excess sorption isotherms for CO2
and methane on the dry Joppe-1 IV coal at 80 jC. The
maximum sorption capacity for CO2 recorded at 55
bar is 17 cm3 STP/g and thus by approximately 20%
lower than the corresponding value at 40 jC. At this
pressure the methane sorption capacity is 10 cm3 STP/
g, while the final value at f 180 bar lies at 14 cm3
STP/g.
4.3. High-pressure CO2 adsorption on dry coals
In the high-pressure CO2 adsorption experiments
on dry coals (Figs. 8 – 10) the highest excess sorption
capacities are observed at 40 jC with maximum
values of 70 Std. cm3/g within limited pressure
ranges. The adsorption isotherms have different
shapes which vary both with temperature and sample.
The 40 jC isotherms show a sharp increase in excess
CO2 sorption capacity between 8 and 10 MPa (80 –
76 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92

Fig. 3. Sorption isotherms for methane on dry and moisture-equilibrated Hengevelde-1 VI coal (Rr = 0.72%) at 40, 60 and 80 jC.

Fig. 4. Sorption isotherms for methane on dry and moisture-equilibrated Joppe-1 IV coal (Rr = 1.19%) at 40, 60 and 80 jC.
 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92 77

Fig. 5. Sorption isotherms for methane on dry and moisture-equilibrated Joppe-1 IX coal (Rr = 1.56%) at 40, 60 and 80 jC.

Fig. 6. Excess sorption isotherms for CO2 and methane measured on dry Joppe-1 IV coal (Rr = 0.72%) at 40 jC.
78 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92

Fig. 7. Excess sorption isotherms for CO2 and methane measured on dry Joppe-1 IV coal at 80 jC.

100 bar), particularly for the HGV-1 VI and the JPE-1 The 60 jC CO2 adsorption isotherms for the dry
IX samples; for the latter sample the sorption capacity coals show different patterns. In one instance (HGV-1
peaks at 70 Std. cm3/g (at f 9 MPa) and then declines VI; Fig. 8) a bimodal shape with maxima around 5
to 60 Std. cm3/g (Fig. 10). and 12 MPa and a minimum at 9 MPa is observed.

Fig. 8. Excess sorption isotherms for CO2 on dry Hengevelde-1 VI coal at 40, 60 and 80 jC.
 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92 79

Fig. 9. Excess sorption isotherms for CO2 on dry Joppe-1 IV coal at 40, 60 and 80 jC.

One isotherm (JPE-1 IV; Fig. 9) shows a single
maximum around 9 MPa followed by a continuous
decline in sorption capacity and one sorption isotherm
(JPE-1 IX; Fig. 10) shows a monotonous increase
with pressure. The 80 jC CO2 isotherms of all three
samples increase monotonously up to pressures
between 6 and 10 MPa (60 – 100 bar) and then remain
either approximately constant (JPE-1 IX) or decrease.
4.4. High-pressure CO2 adsorption on moisture-
equilibrated coals
All high-pressure CO2 adsorption isotherms for
moisture-equilibrated samples shown in Figs. 11 –13
are bimodal with distinct minima in the 8– 10 MPa
(80 – 100 bar) range. In several instances the ‘‘excess
sorption’’ values take negative values in this pressure

Fig. 10. Excess sorption isotherms for CO2 on dry Joppe-1 IX coal at 40, 60 and 80 jC.
80 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92

Fig. 11. Excess sorption isotherms for CO2 on moisture-equilibrated Hengevelde-1 VI coal at 40, 60 and 80 jC.

