Research Papers: Fuel Combustion

Sorption Hysteresis Characterization of CH4 and CO2 on Anthracite, Bituminous Coal, and Lignite at Low Pressure

[+] Author and Article Information
Zhenjian Liu

State Key Laboratory of Coal Mine Disaster
Dynamics and Control,
Chongqing University,
No. 174 Shazhengjie Street, Shapingba District,
Chongqing 400044, China
e-mail: lzyjian@163.com

Zhenyu Zhang

State Key Laboratory of Coal Mine Disaster
Dynamics and Control,
Chongqing University,
No. 174 Shazhengjie Street, Shapingba District,
Chongqing 400044, China
e-mail: zyzhang@cqu.edu.cn

Yiyu Lu

State Key Laboratory of Coal Mine Disaster
Dynamics and Control,
Chongqing University,
No. 174 Shazhengjie Street, Shapingba District,
Chongqing 400044, China
e-mail: luyiyu@cqu.edu.cn

Sing Ki Choi

Commonwealth Scientific and Industrial
Research Organization (CSIRO),
CSIRO Energy, Gate 7,
71 Normanby Road,
Clayton 3168, Victoria, Australia
e-mail: Xavier.Choi@csiro.au

Xiaoqian Liu

State Key Laboratory of Coal Mine Disaster
Dynamics and Control,
Chongqing University,
No. 174 Shazhengjie Street, Shapingba District,
Chongqing 400044, China
e-mail: liuxq@cqu.edu.cn

Contributed by the Advanced Energy Systems Division of ASME for publication in the JOURNAL OF ENERGY RESOURCES TECHNOLOGY. Manuscript received April 2, 2017; final manuscript received July 26, 2017; published online August 22, 2017. Assoc. Editor: Ashwani K. Gupta.

J. Energy Resour. Technol 140(1), 012203 (Aug 22, 2017) (9 pages) Paper No: JERT-17-1148; doi: 10.1115/1.4037483 History: Received April 02, 2017; Revised July 26, 2017

Sorption hysteresis characterization of CH4 and CO2 on lignite, bituminous coal, and anthracite were studied to improve the understanding of the interaction between gas molecules and different ranks of coal and further improve the precision of the adsorption methods in characterizing pore structure at low pressure. Pore structure of three ranks of coal was investigated with scanning electron microscopy (SEM) and nitrogen (N2) adsorption. Then, CH4 and CO2 sorption isotherms were measured using the gravimetric method under 288, 308, and 328 K. The N2 sorption isotherms show that a wide distribution of pore size existed in three coal samples, and with the process of coalification, the specific surface area (SSA) decreased and then increased, while the pore size of coal monotonically decreased. This is confirmed by SEM observation. The measured sorption isotherms were then decomposed into simultaneously running adsorption and absorption branches based on the assumption that the former is totally reversible and the latter completely irreversible. The reconstructed adsorption branches can be well described by both Langmuir model and Dubinin–Radushkevich (D–R) equation. The absorption, which represents the sorption hysteresis portion, increased with pressure, but decreased with temperature. The absorbed amount of gas increased with pressure, but the absorption of CO2 increased concavely with gas pressure while CH4 followed an upward exponential function. Also, the absorption varied with coal rank, following a U-shaped function. This study can provide new insights to CH4 and CO2 sorption hysteresis on coal and other organic geomaterials.

Copyright © 2018 by ASME
Your Session has timed out. Please sign back in to continue.


