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Adsorption equilibria and kinetics of CH4 and N2 on commercial zeolites and carbons

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Abstract

Adsorption equilibria and kinetics are two sets of properties crucial to the design and simulation of adsorption based gas separation processes. The adsorption equilibria and kinetics of N2 and CH4 on commercial activated carbon Norit RB3, zeolite 13X, zeolite 4A and molecular sieving carbon MSC-3K 172 were studied experimentally at temperatures of (273 and 303) K in the pressure range of (5–120) kPa. These measurements were in part motivated by the lack of consistent adsorption kinetic data available in the literature for these systems, which forces the use of empirical estimates with large uncertainties in process designs. The adsorption measurements were carried out on a commercial volumetric apparatus. To obtain reliable kinetic data, the apparatus was operated in its rate of adsorption mode with calibration experiments conducted using helium to correct for the impact of gas expansion on the observed uptake dynamics. Analysis of the corrected rate of adsorption data for N2 and CH4 using the non-isothermal Fickian diffusion (FD) model was also found to be essential; the FD model was able to describe the dynamic uptake observed to better that 1% in all cases, while the more commonly applied isothermal linear driving force model was found to have a relative root mean square deviation of around 10%. The measured sorption kinetics had no dependence on gas pressure but their temperature dependence was consistent with an Arrhenius-type relation. The effective sorption rates extracted using the FD model were able to resolve inconsistencies in the literature for similar measurements.

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References

  • Ahn, H., Yoo, H.-K., Shul, Y., Hyun, S., Lee, C.-H.: Diffusion mechanism of N2 and CH4 in pelletized zeolite 4A, 5A and CaX. J. Chem. Eng. Jpn. 35, 334–345 (2002)

    Article  CAS  Google Scholar 

  • Bae, Y.S., Lee, C.H.: Sorption kinetics of eight gases on a carbon molecular sieve at elevated pressure. Carbon 43, 95–107 (2005)

    Article  CAS  Google Scholar 

  • Bae, J.-S., Su, S., Yu, X.X.: Enrichment of ventilation air methane (VAM) with carbon fiber composites. Environ. Sci. Technol. 48, 6043–6049 (2014)

    Article  CAS  Google Scholar 

  • Bulow, M.: Comments on the publication “ adsorption kinetics of CO2, CO, N2 and CH4 on zeolite LiX pellet and activated carbon granule” by Youngsan Ju, Yongha Park, Dooyoung Park, Jae-Jeon Kim and Chang-Ha Lee. Adsorption 21, 419–432 (2015). https://www.researchgate.net/publication/293333947_Comments_on_the_publication_Adsorption_kinetics_of_CO2_CO_N2_and_CH4_on_zeolite_LiX_pellet_and_activated_carbon_granule_by_Youngsan_Ju_Yongha_Park_Dooyoung_Park_Jae-Jeon_Kim_and_Chang-Ha_Lee_Adsorptio

  • Dantas, T.L.P., Luna, F.M.T., Silva Jr., I.J., Torres, A.E.B., De Azevedo, D.C.S., Rodrigues, A.A., Moreira, R.F.P.M.: Modelling of the fixed-bed adsorption of carbon dioxide and a carbon dioxide-nitrogen mixture on zeolite 13X. Braz. J. Chem. Eng. 28, 533–544 (2011)

    Article  CAS  Google Scholar 

  • Delgado, J.A., Águeda, V.I., Uguina, M.A., Sotelo, J.L., Brea, P., Grande, C.A.: Adsorption and diffusion of H2, CO, CH4, and CO2 in BPL activated carbon and 13X zeolite: evaluation of performance in pressure swing adsorption hydrogen purification by simulation. Ind. Eng. Chem. Res. 53, 15414–15426 (2014)

    Article  CAS  Google Scholar 

  • Do, D.: Analysis of Adsorption Kinetics in a Single Homogeneous Particle, Adsorption Analysis: Equilibria and Kinetics, pp. 519–602. Imperial College Press, London (2011)