interval. The highest excess sorption values for the
moist coals are observed in the 60 and 80 jC
isotherms at pressures in excess of 12 MPa (120
bar). The 40 jC isotherms show a sharp decrease in
excess sorption capacity around 8 MPa (80 bar); in
two instances (HGV-1 IV; JPE-1-IX) the excess
adsorption takes large negative values (  26;  14
Std. cm3/g); above 9 MPa (90 bar) sorption capacities
are positive again and reach values between 8 and 25
Std. cm3/g. The bimodal 60 jC isotherms show a
broader ‘‘valley’’; in one case (JPE-1 IV) excess
sorption values become negative in the 8 –10 MPa
interval; all 60 jC isotherms are characterised by a
small sorption maximum (7– 10 Std. cm3/g) in the
low-pressure range and a large sorption maximum
(17 –35 Std. cm3/g) in the high-pressure range; at very
high pressures ( > 13 MPa) the CO2 sorption capacity
decreases continuously. The 80 jC isotherms are

Fig. 12. Excess sorption isotherms for CO2 on moisture-equilibrated Joppe-1 IV coal at 40, 60 and 80 jC.
 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92
Fig. 13. Excess sorption isotherms for CO2 on moisture-equilibrated Joppe-1 IX coal at 40, 60 and 80 jC.
bimodal with wide ranges (4– 10 MPa; 40– 100 bar)
of negative excess sorption values; the low-pressure
sorption maxima range between 2 and 5 Std. cm3/g; at
high pressures the CO2 sorption capacity increases
dramatically and reaches values between 25 and 45
Std. cm3/g beyond 14 MPa (140 bar).
5. Discussion
5.1. Pressure and temperature effects
The methane isotherms display a normal Lang-
muir-type behavior up to a pressure of about 10 MPa.
Some isotherms reach a clear maximum beyond this
point, which results in a deviation from the Langmuir
equation at higher pressures, since this relation pre-
dicts a monotonous asymptotic approach to a limiting
value at infinite pressure. The effect of pressure
increase on the adsorption capacity of coal for CO2
is evaluated below.
The clear negative effect of temperature on the
adsorption capacity up to a pressure of about 10 MPa
is in agreement with literature data (e.g. Levy et al.,
1997; Bustin and Clarkson, 1998; Kim, 1977; Fails,
1996). It must be noted that the experiments of most
81
of these studies did not reach pressures higher than 10
MPa. The consistent crossover that can be observed in
Figs. 3 –5 indicates that temperature effects are prob-
ably more complex than so far assumed. The most
probable explanation for this crossover is decreasing
influence of the sorbed phase volume with increasing
temperature. At lower temperatures the density differ-
ence between the sorbed phase and the free gas phase
becomes smaller and the excess sorption evaluation,
neglecting the sorbed phase volume, is no longer
justified.
Temperature effects could not be clearly discerned
in the CO2 experiments.
5.2. Coal composition and rank effects
The effect of maceral composition on gas sorption
capacity (GSC) is still a matter of debate. Although
the role of coal type (maceral composition) on gas
adsorption is not fully established, many workers have
indicated that coal maceral composition influences the
GSC of coal. An explanation for the relationship
between composition and GSC may be provided by
the pore structure of the macerals. Clarkson and
Bustin (1996) found a general increase in the total
number of micropores with increasing vitrinite content
82 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92
in Western Canadian Cretaceous coals and stated that
the composition has a definite influence on pore
structure and GSC of coal. According to Crosdale et
al. (1998) coal rank and composition per se do not
appear to be the critical factors in controlling gas
sorption, but rather the influence they exert over pore
structure development.
Various studies report an increase in gas sorption
capacity with increasing vitrinite content (e.g. Lamber-
son and Bustin, 1993; Levine et al., 1993; Beamish and
Gamson, 1993; Crosdale and Beamish, 1993), suggest-
ing a prominent role of this maceral in gas adsorption
on coals. The results of earlier research by Ettinger et al.
(1966), who state that fusinites could adsorb twice as
much methane as vitrinites, are probably related to the
type of fusinite analysed (Crosdale et al., 1998).
Coal rank is generally considered to be the main
parameter affecting the methane adsorption capacity of
coal (Ryan, 1992). According to Yee et al. (1993)
moisture equilibrated coals show an increase of GSC
with increasing rank. Earlier reports on U-shaped
trends can probably be attributed to the fact that these
earlier measurements have been performed on dry
coals (Yee et al., 1993). One possible explanation for
the difference in rank dependency of dry and moist
coal is given by Levine (1991), who postulates that the
influence of moisture on gas sorption could change the
trend to one of increasing gas sorption capacity with
rank, since low rank coals have high affinities for
water. Levy et al. (1997) found a linear increase of