Gunter, W. D. , Gentzis, T. , Rottenfuser, B. A. , and Richardson, R. J. H. , 1997, “ Deep Coal Bed Methane in Alberta, Canada: A Fossil Resource With the Potential of Zero Greenhouse Gas Emissions,” Energy Convers. Manage., 38, pp. 217–222. [CrossRef]
Stopa, J. , and Nawrat, S. , 2012, “ Computer Modeling of Coal Bed Methane Recovery in Coal Mines,” ASME J. Energy Resour. Technol., 134(3), p. 032804. [CrossRef]
Prabu, V. , and Mallick, N. , 2015, “ Coalbed Methane With CO2 Sequestration: An Emerging Clean Coal Technology in India,” Renewable Sustainable Energy Rev., 50, pp. 229–244. [CrossRef]
Zhu, J. F. , Liu, J. Z. , Yang, Y. M. , Cheng, J. , Zhou, J. H. , and Cen, K. F. , 2016, “ Fractal Characteristics of Pore Structures in 13 Coal Specimens: Relationship Among Fractal Dimension, Pore Structure Parameter, and Slurry Ability of Coal,” Fuel Process Technol., 149, pp. 256–267. [CrossRef]
Zou, M. J. , Wei, C. T. , Huang, Z. Q. , Zhang, M. , and Lv, X. C. , 2015, “ Experimental Study on Identification Diffusion Pores, Permeation Pores and Cleats of Coal Samples,” ASME J. Energy Resour. Technol., 138(2), p. 021201. [CrossRef]
Gürdal, G. , and Yalçın, M. N. , 2000, “ Gas Adsorption Capacity of Carboniferous Coals in the Zonguldak Basin (NW Turkey) and Its Controlling Factors,” Fuel, 79(15), pp. 1913–1924. [CrossRef]
Harris, L. A. , and Yust, C. S. , 1976, “ Transmission Electron Microscope Observations of Porosity in Coal,” Fuel, 55(3), pp. 233–236. [CrossRef]
Perera, M. S. A. , Ranjith, P. G. , Choi, S. K. , Airey, D. , and Weniger, P. , 2012, “ Estimation of Gas Adsorption Capacity in Coal: A Review and An Analytical Study,” Int. J. Coal Prep. Util., 32(1), pp. 25–55. [CrossRef]
Ozdemir, E. , and Schroeder, K. , 2009, “ Effect of Moisture on Adsorption Isotherms and Adsorption Capacities of CO2 on Coals,” Energy Fuels, 23(5), pp. 2821–2831. [CrossRef]
Gensterblum, Y. , Merkel, A. , Busch, A. , and Krooss, B. M. , 2013, “ High-Pressure CH4 and CO2 Sorption Isotherms as a Function of Coal Maturity and the Influence of Moisture,” Int. J. Coal Geol., 118, pp. 45–57. [CrossRef]
Wang, Z. , Tang, X. , Yue, G. , Kang, B. , Xie, C. , and Li, X. , 2015, “ Physical Simulation of Temperature Influence on Methane Sorption and Kinetics in Coal: Benefits of Temperature Under 273.15 K,” Fuel, 158, pp. 207–216. [CrossRef]
Weniger, P. , Kalkreuth, W. , Busch, A. , and Krooss, B. M. , 2010, “ High-Pressure Methane and Carbon Dioxide Sorption on Coal and Shale Samples From the Paraná Basin, Brazil,” Int. J. Coal Geol., 84(3–4), pp. 190–205. [CrossRef]
Nie, B. , Liu, X. , Yuan, S. , Ge, B. , Jia, W. , Wang, C. , and Chen, X. , 2016, “ Sorption Characteristics of Methane Among Various Rank Coals: Impact of Moisture,” Adsorption, 22(3), pp. 315–325. [CrossRef]
Bae, J. S. , Bhatia, S. K. , Rudolph, V. , and Massarotto, P. , 2009, “ Pore Accessibility of Methane and Carbon Dioxide in Coals,” Energy Fuels, 23(6), pp. 3319–3327. [CrossRef]
Melnichenko, Y. B. , He, L. , Sakurovs, R. , Kholodenko, A. L. , Blach, T. , Mastalerz, M. , Radliński, A. P. , Cheng, G. , and Mildner, D. F. R. , 2012, “ Accessibility of Pores in Coal to Methane and Carbon Dioxide,” Fuel, 91(1), pp. 200–208. [CrossRef]
Mosher, K. , He, J. , Liu, Y. , Rupp, E. , and Wilcox, J. , 2013, “ Molecular Simulation of Methane Adsorption in Micro- and Mesoporous Carbons With Applications to Coal and Gas Shale Systems,” Int. J. Coal Geol., 109–110, pp. 36–44. [CrossRef]
Du, X. D. , Gu, M. , Duan, S. , and Xian, X. F. , 2016, “ Investigation of CO2–CH4 Displacement and Transport in Shale for Enhanced Shale Gas Recovery and CO2 Sequestration,” ASME J. Energy Resour. Technol., 139(1), p. 012909. [CrossRef]
Fu, H. , Tang, D. , Xu, T. , Xu, H. , Tao, S. , Li, S. , Yin, Z. , Chen, B. , Zhang, C. , and Wang, L. , 2017, “ Characteristics of Pore Structure and Fractal Dimension of Low-Rank Coal: A Case Study of Lower Jurassic Xishanyao Coal in the Southern Junggar Basin, NW China,” Fuel, 193, pp. 254–264. [CrossRef]
Wang, K. , Wang, G. , Ren, T. , and Cheng, Y. , 2014, “ Methane and CO2 Sorption Hysteresis on Coal: A Critical Review,” Int. J. Coal Geol., 132, pp. 60–80. [CrossRef]
Battistutta, E. , Hemert, P. V. , Lutynski, M. , Bruining, H. , and Wolf, K. H. , 2010, “ Swelling and Sorption Experiments on Methane, Nitrogen and Carbon Dioxide on Dry Selar Cornish Coal,” Int. J. Coal Geol., 84(1), pp. 39–48. [CrossRef]
Harpalani, S. , Prusty, B. K. , and Dutta, P. , 2006, “ Methane/CO2 Sorption Modeling for Coalbed Methane Production and CO2 Sequestration,” Energy Fuels, 20(4), pp. 1591–1599. [CrossRef]
Romanov, V. , and Soong, Y. , 2008, “ Long-Term CO2 Sorption on Upper Freeport Coal Powder and Lumps,” Energy Fuels, 22(2), pp. 1167–1169. [CrossRef]
