Skip to main content
Log in

On the porous structure of coals: Evidence for an interconnected but constricted micropore system and implications for coalbed methane recovery

  • Published:
Adsorption Aims and scope Submit manuscript

Abstract

An experimental and theoretical study of adsorption and diffusion of carbon dioxide and methane in coals of widely varying rank was carried out. Low pressures adsorption isotherms of CO2 were obtained and analyzed using Dubinin's theory of volume filling of micropores. High-pressure adsorption isotherms of CH4 were obtained and analyzed using tracer pulse chromatography in conjunction with an appropriate adsorption/diffusion model. A preliminary129Xe NMR analysis of chemical shifts experienced by xenon atoms in particles of different sizes is also reported.

The heretofore undocumented and/or underestimated effects of activated diffusion of CO2 at 273–298 K complicate the elucidation of the true microporous structure of coals, especially its dependence on coal rank. Activated diffusion of both CO2 and methane at room temperature does not allow reliable estimates of coalbed gas content to be made. A model of an interconnected network of pores which includes randomly distributed, numerous and ultramicroporous constrictions (at any size scale) is consistent with all these experimental and theoretical findings.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  • Anderson, S., Ph.D. Thesis, The Pennsylvania State University, 1997.

  • Boehm, H.P., B. Tereczki, and K. Schanz, “Blocking of Pores in Porous Carbons by Chemisorption.”, inAdsorption at the Gas-Solid and Liquid-Solid Interface, J. Rouquerol and K.S.W. Sing (Eds.), pp. 395–401, Elsevier, Amsterdam, 1982.

    Google Scholar 

  • Bojan, M.J., R.P. Danner, C.V. Menon, G. Mitchell, L.R. Radovic, and W.A. Steele, “Adsorption and Transport in Coalbed Reservoirs,” Gas Research Institute, Final Report, 1994.

  • Bojan, M.J., G. Mitchell, L.R. Radovic, and W.A. Steele, “Adsorption and Transport in Coalbed Reservoirs,” Gas Research Institute, Report # GRI-91/0375, 1992.

  • Carrasco-Marin, F., M.V. López-Ramón, and C. Moreno-Castilla, “Applicability of the Dubinin-Radushkevich Equation to CO2 Adsorption on Activated Carbons,”Langmuir,9, 2758–2760 (1993).

    Google Scholar 

  • Close, J.C., T.J. Pratt, and M.J. Mavor, “Evaluation of the Cooperative Research Well Valencia Canyon 32-1,” Gas Research Institute, Report #GRI-92/0016, 1992.

  • Danner, R.P., M.P. Nicoletti, and R.S. Al-Almeeri, “Determination of Gas Mixture Adsorption Equilibria by the Tracer-Pulse Technique,”Chem. Eng. Sci.,35, 2129–2133 (1980).

    Google Scholar 

  • Demarquay, J. and J. Fraissard, “129Xe NMR of Xenon Adsorbed on Zeolites. Relationship Between the Chemical Shift and the Void Space,”Chem. Phys. Lett.,136, 314–318 (1987).

    Google Scholar 

  • Derbyshire, F.J., “Catalysis in Coal Liquefaction,” International Energy Agency Report, IEACR/08, 1985.

  • Dubinin, M.M., “Physical Adsorption of Gases and Vapors in Micropores,” inProgress in Surface and Membrane Science, D.A. Cadenhead, J.F. Danielli, and M.D. Rosenberg (Eds.), pp. 1–70. Academic Press, New York, 1975.

    Google Scholar 

  • Dubinin, M.M., “Fundamentals of the Theory of Adsorption in Micropores of Carbon Adsorbents: Characteristics of Their Adsorption Properties and Microporous Structures,”Pure Appl. Chem.,61, 1841–1843 (1989).