GSC with increasing carbon content for moisture
equilibrated coals. Research of Coppens (1967), based
on adsorption experiments, also showed that there is an
increase of GSC with an increase in rank in the Belgian
part of the Campine Basin. However, on a global scale
there are statistically no significant linear or non-linear
correlations between rank and adsorption capacity
(Bustin and Clarkson, 1998).
In the experiments reported here, the effects of
maceral composition and of rank could not be clearly
discerned within the selected set of samples. Given
the small variation in vitrinite content (Table 1), it was
initially assumed that rank effects would be predom-
inant and overprint possible maceral effects. Compar-
ison of the isotherms, for both CH4 and CO2, in this
study does not reveal any distinct and systematic rank-
dependent trends between the samples. Probably, the
maceral effects are larger than initially assumed.
5.3. Moisture effects
It is generally found that increasing moisture con-
tent results in a reduction of GSC. One possible
explanation is that the accessible micropore volume
in moist coals is much less than in dry coals, due to
either a reduction of pore size due to water adsorption
or to swelling of the coal (Seewald and Klein, 1986).
Studies of Australian and United States coals have
shown a linear decrease in methane adsorption
capacity with increasing moisture content. Above a
certain moisture concentration, the GSC does not
decrease any further because all possible adsorption
sites for water are occupied. This moisture content is
considered to be the maximum capacity of the partic-
ular coal for adsorption of water (Joubert et al., 1974;
Levy et al., 1997; Bustin and Clarkson, 1998). Accord-
ing to Mavor et al. (1990) as little as 1% moisture may
reduce the adsorption capacity by 25%, and 5%
moisture results in a loss of adsorption capacity of
65% (Lama and Bodziony, 1996). Clearly, the results
of the methane experiments of this study, a reduction
of 20 – 25% for the moisture-equilibrated coals as
compared to dry coals, support these observations.
The reduction of GSC by more than 20% also supports
the conclusions of Bustin and Clarkson (1998), who
state that the role of moisture during ad-/desorption of
coal gas is beyond that of a simple contaminant, e.g.
ash content, that can be corrected for by calculating the
results on a dry basis. Water competes for adsorption
sites on the coal surface and may block the access of
gas to the micropore system (Yee et al., 1993; Laxmi-
narayana and Crosdale, 1999).
The effect of moisture on CO2 adsorption appears
to be even more complex, considering the differences
in the shape of the isotherms of experiments on dry
and on moist coals. In general, it can be observed that
carbon dioxide sorption capacities for the moisture-
equilibrated coals are usually lower than for the dry
samples.
5.4. Low-pressure (<6 MPa) CO2 adsorption on dry
coals
The low-pressure CO2 isotherms on dry coals
display ‘‘normal’’ Langmuir-type adsorption behavior
with increasing pressure. The 40 jC isotherm (Fig. 6)
shows that, in molar units, the quantity of CO2
 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92
adsorbed on the dry coal at 55 bar is 1.6 times the
quantity of methane adsorbed, i.e. the ‘‘exchange
ratio’’ (n(CO2 ads.)/n(CH4 ads.) is less than 2. At lower
pressures this ratio approaches a value of 2. The molar
sorption capacity of CO2 of the 80 jC isotherm at the
final pressure level is 1.7 times that of CH4, i.e. close
to the value observed in the 40 jC experiment. In
general, comparison of the experimental excess sorp-
tion data determined in this study shows that, up to a
pressure of about 6 MPa (60 bar), the adsorption of
CO2 is about twice the adsorption of pure CH4. This is
in good agreement with earlier research (e.g. Fulton et
al., 1980; Reznik et al., 1984; Puri and Yee, 1990;
Stevenson et al., 1991; Arri et al., 1992; Hall et al.,
1994; Stevens and Pekot, 1999; Wolf et al., 1999).
5.5. High-pressure CO2 adsorption experiments
Clearly, the shapes of the high-pressure CO2 iso-
therms are more complex than the CH4 isotherms.
Especially, the negative excess sorption values in the
8 – 10 MPa pressure interval were unexpected but
could be attributed, at least partly, to the inadequacy
Fig. 14. Comparison of absolute sorption isotherms for CO2 at 40 jC on the three coals investigated in this study.
83
of the Gibbs approach for a strongly non-ideal gas at
high pressures and comparatively low temperatures.
Up to now only a limited number of comparable
high-pressure adsorption data for CO2 on coals have
been reported in the published literature. Hall et al.
(1994) have conducted experiments of up to 12 MPa
(1800 psi). Therefore, the sorption isotherms meas-
ured in the present study, at pressures of up to 20
MPa, represent a unique data-set. Due to the lack of
reference data, the reliability and consistency of our
experimental results can presently only be established
