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Carbon dioxide, methane and nitrogen

high pressure sorption capacities of


bituminous South African coals
Gregory N. Okolo*,a, Raymond C. Eversona, Hein W.J.P. Neomagusa,
Mokone J. Robertsa, Richard Sakurovsb, Miheala Grigoreb
a

Coal Research Group, Unit for Energy Systems, School of Chemical and Minerals Engineering, North-West
University, Potchefstroom Campus, Private Bag X6001, Potchefstroom 2520, South Africa.
b

CSIRO Energy Technology, P. O Box 52, North Ryde NSW 1670, Australia

*Corresponding author- Tel: +27 18 299 1539; Email address: 22006303@nwu.ac.za

27-28th November, 2014

Background & Motivation[1-7]


Greenhouse gases (GHGs) are largely responsible for global climate change.
CO2 is the most prevalent GHGs. Global CO2 atmospheric concentration from
280 ppm in the pre-industrial era to over 390 ppm in 2012; mostly from fossil
fuels[1].
CO2 captured from point sources can be sequestered in deep geologic locations:
oceans; saline aquifers; depleted oil & gas wells; and unmineable coal seams [2-7].
The sorption capacity of geologic CO2 sink e.g. coal seam gives insight into its
storage capacity.
Gravimetric adsorption technique has been found to have some advantages over
volumetric adsorption method.
Using the fluid density instead of the saturation pressure eliminates the
uncertainty of saturation pressure at supercritical conditions.
Fitting of experimental
to different
model can be used
to01-02-2013.
describe the
Dlugokencky E., Tans data
P. 2012. NOAA/ESRL
(www.esrl.noaa.gov/gmd/ccgg/trends/)
AssessedMarchetti C. Climate Change, 1977;1:59-68.
adsorption mechanism
at Annual
supercritical
conditions.
Herzog HJ, Drake EM.
Review of Energy and
the Environment, 1996;21:145-166.
[1]
[2]
[3]

Bachu S. Energy Conversion & Management, 2000;41:953-970.


Gentzis T. International Journal of Coal Geology, 2000;43:287-305.
[6]
Bachu S, Bonijoly D, Bradshaw J, et al., International Journal of Greenhouse Gas Control, 2007;1:430-443.
[7]
Busch A, Gensterblum Y. International Journal of Coal Geology, 2011;87:49-71.
[4]
[5]

Background Information

Figure 1: Global greenhouse gas (GHG) emissions [1]

South Africa produces over 40% of anthropogenic


CO2 emitted in Africa and is ranked 11th CO2 emitter in
the world[8].
[8]

Metz et al., (2005). IPCC Special report on carbon dioxide capture and storage

Background Information

Figure 2: Indicators of global warming[9]


Evidence of Climate Change. www.climate-change-guide.com. Accessed:26th July, 2013.

[9]

Background Information
Of the 440 Million tonnes of CO2
emitted per annum in South Africa:

91.8

4.3
6.6
44.9

About 320 Mton CO2 (72.7%) is


sequestrable
222.4

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About 32 Mton (7.2%) is captureready: does not require concentration


prior to capture

Eskom (50.5%)

Sasol (15.9%)

Industrial processes (10.2%)

Mining Operations (1.5%)

Refineries (1.0%)

Others (20.9%)

Others (about 92 Mton (21%)) are from moving source: transportation, agriculture waste
sector etc.

Figure 3: Distribution of large-scale industrial CO 2 emissions in South Africa2009 (Mton CO2 per annum)[10]
Viljoen et al., (2010). Technical report on the geological storage of carbon dioxide in South Africa

[10]

Background Information
Table 1: Estimated CO2 storage capacity of South Africas unmineable coal fields[10]
Basins/
Area

Amersfoort/
Utrecht
Ellisras
Welkom/
Hennenman
Kroonstad
Springbok Flats
Somkele
Pafuri
Kangwane
Newcastle/
Ladysmith
Edenville
Tuli
Heilbron
Frankfort
Nongoma

Depth
Interval (m)