    Google Scholar 

  • Dybowski, C., N. Bansal, and T.M. Duncan, “NMR Spectroscopy of Xenon in Confined Spaces: Clathrates, Intercalates, and Zeolites,” inAnnual Review of Physical Chemistry, H.L. Strauss, G.T. Babcock, and S.R. Leone (Eds.), pp. 433–464. Annual Reviews Inc., Palo Alto, CA, 1991.

    Google Scholar 

  • Eddy, G.E. and C.T. Rightmire, “Relationship of Methane Content of Coal Rank and Depth: Theoretical vs. Observed,” inSPE/DOE Unconventional Gas Recovery Symposium, pp. 117–122, Pittsburgh, PA, 1982.

  • Franklin, R., “A Study of the Fine Structure of Carbonaceous Solids by Measurements of True and Apparent Densities,”Trans. Faraday Soc.,45, 274–286 (1949).

    Google Scholar 

  • Gallegos, D.P., K. Munn, D.M. Smith, and D.L. Stermer, “A NMR Technique for the Analysis of Pore Structure: Application to Materials with Well-Defined Pore Structure,”J. Colloid Interf. Sci.,119, 127–140 (1987).

    Google Scholar 

  • Garrido, J., A. Linares-Solano, J.M. Martín-Martínez, M. Molina-Sabio, F. Rodriguez-Reinoso, and R. Torregrosa, “Use of N2 vs. CO2 in the Characterization of Activated Carbons,”Langmuir,3, 76–81 (1987).

    Google Scholar 

  • Hirsch, P.B., “X-ray Scattering from Coals,”Proc. Roy. Soc., (London),A226, 143–169 (1954).

    Google Scholar 

  • Hufton, J.R., Ph.D. Thesis, The Pennsylvania State University, 1992.

  • Joubert, J.I., C.T. Grein, and D. Bienstock, “Sorption of Methane in Moist Coal,”Fuel,52, 181–185 (1973).

    Google Scholar 

  • Joubert, J.I., C.T. Grein, and D. Bienstock, “Effect of Moisture on the Methane Capacity of American Coals,”Fuel,53, 186–191 (1974).

    Google Scholar 

  • Kaplan, J.I. and G. Fraenkel,NMR of Chemically Exchanging Systems, Academic Press, New York, 1980.

    Google Scholar 

  • Kim, A.G., “Estimating Methane Content of Bituminous Coalbeds from Adsorption Data,” Bureau of Mines Report #8245, 1977.

  • King, G.R. and T. Ertekin, “State-of-the-Art in Modeling of Unconventional Gas Recovery,” inSPE Joint Rocky Mountain Regional/Low Permeability Reservoir Symposium, pp. 173–191. Denver, CO, 1989.

  • Kobayashi, M., E. Ishikawa, and Y. Toda, “Experimental Relation Between DR Equation and Langmuir Equation for Various Adsorbates on Many Carbons,”Carbon,31, 990–992 (1993).

    Google Scholar 

  • Larsen, J.W., P. Hall, and P.C. Wernett, “Pore Structure of the Argonne Premium Coals,”Energy Fuels,9, 324–330 (1995).

    Google Scholar 

  • Larsen, J.W. and P. Wernett, “Pore Structure of Illinois No. 6 Coal,”Energy Fuels,2, 719–720 (1988).

    Google Scholar 

  • Larsen, J.W. and P.C. Wernett, “The Argonne Coasl Do Not Have an Extended Inter-Connected Pore Network,” inAmerican Chemical Society Preprints (Division of Fuel Chemistry), pp. 849–855, San Francisco, 1992.

  • Levine, J.R., “Oversimplifications Can Lead to Faulty Coalbed Gas Reservoir Analysis.”Oil and Gas Journal, pp. 63–69. Nov. 23, 1992.

  • Lizzio, A.A., S.N. Vyas, and M. Rostam-Abadi, “Synthesis of Carbon Molecular Sieves From Illinois Coal: Carbon vs. Oxygen Deposition,” inCarbon '94, Granada, Spain, pp. 530–531.