by detailed scrutiny of the experimental evaluations
and systematic comparison of the results of the
various experiments. Due to the unexpected properties
of the CO2 sorption isotherms, particularly for the
moist samples the experimental measurements have
been thoroughly reviewed and great care has been
taken to eliminate experimental artefacts. Reproduci-
bility measurements and duplicate runs have been
conducted to corroborate the experimental results.
Because experimental errors can be largely ruled
out, it is concluded that the initial assumptions sta-
ted above are not valid for high-pressure CO2
84 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92
Fig. 15. Comparison of absolute sorption isotherms for CO2 at 40 jC on Joppe-1 IX coal with results by Hall et al. (1994) on wet Fruitland coal
at 115 jF.
adsorption on coal. The evaluation of the high-
pressure CO2 adsorption experiments in terms of
excess sorption (Gibbs sorption) reveals substantial
deviations of the isotherm from the ‘‘normal’’ shape
indicating a strong volumetric effect. This effect
could be due to the formation of a voluminous
adsorbed phase at high pressures or/and to swelling
of the coal matrix. Given the differences in the CO2
sorption isotherms for dry and moist coals, water
appears to play an important role by enhancing
either the formation of a voluminous (low specific
density) sorbed phase or the swelling process of the
solid coal.
In order to examine the influence of the effect of
the adsorbed phase, absolute sorption isotherms have
been computed for CO2 adsorption on the moist coals.
Following the approach of Hall et al. (1994) the
specific volume of the adsorbed CO2 phase was taken
as the van der Waals co-volume of 42.8 cm3/gmol,
corresponding to 1028 kg/m3. The 40 jC absolute
sorption isotherms for the three moisture-equilibrated
coals resulting from this evaluation are shown in Fig.
14. Evidently, even the explicit consideration of the
sorbed phase volume does not remove the distinct
decline in the adsorption isotherms in the 80 –100 bar
pressure interval. It is also obvious that the extent of
this decline is not directly related to the rank of the
coals nor to the maceral composition. On the other
hand, a tendency of increasing absolute CO2 sorption
capacity with coal rank is observed both in the low-
and the high-pressure region.
Fig. 15 shows a comparison of the 40 jC absolute
sorption isotherm for the moist Joppe-1 IX coal
measured in this study with the 115 jF (46.11 jC)
corresponding isotherms for wet Fruitland coal by
Hall et al. (1994). While the isotherms from these
two studies show nearly perfect agreement in the low-
pressure range, they deviate strongly beyond f 7
MPa. The decline in adsorption isotherms observed
repeatedly in the present study is not evident in the
results of Hall et al. (1994). Furthermore, the absolute
CO2 sorption capacity of the wet Fruitland coal
increases in a much smaller pressure interval than
the sorption capacity of the Joppe-1 IX coal and the
 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92
other Pennsylvanian coals studied in our laboratory.
Further investigations are required to reveal in more
detail the high-pressure CO2 sorption behavior of
coals of different rank and maceral composition.
In conclusion, the CO2 sorption behaviour appears
to be very sensitive to small variations in the exper-
imental conditions and the sample properties (e.g.
moisture content) in the high pressure regime ( P > 6
MPa). The variability of the observed CO2 adsorption
curves indicates that a quantitative prediction of the
sorption capacity of moist coals for this gas is prob-
lematic. It is expected that, with an increasing exper-
imental database, an improved appreciation and
understanding of the various types of experimental
curves will emerge so that the observations can be
related to specific properties of the coals and the
underlying physico-chemical processes.
6. Summary and conclusions
A comprehensive data-set for methane and carbon
dioxide adsorption on dry and moisture-equilibrated
Pennsylvanian coals from The Netherlands up to 20
MPa has been obtained during this study. While the
results of methane sorption tests on dry coals essen-
tially confirmed earlier experimental work, the exten-
sion of the experiments to moist coals and to
supercritical carbon dioxide revealed an increasing
complexity of the gas sorption behavior. Pilot meas-
urements of CO2 adsorption at low pressures ( < 6
MPa) on one dry coal (Joppe-1 IV, dried at 105 jC)
yielded maximum adsorption capacities of 21 and 17
m3 STP/g coal at 40 and 80 jC, respectively.
The high-pressure CO2 adsorption isotherms for
dry and moist coals show strong differences. For the
dry coals the highest CO2 excess sorption capacities
are observed at 40 jC with maximum values of 70
Std. cm3/g within limited pressure ranges. Particularly
the excess sorption curves recorded at the lower
temperatures (40 and 60 jC) exhibit distinct structures