    Google Scholar 

  • Friedrich, D., Mangano, E., Brandani, S.: Automatic estimation of kinetic and isotherm parameters from ZLC experiments. Chem. Eng. Sci. 126, 616–624 (2015)

    Article  CAS  Google Scholar 

  • Giesy, T.J., Wang, Y., LeVan, M.D.: Measurement of mass transfer rates in adsorbents: new combined-technique frequency response apparatus and application to CO2 in 13X zeolite. Ind. Eng. Chem. Res. 51, 11509–11517 (2012)

    Article  CAS  Google Scholar 

  • Glueckauf, E., Coates, J.I.: Theory of chromatography. Part IV. The influence of incomplete equilibrium on the front boundary of chromatograms and on the effectiveness of separation. J. Chem. Soc. 241, 1315–1321 (1947)

    Article  Google Scholar 

  • Guan, C., Yang, C., Wang, K.: Adsorption kinetics of methane on a template-synthesized carbon powder and its pellet. Asia-Pac. J. Chem. Eng. 6, 294–300 (2011)

    Article  CAS  Google Scholar 

  • Haq, N., Ruthven, D.M.: Chromatographic study of sorption and diffusion in 4A zeolite. J. Colloid Interface Sci. 112, 154–163 (1986)

    Article  CAS  Google Scholar 

  • Hedin, N., Andersson, L., Bergström, L., Yan, J.: Adsorbents for the post-combustion capture of CO2 using rapid temperature swing or vacuum swing adsorption. Appl. Energy 104, 418–433 (2013)

    Article  CAS  Google Scholar 

  • Hossain, M.I.: Volume swing frequency response method for determining mass transfer mechanisms in microporous adsorbents. Doctoral dissertation. http://scholarcommons.sc.edu/etd/2585. (2014)

  • Hossain, M.I.: Volumetric swing frequency response method for determining mass transfer mechanisms in microporous adsorbents. Doctoral dissertation. College of Engineering and Computing, University of South Carolina (2014)

  • Hu, X., Mangano, E., Friedrich, D., Ahn, H., Brandani, S.: Diffusion mechanism of CO2 in 13X zeolite beads. Adsorption 20, 121–135 (2014)

    Article  CAS  Google Scholar 

  • Jayaraman, A., Hernandez-Maldonado, A.J., Yang, R.T., Chinn, D., Munson, C.L., Mohr, D.H.: Clinoptilolites for nitrogen/methane separation. Chem. Eng. Sci. 59, 2407–2417 (2004)

    Article  CAS  Google Scholar 

  • Jee, J.-G., Kim, M.-B., Lee, C.-H.: Pressure swing adsorption processes to purify oxygen using a carbon molecular sieve. Chem. Eng. Sci. 60, 869–882 (2005)

    Article  CAS  Google Scholar 

  • Jensen, N.K., Rufford, T.E., Watson, G., Zhang, D.K., Chan, K.I., May, E.F.: Screening zeolites for gas separation applications involving methane, nitrogen, and carbon dioxide. J. Chem. Eng. Data 57, 106–113 (2011)

    Article  Google Scholar 

  • Ju, Y., Park, Y., Park, D., Kim, J.-J., Lee, C.-H.: Adsorption kinetics of CO2, CO, N2 and CH4 on zeolite LiX pellet and activated carbon granule. Adsorption 21, 419–432 (2015)

    Article  CAS  Google Scholar 

  • Kocirik, M., Struve, P., Bulow, M.: Analytical solution of simultaneous mass and heat transfer in zeolite crystals under constant-volume/variable-pressure conditions. J. Chem. Soc. 80, 2167–2174 (1984)

    CAS  Google Scholar 

  • Lee, L.-K., Ruthven, D.M.: Analysis of thermal effects in adsorption rate measurements. J. Chem. Soc. 75, 2406–2422 (1979)

    CAS  Google Scholar 

  • Lee, K.B., Beaver, M.G., Caram, H.S., Sircar, S.: Novel thermal-swing sorption-enhanced reaction process concept for hydrogen production by low-temperature steam methane reforming. Ind. Eng. Chem. Res. 46, 5003–5014 (2007)