Monson, P. A. , 2012, “ Understanding Adsorption/Desorption Hysteresis for Fluids in Mesoporous Materials Using Simple Molecular Models and Classical Density Functional Theory,” Microporous Mesoporous Mater., 160, pp. 47–66. [CrossRef]
Neimark, A. V. , Ravikovitch, P. I. , and Vishnyakov, A. , 2000, “ Adsorption Hysteresis in Nanopores,” Phys. Rev. E., 62(2), pp. 1493–1496. [CrossRef]
Busch, A. , Gensterblum, Y. , and Krooss, B. M. , 2003, “ Methane and CO2 Sorption and Desorption Measurements on Dry Argonne Premium Coals: Pure Components and Mixtures,” Int. J. Coal Geol., 55(2–4), pp. 205–224. [CrossRef]
McBain, J. W. , 1935, “ An Explanation of Hysteresis in the Hydration and Dehydration of Gels,” J. Am. Chem. Soc., 57(4), pp. 699–700. [CrossRef]
Seaton, N. A. , 1991, “ Determination of the Connectivity of Porous Solids From Nitrogen Sorption Measurements,” Chem. Eng. Sci., 46(8), pp. 1895–1909. [CrossRef]
Libby, B. , and Monson, P. A. , 2004, “ Adsorption/Desorption Hysteresis in Inkbottle Pores: A Density Functional Theory and Monte Carlo Simulation Study,” Langmuir, 20(10), pp. 4289–4294. [CrossRef] [PubMed]
Thommes, M. , Smarsly, B. , Groenewolt, M. , Ravikovitch, P. I. , and Neimark, A. V. , 2006, “ Adsorption Hysteresis of Nitrogen and Argon in Pore Networks and Characterization of Novel Micro- and Mesoporous Silicas,” Langmuir, 22(2), pp. 756–764. [CrossRef] [PubMed]
Clarkson, C. R. , and Bustin, R. M. , 2000, “ Binary Gas Adsorption/Desorption Isotherms: Effect of Moisture and Coal Composition Upon Carbon Dioxide Selectivity Over Methane,” Int. J. Coal Geol., 42(4), pp. 241–271. [CrossRef]
Jessen, K. , Guo, Q. T. , and Kovscek, A. R. , 2008, “ Laboratory and Simulation Investigation of Enhanced Coalbed Methane Recovery by Gas Injection,” Transp. Porous Media., 73(2), pp. 141–159. [CrossRef]
Ozdemir, E. , Morsi, B. I. , and Schroeder, K. , 2004, “ CO2 Adsorption Capacity of Argonne Premium Coals,” Fuel, 83(7–8), pp. 1085–1094. [CrossRef]
Medek, J. , Weishauptova, Z. , and Kovar, L. , 2006, “ Combined Isotherm of Adsorption and Absorption on Coal and Differentiation of Both Process,” Microporous Mesoporous Mater., 89(1–3), pp. 276–283. [CrossRef]
Huang, W. , Peng, Pa. , Yu, Z. , and Fu, J. , 2003, “ Effects of Organic Matter Heterogeneity on Sorption and Desorption of Organic Contaminants by Soils and Sediments,” Appl. Geochem., 18(7), pp. 955–972. [CrossRef]
Wang, F. , and Cheng, Y. P. , 2014, “ Influence of Coalification on the Pore Characteristics of Middle-High Rank Coal,” Energy Fuels, 28(9), pp. 5729–5736. [CrossRef]
Li, D. , Liu, Q. , Weniger, P. , Gensterblum, Y. , Busch, A. , and Krooss, B. M. , 2010, “ High-Pressure Sorption Isotherms and Sorption Kinetics of CH4 and CO2 on Coals,” Fuel, 89(3), pp. 569–580. [CrossRef]
Lee, H. H. , Kim, H. J. , Shi, Y. , Keffer, D. , and Lee, C. H. , 2013, “ Competitive Adsorption of CO2/CH4 Mixture on Dry and Wet Coal From Subcritical to Supercritical Conditions,” Chem. Eng. J., 230, pp. 93–101. [CrossRef]
Dutta, P. , Bhowmik, S. , and Das, S. , 2011, “ Methane and Carbon Dioxide Sorption on a Set of Coals From India,” Int. J. Coal. Geol., 85(3–4), pp. 289–299. https://doi.org/10.1016/j.coal.2010.12.004
Pognon, G. , Brousse, T. , and Bélanger, D. , 2011, “ Effect of Molecular Grafting on the Pore Size Distribution and the Double Layer Capacitance of Activated Carbon for Electrochemical Double Layer Capacitors,” Carbon, 49(4), pp. 1340–1348. [CrossRef]
Goodman, A. L. , Busch, A. , Duffy, G. J. , Gasem, K. A. M. , Gensterblum, Y. , Krooss, B. M. , Levy, J. , Ozdemir, E. , Pan, Z. , Robinson, R. L. , Schroeder, K. , Sudibandriyo, M. , and White, C. M. , 2004, “ An Inter-Laboratory Comparison of CO2 Isotherms Measured on Argonne Premium Coal Samples,” Energy Fuels, 18(4), pp. 1175–1182. [CrossRef]
Sing, K. S. W. , Everett, D. H. , Haul, R. A. W. , Mouscou, L. , Pierotti, R. A. , Rouquerol, J. , and Siemieniewska, T. , 1985, “ Reporting Physisorption Data for Gas/Solid Systems With Special Reference to the Determination of Surface Area and Porosity,” Pure Appl. Chem., 57(4), pp. 603–619. https://doi.org/10.1351/pac198557040603
Raymundo-Piñero, E. , Kierzek, K. , Machnikowski, J. , and Béguin, F. , 2006, “ Relationship Between the Nanoporous Texture of Activated Carbons and Their Capacitance Properties in Different Electrolytes,” Carbon, 44(12), pp. 2498–2507. [CrossRef]
Shagafi, A. , 2010, “ Potential for ECBM and CO2 Storage in Mixed Gas Australian Coals,” Int. J. Coal Geol., 82(3–4), pp. 240–251. [CrossRef]
Merkel, A. , Gensterblum, Y. , Krooss, B. M. , and Amann, A. , 2015, “ Competitive Sorption of CH4, CO2 and H2O on Natural Coals of Different Rank,” Int. J. Coal Geol., 150–151, pp. 181–192. [CrossRef]
Yang, R. T. , 1987, Gas Separation by Adsorption, Butterworth-Heinemann, Boston, MA.