CO2 Adsorption
Capacity/Tonne
of coal (m3)

CO2 Storage
Capacity
(MtCO2)

Gas Content
(wt %, adb)

300-550

2227

331.8

NA

800

10

300-800

1722

293.4

23-26

1440

300-550

1721

154.4

NA

936

300-550

1721

100.3

NA

2300

300-550

1722

84.4

28-35

360
420
195

5
3
6

300-800
300-800
300-800

2227
2226
2226

82.9
56.9
52.8

6-8
22-27
7-24

936

300-550

2227

43.1

NA

360
150
288
216
75

2
3
1
1
1.5

300-550
300-550
300-550
300-550
300-550

1721
2227
1721
2227
2227

25.7
20.7
10.3
10
5.2

32-36
NA
NA
7-24

Area
(km2)

Seam
Thickness
(m)

3600

Total Estimated CO2 Storage capacity of unmineable coal seams

1271.9

Viljoen et al., (2010). Technical report on the geological storage of carbon dioxide in South Africa

[10]

Aims & Objectives


To determine the CO2, CH4, and N2 sorption
capacities at supercritical conditions, using a
gravimetric technique.
Identify a model that can describe the adsorption
process.
Correlate the sorption capacities of the samples with
the coal properties.

Research Methods

ROM coal seam samples


Characterisation techniques
Standard
properties:
Proximate;
Ultimate;
Total Sulphur;
Reflectance
properties;
Maceral
compositions;
XRD Mineral
analysis

HPGA Experiments with


CO2, CH4 and N2 at 55 C,
upto 16.4 MPa

Physicalstructural
properties:
LPGA (CO2 and N2);
MIP;
Helium pycnometry;
SAXS.

Correlate
HPGA results
with sample
properties
Figure 4: Research methods
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HPGA experimental facility

Figure X: High pressure gravimetric adsorption system


Fig. 5: Schematic of the HPGA system
Experimental Conditions
Sample mass
Isothermal adsorption temperature
Pressure
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225 5 g
55 0.2 C
Ambient 16.2 MPa

PAGE: 9

HPGA experimental facility

Fig. 6: Schematic of the HPGA system


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PAGE: 9

PAGE: 4

Characterisation Results- Standard Analyses


Table 2: Summary of the conventional properties of coal samples
Sample ID

Coal FOZ Coal DEN


Proximate Analysis (wt. %, adb)

Coal OGS

Coal TKD

Inherent moisture

3.3

4.0

2.7

0.7

Ash content

22.0

25.9

24.5

16.8

Volatile Matter

26.6

21.5

22.4

22.0

Fixed carbon

48.1

48.6

50.4

60.5

Gross Calorific Value (MJ/kg) (adb)


23.5
21.6
Ultimate Analysis (wt. %, dafb)

23.3

29.6

Carbon

78.5

78.7

81.3

86.9

Hydrogen

4.9

4.4

4.7

5.1

Nitrogen

2.0

2.2

2.0

2.1

Oxygen

13.2

13.0

10.6

4.8

Total sulphur content

1.4

1.7

1.3

1.0

Free Swelling Index (FSI)

0.0

0.0

0.5

8.5

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Characterisation Results- Petrographic Analysis

Table 3: Summary of maceral compositions and reflectance properties of samples


Sample ID

Coal FOZ

Coal DEN

Coal OGS

Coal TKD

Maceral analysis (vol. %, mmb)


Vitrinite

36

20

21

68

Liptinite

Inertinite

45

59

57

23

Visible minerals

14

18

17

54
41
Reflectance properties (%)

42

72

Total reactive macerals

Mean vitrinite random reflectance (Rr, %)

0.63

0.65

0.69

1.2

Mean total maceral reflectance (Rsc, %)

1.05

1.24

1.19

1.5

Medium
Rank C

Medium
Rank C

Medium
Rank C

Medium
Rank B

Rank (Bituminous)

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Characterisation Results Physical-structural properties1,7,9-12]


