Abstract
Gases like CO2 and CH4 are able to adsorb on the coal surface, but also to dissolve into its structure causing the coal to swell. In this work, the binary adsorption of CO2 and CH4 on a dry coal (Sulcis Coal Province, Italy) and its swelling behavior are investigated. The competitive adsorption measurements are performed at 45 °C and up to 190 bar for pure CO2, CH4 and four mixtures of molar feed compositions of 20.0, 40.0, 60.0 and 80.0% CO2 using a gravimetric-chromatographic technique. The results show that carbon dioxide adsorbs more favorably than methane leading to an enrichment of the fluid phase in CH4. Coal swelling is determined using a high-pressure view cell, by exposing a coal disc to CO2, CH4 and He at 45 and 60 °C and up to 140 bar. For CO2 and CH4 a maximum swelling of about 4 and 2% is found, whereas He shows negligible swelling. The presented adsorption and swelling data are then discussed in terms of fundamental, thermodynamic aspects of adsorption and properties which are crucial for an ECBM operation, i.e. the CO2 storage capacity and the dynamics of the replacement of CH4 by CO2.
Similar content being viewed by others
References
Arri, L.E., Yee, D., Morgan, W.D., Jeansonne, M.W.: Modeling coalbed methane production with binary gas sorption. SPE Paper 24363, Presented at the SPE Rocky Mountain Regional Meeting, Casper, Wyoming, May 18–21, 1992
Bae, J.S., Bhatia, S.K.: High-pressure adsorption of methane and carbon dioxide on coal. Energy Fuels 20, 2599–2607 (2006)
Bonavoglia, B., Storti, G., Morbidelli, M., Rajendran, A., Mazzotti, M.: Sorption and swelling of semicrystalline polymers in supercritical CO2. J. Polym. Sci. Part B Polym. Phys. 44, 1531–1546 (2006)
Busch, A., Gensterblum, Y., Krooss, B.M.: Methane and CO2 sorption and desorption measurements on dry Argonne premium coals: pure components and mixtures. Int. J. Coal Geol. 55, 205–224 (2003)
Busch, A., Gensterblum, Y., Krooss, B.M., Siemons, N.: Investigation of high-pressure selective adsorption/desorption CO2 and CH4 on coals: An experimental study. Int. J. Coal Geol. 66, 53–68 (2006)
Ceglarska-Stefanska, G., Zarebska, K.: Sorption of carbon dioxide-methane mixtures. Int. J. Coal Geol. 62, 211–222 (2005)
Chaback, J.J., Morgan, W.D., Yee, D.: Sorption of nitrogen, methane, carbon dioxide and their mixtures on bituminous coals at in-situ conditions. Fluid Phase Equilib. 117, 289–296 (1996)
DeGance, A.E., Morgan, W.D., Yee, D.: High-Pressure Adsorption of Methane, Nitrogen and Carbon-Dioxide on Coal Substrates. Fluid Phase Equilib. 82, 215–224 (1993)
Di Giovanni, O., Dörfler, W., Mazzotti, M., Morbidelli, M.: Adsorption of supercritical carbon dioxide on silica. Langmuir 17, 4316–4321 (2001)
Dreisbach, F., Staudt, R., Keller, J.U.: High pressure adsorption data of methane, nitrogen, carbon dioxide and their binary and ternary mixtures on activated carbon. Adsorption 5, 215–227 (1999)
Dreisbach, F., Seif, R., Lösch, H.W.: Gravimetric measurement of adsorption equilibria of gas mixture CO/H2 with a magnetic suspension balance. Chem. Eng. Technol. 25, 1060–1065 (2002)
Fitzgerald, J.E., Pan, Z., Sudibandriyo, M., Robinson, R.L. Jr., Gasem, K.A.M., Reeves, S.: Adsorption of methane, nitrogen, carbon dioxide and their mixtures on wet Tiffany coal. Fuel 84, 2351–2363 (2005)
Fitzgerald, J.E., Robinson, R.L. Jr., Gasem, K.A.M.: Modeling high-pressure adsorption of gas mixtures on activated carbon and coal using a simplified local-density model. Langmuir 22, 9610–9618 (2006)
Harpalani, S., Schraufnagel, R.A.: Shrinkage of coal matrix with release of gas and its impact on permeability of coal. Fuel 69, 551–556 (1990)
Hocker, T., Rajendran, A., Mazzotti, M.: Measuring and Modeling Supercritical adsorption in porous solids. Carbon dioxide on 13X zeolite and on silica gel. Langmuir 19, 1254–1267 (2003)
IPCC: IPCC Special Report on Carbon Dioxide Capture and Storage. Cambridge University Press, Cambridge (2005)
IPCC, Climate Change 2007: The Physical Science Basis. Summary for Policymakers. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, available online at http://www.ipcc.ch (2007)
Karacan, C.O.: Heterogeneous sorption and swelling in a confined and stressed coal during CO2 injection. Energy Fuels 17, 1595–1608 (2003)
Keller, J.U., Staudt, R.: Gas Adsorption Equilibria: Experimental Methods and Adsorptive Isotherms. Springer, New York (2005)
Keller, J.U., Dreisbach, F., Rave, H., Staudt, R., Tomalla, M.: Measurement of gas mixture adsorption equilibria of natural gas compounds on microporous sorbents. Adsorption 5, 199–214 (1999)