  • Mahajan, O.P., “Coal Porosity,” inCoal Structure, R.A. Meyers (Ed.). pp. 51–86, Academic Press, New York, 1982.

    Google Scholar 

  • Mahajan, O.P., “CO2 Surface Area of Coals: The 25-year Paradox,”Carbon,29, 735–742 (1991).

    Google Scholar 

  • Marsh, H.. “Adsorption Methods to Study Microporosity in Coals and Carbons—A Critique,”Carbon,25, 49–58 (1987).

    Google Scholar 

  • Mavor, M.J., L.B. Owen, and T.J. Pratt, “Measurement and Evaluation of Coal Sorption Isotherm Data,” in65th Annual Technical Conference and Exhibition of the Society of Petroleum Engineers, New Orleans, LA, SPE #20728, 1990.

  • McCulloch, C.M. and W.P. Diamond, “Inexpensive Method Helps Predict Methane Content of Coal Beds,”Coal Age, pp. 102–106. June 1976.

  • McElhiney, J.E., R.A. Koenig, and R.A. Schraufnagel, “Evaluation of Coalbed-Methane Reserves Involves Different Techniques,”Oil and Gas Journal, pp. 63–72. Oct. 30, 1989.

  • Menon, V.C. The Pennsylvania State University, unpublished work (1996).

  • Moudrakovski, J.L., C.I. Ratcliffe, and J.A. Ripmeester, “Application of129Xe 2D-EXSY NMR to Intra- and Interparticle Exchange in Zeolites,”Appl. Magn. Reson.,8, 385–399 (1995).

    Google Scholar 

  • Nandi, S.P. and P.L. Walker, Jr., “Activated Diffusion of Methane From Coals at Elevated Pressures,”Fuel,54, 81–86 (1975).

    Google Scholar 

  • Oberholtzer, J.E. and L.B. Rogers, “Effects of Micropores on Peak Shape and Retention Volume in Gas-Solid Chromatography,”Anal. Chem.,41, 1590–1594 (1969).

    Google Scholar 

  • Olague, N.E. and D.M. Smith, “Diffusion of Gases in American Coals,”Fuel,68, 1381–1387 (1989).

    Google Scholar 

  • Patel, R.L., S.P. Nandi, and P.L. Walker, Jr., “Molecular Sieve Characteristics of Slightly Activated Anthracite,”Fuel,51, 47–51 (1972).

    Google Scholar 

  • Peterson, D.L., F. Helfferich, and R.J. Carr, “Measurement of Phase Equilibria at High Pressures by Tracer-Pulse Chromatography,”AIChE J.,12, 903–905 (1966).

    Google Scholar 

  • Rightmire, C.T., “Coalbed Methane Resource,” inCoalbed Methane Resources of the United States, C.T. Rightmire, G.E. Eddy, and J.N. Kirr (Eds.), pp. 1–13, The American Association of Petroleum Geologists, Tulsa, OK, 1984.

    Google Scholar 

  • Ripmeester, J.A. and C.I. Ratcliffe, “On the Application of129Xe NMR to the Study of Microporous Solids,”J. Phys. Chem.,94, 7652–7656 (1990).

    Google Scholar 

  • Ripmeester, J.A. and C.I. Ratcliffe, “129Xe NMR Spectroscopy in Microporous Solids: The Effect of Bulk Properties,”Anal. Chimica Acta,283, 1103–1112 (1993).

    Google Scholar 

  • Rodriguez-Reinoso, F. and A. Linares-Solano, “Microporous Structure of Activated Carbons as Revealed by Adsorption Methods,” inChemistry and Physics of Carbon, P.A. Thrower (Ed.) vol. 21, pp. 1–146, Marcel Dekker, New York, 1989.

    Google Scholar 

  • Rolniak, P.D. and R. Kobayashi, “Adsorption of Methane and Several Mixtures of Methane and Carbon Dioxide at Elevated Pressures and Near Ambient Temperatures on 5A and 13X Molecular Sieves by Tracer Perturbation Chromatography,”AIChE J. 26, 616–625 (1980).