with local maxima while the 80 jC isotherms are
usually less structured.
Carbon dioxide sorption capacities for the mois-
ture-equilibrated coals are usually lower than for the
dry samples in the low pressure range. All CO2
adsorption isotherms for moist samples are bimodal
with distinct minima in the 8 – 10 MPa (80 –100 bar)
85
range. Beyond this range CO2 adsorption capacity
increases with increasing pressure. High-temperature
(80 jC) sorption capacities for CO2 are very low ( < 5
Std. cm3/g) in the low-pressure range but reach much
higher levels (25 – 50 Std. cm3/g) above 12 MPa.
The fact that the distinct decline in the CO2 excess
sorption curves is only observed for moisture-equili-
brated coals and does not or only marginally occur in
the dry coal experiments is considered as a strong
argument against systematic experimental errors.
The experimental results for the CO2 adsorption on
the moist coals, and to some extent on the dry coals,
indicate the occurrence of an important volumetric
effect in the pressure range from f 80 to 120 bar (8 –
12 MPa). Apart from the formation of a voluminous
sorbed phase this effect is likely to be due to coal
swelling. The volume increase of the condensed phase
(solid coal + adsorbed CO2) was estimated to amount
to more than 20% of the initial coal volume in certain
pressure intervals.
Evaluations of the experimental data for CO2
adsorption on moist coals in terms of absolute sorp-
tion were performed assuming a constant specific
density of 1028 kg/m3 for the adsorbed CO2. While
these evaluations show good agreement with literature
data (Hall et al., 1994) in the low-pressure range (up
to f 8 MPa) and for total CO2 sorption capacity at
high pressures, the anomalies (decreasing and nega-
tive sorption values) in the 8– 12 MPa pressure range
persist, underlining the importance of the volumetric
effect. It remains to be examined whether this phe-
nomenon observed in this study on the powdered coal
equally affects solid coal. This might have important
implications for ECBM and CO2 sequestration tech-
niques.
One further important issue of direct relevance for
CO2 storage in coals is the investigation of the
sorption behaviour of methane and carbon dioxide
mixtures which involves direct competition of the two
molecules for the available sorption sites. The effects
of moisture content and coal composition on the
selectivity of CO2 adsorption have been studied
recently by Clarkson and Bustin (2000).
6.1. Units and conversion factors
The adsorption capacities in this paper are ex-
pressed in standard cm3 per gram of coal (Std. cm3/
86 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92
g coal) corresponding to standard m3 per ton of coal
(Std. m3/t coal). Here ‘‘standard conditions’’ refers to
a temperature of 15 jC (288.15 K; 59 jF) and
atmospheric pressure (101 325 Pa; 1.01325 bar; 14.7
psi). The molar volume (Vm) of an ideal gas at these
conditions is 0.02364 m3/mol (0.835 ft3/mol). Con-
version into mass units can be accomplished using the
following factors:
1 Std. m3 CH4 = 0.677 kg
1 Std. m3 CO2 = 1.86 kg
Acknowledgements
This project has been performed under Programme
number 234.1 with NOVEM BV, the Netherlands
Agency for Energy and the Environment (see Hame-
linck et al., 2001). We thank Prof. W. Wagner of
Ruhruniversität Bochum for providing the EOS
software for methane and carbon dioxide. Furthermore,
we gratefully acknowledge the support by Dirk Prinz
and Roland Gaschnitz in experimental matters and
design of the evaluation procedures. The final manu-
script benefited from thorough reviews by J. Close and
C. Clarkson who provided helpful information and
suggestions on theoretical and technical aspects.
Fig. 16. Effect of error in temperature measurement (measuring-cell) on the excess sorption of methane. Experimental temperature: 40 jC.
Isotherms calculated for 39.5, 40 and 40.5 jC.
Appendix A. Experimental errors and
reproducibility
Experimental errors and reproducibility problems
of the adsorption measurements can be expected to
arise from errors in temperature and pressure record-
ings. Generally, the calibration measurements con-
ducted repeatedly during this study showed a good
reproducibility. Thus, the variation in the volumes of
the reference-cell and the measuring-cell determined
in the calibration tests was in the range of 1.5%. In the
following section the potential effects of errors in
temperature and pressure measurements are evaluated
for the methane and carbon dioxide sorption iso-
therms.
A.1. Temperature effect
Temperatures of the oven accommodating the
measuring-cell and the thermostated chamber contain-
ing the reference-cell varied by no more than 0.2 jC.
In order to demonstrate the effect of temperature
variations on the results of the adsorption experi-
ments, evaluations were carried out with temperature
values deviating by F 0.5 jC from the measured
values. This temperature variation was performed
 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92 87