Krooss, B.M., van Bergen, F., Gensterblum, Y., Siemons, N., Pagnier, H.J.M., David, P.: High-pressure methane and carbon dioxide adsorption on dry and moisture-equilibrated Pennsylvanian coals. Int. J. Coal Geol. 51, 69–92 (2002)
Larsen, J.W.: The effects of dissolved CO2 on coal structure and properties. Int. J. Coal Geol. 57, 63–70 (2004)
Mazumder, S., van Hemert, P., Busch, A., Wolf, K.-H.A.A., Tejera-Cuesta, P.: Flue gas and pure CO2 sorption properties of coal: A comparative study. Int. J. Coal Geol. 67, 267–279 (2006)
Milewska-Duda, J., Duda, J., Nodzenski, A., Lakatos, J.: Absorption and adsorption of methane and carbon dioxide in hard coal and active carbon. Langmuir 16, 5458–5466 (2000)
Ottiger, S., Pini, R., Storti, G., Mazzotti, M., Bencini, R., Quattrocchi, F., Sardu, G., Deriu, G.: Adsorption of pure carbon dioxide and methane on dry coal from the Sulcis Coal Province (SW Sardinia, Italy). Environ. Prog. 25, 355–364 (2006)
Pan, Z., Connell, L.D.: A theoretical model for gas adsorption-induced coal swelling. Int. J. Coal Geol. 69, 243–252 (2007)
Pini, R., Ottiger, S., Rajendran, A., Storti, G., Mazzotti, M.: Reliable measurement of near-critical adsorption by gravimetric method. Adsorption 12, 393–403 (2006)
Quattrocchi, F., Bencini, R., Amorino, C., Basili, R., Caddeo, G., Cantucci, B., Cara, R., Cauli, G., Cinti, D., Deidda, C., Deriu, G., Fadda, A., Fadda, M., Fandino, V., Faranzena, S., Giannelli, A., Galli, G., Mazzotti, M., Ottiger, S., Pizzino, L., Pini, R., Sardu, G., Storti, G., Voltattorni, N.: Feasibility study (I stage) of CO2 geological storage by ECBM techniques in the Sulcis coal province (SW Sardinia, Italy). In Proceedings of the 8th International Conference on Greenhouse Gas Control Technologies, Trondheim, Norway, June 19–22, 2006
Rajendran, A., Bonavoglia, B., Forrer, N., Storti, G., Mazzotti, M., Morbidelli, M.: Simultaneous measurement of swelling and sorption in a supercritical CO2-poly(methyl methacrylate) system. Ind. Eng. Chem. Res. 44, 2549–2560 (2005)
Reeves, S., Taillefert, A., Pekot, L., Clarkson, C.: The Allison unit CO2-ECBM pilot: a reservoir modeling study. Topical report, US Department of Energy, available online at http://coal-seq.com (2003)
Reucroft, P.J., Sethuraman, A.R.: Effect of pressure on carbon-dioxide induced coal swelling. Energy Fuels 1, 72–75 (1987)
Scherer, G.W.: Dilatation of porous-glass. J. Am. Ceram. Soc. 69, 473–480 (1986)
Shimada, S., Li, H.Y., Oshima, Y., Adachi, K.: Displacement behavior of CH4 adsorbed on coals by injecting pure CO2, N2, and CO2–N2 mixture. Environ. Geol. 49, 44–52 (2005)
Sircar, S.: Excess properties and thermodynamics of multicomponent gas adsorption. J. Chem. Soc. Faraday Trans. I 81, 1527–1540 (1985a)
Sircar, S.: Excess properties and column dynamics of multicomponent gas adsorption. J. Chem. Soc. Faraday Trans. I 81, 1541–1545 (1985b)
St. George, J.D., Barakat, M.A.: The change in effective stress associated with shrinkage from gas desorption in coal. Int. J. Coal Geol. 45, 105–113 (2001)
Stevenson, M.D., Pinczewski, W.V., Somers, M.L., Bagio, S.E.: Adsorption/desorption of multicomponent gas mixtures at in-seam conditions. SPE Paper 23026, Presented at the SPE Asia-Pacific Conference, Perth, Western Australia, November 4–7, 1991
Van Bergen, F.: Field experiment of CO2-ECBM in the upper Silesian basin of Poland. Presented at the 5th International Forum on Geologic Sequestration of CO2 in Deep, Unmineable Coalseams (Coal-Seq V), Houston TX, November 8–9, 2006
Wong, S., Law, D., Deng, X., Robinson, J., Kadatz, B., Gunter, W.D., Ye, J., Feng, S., Fan, Z.: Enhanced coalbed methane—micro-pilot test at South Qinshui, Shanxi, China. In Proceedings of the 8th International Conference on Greenhouse Gas Control Technologies, Trondheim, Norway, June 19–22, 2006
Yamaguchi, S., Ohga, K., Fujioka, M., Nako, M., Muto, S.: Field experiment of Japan CO2 geosequestration in coal seams project (JCOP). In Proceedings of the 8th International Conference on Greenhouse Gas Control Technologies, Trondheim, Norway, June 19–22, 2006
Zehnder, B.: NIR-spektroskopische Bestimmung von Stoffaustauschkoeffizienten und Gleichgewichtslöslichkeiten in Fluid-Fluid-Systemen unter überkritischen Bedingungen. Dissertation Nr. 9657. ETH Zurich, Switzerland (1992)
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Ottiger, S., Pini, R., Storti, G. et al. Competitive adsorption equilibria of CO2 and CH4 on a dry coal. Adsorption 14, 539–556 (2008). https://doi.org/10.1007/s10450-008-9114-0
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10450-008-9114-0