    Google Scholar 

  • Ruppel, T.C., C.T. Grein, and D. Bienstock, “Adsorption of Methane on Dry Coal at Elevated Pressure,”Fuel,53, 152–162 (1974).

    Google Scholar 

  • Smith, D.M. and F.L. Williams, “Adsorption and Diffusion in Western United States Coals,” inCoal Science and Chemistry, A. Volborth, (Ed.), pp. 381–403, Elsevier, Amsterdam, 1987.

    Google Scholar 

  • Spencer, D.H.T. and R.L. Bond, “The Determination and Use of Specific Surface Values for Coals,”Adv. Chem. Ser.,55, 724–730 (1966).

    Google Scholar 

  • Stoeckli, F., D. Huguenin, A. Greppi, T. Jakubov, A. Pribylov, S. Kalashnikov, A. Fomkin, A. Pulin, N. Regent, and V. Serpinski, “On the Adsorption of CO2 by Active Carbons,”Chimia,47, 213–214, (1993).

    Google Scholar 

  • Suh, D.J., T.-J. Park, S.-K. Ihm, and R. Ryoo, “129Xe NMR Spectroscopy of Xenon Gas Adsorbed on Amorphous Carbons,”J. Phys. Chem.,95, 3767–3771 (1991).

    Google Scholar 

  • Tomita, A., T. Tano, Y. Oikawa, and Y. Tamai, “Gasification of Coals Treated with Non-Aqueous Solvents. 5. Properties of Coals Treated with Liquid Ammonia,”Fuel,58, 609–613 (1979).

    Google Scholar 

  • Tsiao, C. and R.E. Botto, “129Xe NMR Investigation of Coal Micropores,”Energy Fuels,5, 87–92 (1991).

    Google Scholar 

  • van der Sommen, J., P. Zwietering, B.J.M. Eillebrecht, and D.W. van Krevelen, “Chemical Structure and Properties of Coal. XII. Sorption Capacity for Methane.”Fuel,34, 444–448 (1955).

    Google Scholar 

  • Walker, P.L., “Microporosity in Coal: Its Characterization and Implications for Coal Utilization,”Phil. Trans. R. Soc. Lond. A,300, 65–81 (1981).

    Google Scholar 

  • Walker, P.L., Jr. and O.P. Mahajan, “Methane Diffusion in Coals and Chars,” inAnalytical Methods for Coal and Coal Products, C. Karr (Ed.), pp. 163–188, Academic Press, 1978.

  • Walker, P.L. and O.P. Mahajan, “Pore Structure in Coals,”Energy Fuels,7, 559–560 (1993).

    Google Scholar 

  • Wernett, P.C., J.W. Larsen, O. Yamada, and H.J. Yue, “Determination of the Average Micropore Diameter of an Illinois No. 6 Coal by Xe-129 NMR,”Energy Fuels,4, 412–413 (1990).

    Google Scholar 

  • Yang, R.T. and J.T. Saunders, “Adsorption of Gases on Coals and Heat-Treated Coals at Elevated Temperature and Pressure. 1. Adsorption from Hydrogen and Methane as Single Gases,”Fuel,64, 616–620 (1985).

    Google Scholar 

  • Yee, D., J.P. Seidle, and W.B. Hanson, “Gas Sorption on Coal and Measurement of Gas Content,” inHydrocarbons from Coal, B.E. Law and D.D. Rice (Eds.), pp. 203–218. The American Association of Petroleum Geologists, Tulsa, OK, 1993.

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Radovic, L.R., Menon, V.C., Leon Y Leon, C.A. et al. On the porous structure of coals: Evidence for an interconnected but constricted micropore system and implications for coalbed methane recovery. Adsorption 3, 221–232 (1997). https://doi.org/10.1007/BF01650133

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF01650133

Keywords

Navigation