Fig. 17. Effect of error in temperature measurement in the reference-cell on the excess sorption results of methane, assuming F 0.5 jC
deviation.

both for the temperature in the reference-cell and in possible influence of errors in the pressure measure-
the measuring-cell. ments the measured pressures were varied by F 0.5 bar.

A.2. Pressure effect A.3. Methane isotherms

As stated in the Experimental section the precision The results of the analysis of temperature and
of the pressure transducers used in these experiments is pressure errors for a methane adsorption experiment
0.05% of the full scale value (25 MPa), corresponding on dry coal are shown in Fig. 16 (variation of
to 0.0125 MPa (0.125 bar). In order to assess the measuring-cell temperature), Fig. 17 (variation of

Fig. 18. Effect of error in pressure measurements on the excess sorption results of methane, assuming F 0.5 bar deviation.
88 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92

Fig. 19. Effect of error in temperature measurement (measuring-cell) on the excess sorption of carbon dioxide. Experimental temperature: 40 jC.
Isotherms calculated for 39.5, 40 and 40.5 jC.

reference-cell temperature) and Fig. 18 (pressure var-
iation). Evidently, a temperature variation of F 0.5 jC
(i.e. substantially larger than the expected experimen-
tal variation) results in significant variations of the
methane sorption isotherms only above 60 bar. When
approaching the final pressure ( f 200 bar) the errors
in the sorption isotherms reach approximately F 10%.
The shapes of the sorption isotherms remain essen-
tially unchanged.
A F 0.5 bar pressure variation results in variations
of the methane adsorption isotherms of approximately
F 5% over the entire pressure range.