Table 4: Summary of physical-structural properties of samples
Properties / Sample ID
D-R micropore surface area (m2/g)
D-R micropore volume x10-2, cm/g
Average micropore diameter ()
Porosity (%) (3 dp 5)

Method used Coal FOZ Coal DEN Coal OGS Coal TKD
CO2 Adsorption Results
D-R
D-R
H-K
CO2 Ads data
N2 Adsorption Results

BET surface area (m2/g)


BET adsorption total pore volume x10-2 (cm/g)
BJH Desorption average pore diameter (4V/A)
Porosity (%) (17 Dp 500 )
Total pore area (m2/g)
Total intrusion pore volume x10-2 (cm3/g)
Average pore diameter (4V/A) ()
Porosity (%) (30 Dp 600000 )
Bulk density (kg/m3)
Specific Surface Area (m2/g)
Microporosity (%)
Mesoporosity (%)
Macroporosity (%)

127.9
5.1
3.87

129.3
5.2
3.85

117.8
4.7
3.89

107.3
4.3
4.1

5.36

5.27

4.58

2.91

BET
BET
BJH
N2 Ads data
MIP Measurements

3.6
1.32
187

5.7
1.47
125

2.9
1.01
196

2.6
1.02
261

2.23

1.6

1.32

2.63

MIP
MIP
MIP
MIP
MIP
SAXS measurements

13.9
4.4
127
6.2
1295

14.1
3.9
111
6.1
1455

12.5
5.2
168
7.1
1367

10.9
5.7
208
7.6
1206

162.6
10.3
8.6
11

171.7
10.1
7.7
9.9

158.2
9.5
8.6
10.5

147.4
8.7
6.6
11.1

SAXS
SAXS
SAXS
SAXS

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Characterisation Results XRD mineral analysis[1,7,9-12]


Table 5: Crystalline mineral phase abundance in the samples
Mineral
phase / Sample Chemical formula Coal FOZ Coal DEN Coal OGS Coal TKD
ID
Al2Si2O5(OH)4
Kaolinite
52.3
36.9
57.2
48.6
Quartz
Dolomite
Calcite
Microcline
Pyrite
Muscovite
Rutile
Siderite

SiO2

18.5

36.0

21.3

26.7

CaMg(CO3)2

7.7

8.2

3.9

6.0

CaCO3

7.5

5.3

5.6

2.0

KAlSi3O8

5.9

4.6

3.6

2.4

FeS2

4.0

4.8

2.9

2.3

KAll2AlSi3O10(OH)2

3.5

3.8

4.6

8.6

TiO2

0.4

0.4

0.1

0.9

FeCO3

0.2

0.0

0.6

2.6

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HPGA results- Adsorption isotherms


(a)

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(b)

(c)

(d)

Figure 7: CO2, CH4 and N2 isotherms of coals: (a) FOZ; (b) DEN; (c) OGS, and (d)
TKD
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HPGA results- Comparison of HP adsorption isotherms

Figure 8: Comparison of HP adsorption isotherms: (a) CO 2; (b) CH4; and (c)N2


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HPGA results- model fittings- CO2: D-R and MD-R

PAGE: 9

[1,7,9-12]

Figure 9: Fitting of D-R and MD-R model data to the experimental CO2 HP adsorption data
of the samples
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HPGA results- model fittings- CH4: D-R and MD-R

PAGE: 9

[1,7,9-12]

Figure 10: Fitting of D-R and MD-R model data to the experimental CH4 HP adsorption
data of the samples
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HPGA results- model fittings- N2: D-R and MD-R

PAGE: 9

[1,7,9-12]

Figure 11: Fitting of D-R and MD-R model data to the experimental N2 HP adsorption data
of the samples
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HPGA results: Sorption properties of samples


Properties / Sample ID
Sorption Capacity, W0
Affinity constant, D
Heat of sorption, Es
Proportionality constant, k
ESS
RMS Residuals
QOF (%)

Sorption Capacity, W0
Affinity constant, D
Heat of sorption, Es
Proportionality constant, k
ESS
RMS Residuals
QOF (%)