Grahic Jump Location
Fig. 1

Schematic diagram of experimental setup

Grahic Jump Location
Fig. 2

N2 adsorption and desorption isotherms of the three coal samples at 77 K

Grahic Jump Location
Fig. 3

Cumulated surface area versus pore width of the coal samples

Grahic Jump Location
Fig. 4

Pore size distribution of the three coal samples

Grahic Jump Location
Fig. 5

SEM images of coal samples at a magnification time of 5000

Grahic Jump Location
Fig. 6

Sorption isotherms of CO2 (a) and CH4 (b) on coals at 288, 308, and 328 K

Grahic Jump Location
Fig. 7

Division of the sorption isotherms at 308 K

Grahic Jump Location
Fig. 8

Langmuir fitting of adsorption at 288, 308, and 328 K: (a) CO2 and (b) CH4

Grahic Jump Location
Fig. 9

D-R fitting of adsorption at 288, 308, and 328 K: (a) CO2 and (b) CH4

Grahic Jump Location
Fig. 10

Gas absorption on coal at 288, 308, and 328 K: (a) CO2 and (b) CH4



Some tools below are only available to our subscribers or users with an online account.

Related Content

Customize your page view by dragging and repositioning the boxes below.

Related Journal Articles
Related eBook Content
Topic Collections

Sorry! You do not have access to this content. For assistance or to subscribe, please contact us:

  • TELEPHONE: 1-800-843-2763 (Toll-free in the USA)
  • EMAIL: asmedigitalcollection@asme.org
Sign In