Fig. 20. Effect of error in temperature measurement in the reference-cell on the excess sorption results of carbon dioxide, assuming F 0.5 jC
deviation.
 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92 89

Fig. 21. Effect of error in pressure measurements on the excess sorption results of carbon dioxide, assuming F 0.5 bar deviation.

A.4. Carbon dioxide isotherms
The effects of errors in temperature and pressure
measurements on the carbon dioxide excess sorption
isotherms are shown in Figs. 19 –21 for the moisture-
equilibrated Joppe-1 IX coal. It is evident that errors in
the temperature of the reference-cell have the strongest
impact on the excess sorption values reaching up to
F 20% in the high-pressure region. Errors in the
measuring-cell temperature and in the pressure record-
ing result in significantly smaller errors in the excess
sorption values. It is important to note that the overall
shape of the excess sorption curves is unaffected by the
errors in temperature and pressure measurements,

Fig. 22. Cumulative amounts of CO2 in the measuring-cell with void volumes of 4.0549 and 3.662 cm3, respectively, during blind experiments
(no coal) at 40 jC. The corresponding curve for an intermediate void volume of 3.8066 cm2 was calculated by linear interpolation.
90 B.M. Krooss et al. / International Journal of Coal Geology 51 (2002) 69–92

Fig. 23. Cumulative amount of CO2 in the measuring-cell determined in the coal adsorption experiment and for the ‘‘no-sorption’’ case. The
excess sorption represents the difference between the sorption and the no-sorption curve. Evidently, the subtraction yields a positive excess
sorption in the high- and low-pressure regions while negative values occur in the 80 – 100 bar range.

indicating that the observed effect of declining and
negative excess sorption values in the 80– 120 bar
pressure range is not primarily due to experimental
errors.
A.5. Investigation of causes for unexpected CO2
excess sorption isotherms
The high-pressure excess sorption isotherms for
carbon dioxide, particularly on moisture-equilibrated
coals, measured during this study showed unexpected
excursions in the 80 –120 bar pressure range. These
observations gave rise to concerns about the exper-
imental procedure and prompted us to perform a
number of tests to substantiate the findings. In order
to exclude any systematic experimental errors the
following procedure was used to verify the experi-
mental results on CO2 adsorption on coals.
(1) At a given experimental temperature two
‘‘blind experiments’’ were performed with stainless
steel cylinders placed in the measuring-cell. The
volumes of the steel cylinders were such that the
resulting void volumes in the measuring-cell (4.0549
cm3 and 3.662 cm3) bracketed the void volume in the
actual coal adsorption experiment. For each blind
experiment the quantity of CO2 stored in the measur-
ing-cell was recorded as a function of pressure over
the entire experimental pressure range (Fig. 22).
(2) Based on these two curves another curve
corresponding to the void volume of the subsequent
coal adsorption experiment was calculated by linear
interpolation. This curve, shown also in Fig. 22 (for a
void volume of 3.8066 cm3), represents the ‘‘no-
sorption’’ case.
(3) The ‘‘no-sorption’’ curve was then compared
with the cumulative CO2 curve measured in the coal
adsorption experiment (Fig. 23). Subtraction of the
‘‘no-sorption’’ curve from the coal adsorption curve
yields the excess sorption. As evident from Fig. 23
this subtraction yields negative values in the 80– 100
bar pressure range.
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