Sorption Capacity, W0
Affinity constant, D
Heat of sorption, Es
Proportionality constant, k
ESS
RMS Residuals
QOF (%)

FOZ
D-R
MD-R
86.9
60.6
0.076
0.049
9.9
12.3
0.035
454.3
4.6
7.13
0.54
81.4
97.4
18.1
0.090
9.1
1.97
0.47
92.6

13.3
0.070
10.3
0.034
0.18
0.12
94.4

21.7
0.130
7.6
1.88
0.38
87.1

13.2
0.099
8.7
0.032
0.11
0.09
94.9

Carbon dioxide CO2


DEN
OGS
D-R
MD-R
D-R
MD-R
65.4
56.3
71.6
51.4
0.060
0.051
0.068
0.045
11.1
12.1
10.5
12.8
0.013
0.029
100.2
4.2
454.3
4.6
2.78
0.57
5.91
0.60
91.4
97.3
81.4
97.4
Methane CH4
13.6
12.1
15.1
11.4
0.079
0.071
0.084
0.067
9.7
10.2
9.4
10.6
0.011
0.027
1.97
0.18
1.97
0.18
0.20
0.12
0.39
0.12
92.6
94.4
92.6
94.4
Nitrogen N2
14.8
12.1
18.1
13.1
0.116
0.104
0.124
0.104
8.0
8.5
7.8
8.5
0.010
-0.019
0.26
0.06
0.87
0.28
0.14
0.07
0.26
0.15
95.1
94.5
90.1
94.4
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PAGE: 9

TKD
D-R
MD-R
57.7
40.7
0.070
0.046
10.3
12.7
0.024
454.3
4.6
5.01
0.86
81.4
97.4
12.9
0.092
9.0
2.87
0.39
90.8

10.1
0.077
9.9
0.020
0.19
0.29
94.9

15.0
0.118
7.9
0.94
0.27
87.6

10.4
0.096
8.8
0.018
0.31
0.15
95.3

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HPGA results- Comparison of sorption capacities of samples

Figure 12: Sorption capacities of the samples


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HPGA results- Comparison of sorption capacities of samples

Figure 13: Affirnity constant, D, of samples


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HPGA results- Comparison of sorption capacities of samples

Figure 14: Sorption capacity of CO2 vs sorption capacities of CH4 and N2


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HPGA results- Comparison of sorption capacities of samples

Figure 15: Sorption capacity of CO2 vs vitrinite reflectance of samples


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HPGA results- Comparison of sorption capacities of samples

Figure 16: Sorption capacity of CO2 vs micropore volume


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PAGE: 9

HPGA results- Comparison of sorption capacities of samples

Figure 17: Sorption capacity of CO2 vs SAXS microporosity


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PAGE: 9

HPGA results- Comparison of sorption capacities of samples

Figure 15: Sorption capacity of CO2 vs ash yeilds


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Conclusion
For the adsorbate gases, the affirnity constant of the samples increased in the order: CO 2 <
CH4 < N2.
The adsorption energy of the samples for the three adsorbate gases was low (<13 kJ/mol),
indicating that physical adsorption was the dominating sorption mechanism.
The sorption capacities of the samples increased with increasing microporosity and
micropore volume; but decreased with increasing vitrinite reflectance of the coals.
The excess sorption capacity of the samples fitted the Modified Dubinin-Radushkevich
(MD-R) model satisfactorily.
Sorption capacity of the samples increased in the order: TKD < OGS < DEN < FOZ
MD-R fitted the experimental data better than D-R with higher QOF.

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Acknowledgement
This work is based on the research supported by
the South African Research Chairs Initiative of
the Department of Science and Technology
(DST) and National Research Foundation
(NRF) of South Africa.
Any opinion, finding, conclusion or recommendation expressed in this material is that of the author(s) and the NRF does not accept any liability in this regard.

Dr. Jayita Bandyopadhyay (CSIR)


Mr. Johan de Korte (CSIR)
Coal Samples:

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