    Article  CAS  Google Scholar 

  • Malek, A., Farooq, S.: Kinetics of hydrocarbon adsorption on activated carbon and silica gel. AIChE J. 43, 761–776 (1997)

    Article  CAS  Google Scholar 

  • Mohr, R.J., Vorkapic, D., Rao, M.B., Sircar, S.: Pure and binary gas adsorption equilibria and kinetics of methane and nitrogen on 4A zeolite by isotope exchange technique. Adsorption 5, 145–158 (1999)

    Article  CAS  Google Scholar 

  • Moon, D.-K., Kim, Y.-H., Ahn, H., Lee, C.-H.: Pressure swing adsorption process for recovering H2 from the effluent gas of a melting incinerator. Ind. Eng. Chem. Res. 53, 15447–15455 (2014)

    Article  CAS  Google Scholar 

  • Mulgundmath, V.P., Tezel, F.H., Hou, F., Golden, T.C.: Binary adsorption behaviour of methane and nitrogen gases. J. Porous Mater. 19, 455–464 (2012)

    Article  CAS  Google Scholar 

  • Olajossy, A.: Effective recovery of methane from coal mine methane gas by vacuum pressure swing adsorption: a pilot scale case study. Chem. Eng. Sci. 1, 46–54 (2013)

    Article  Google Scholar 

  • Park, Y., Ju, Y., Park, D., Lee, C.-H.: Adsorption equilibria and kinetics of six pure gases on pelletized zeolite 13X up to 1.0 MPa: CO2, CO, N2, CH4, Ar and H2. Chem. Eng. J. 292, 348–365 (2016)

    Article  CAS  Google Scholar 

  • Rufford, T.E., Smart, S., Watson, G.C.Y., Graham, B.F., Boxall, J., da Costa, J.C.D., May, E.F.: The removal of CO2 and N2 from natural gas: a review of conventional and emerging process technologies. J. Petrol. Sci. Eng. 94–95, 123–154 (2012)

    Article  Google Scholar 

  • Rufford, T.E., Watson, G.C.Y., Saleman, T.L., Hofman, P.S., Jensen, N.K., May, E.F.: Adsorption equilibria and kinetics of methane + nitrogen mixtures on the activated carbon Norit RB3. Ind. Eng. Chem. Res. 52, 14270–14281 (2013)

    Article  CAS  Google Scholar 

  • Ruthven, D.M.: Principles of Adsorption and Adsorption Processes. Wiley, New York (1984)

    Google Scholar 

  • Ruthven, D.M., Lee, L.-K., Yucel, H.: Kinetics of non-isothermal sorption in molecular sieve crystals. AIChE J. 26, 16–23 (1980)

    Article  CAS  Google Scholar 

  • Ruthven, D.M., Farooq, S., Knaebel, K.S.: Pressure Swing Adsorption. VCH Publishers Inc., New York (1994)

    Google Scholar 

  • Rynders, R.M., Rao, M.B., Sircar, S.: Isotope exchange technique for measurement of gas adsorption equilibria and kinetics. AIChE J. 43, 2456–2470 (1997)

    Article  CAS  Google Scholar 

  • Saleman, T.L.: Adsorption-Based Separations of Gaseous Nitrogen and Methane Mixtures. School of Mechanical and Chemical Engineering, The University of Western Australia, Perth (2016)

    Google Scholar 

  • Saleman, T.L., Xiao, G., Li, G., May, E.: Robust high-pressure measurements of N2 and CH4 sorption equilibrium and kinetics with an improved dynamic column breakthrough technique. Adsorption (submitted)

  • Saleman, T.H., Watson, G.Y., Rufford, T., Hofman, P., Chan, K.I., May, E.: Capacity and kinetic measurements of methane and nitrogen adsorption on H+-mordenite at 243–303 K and pressures to 900 kPa using a dynamic column breakthrough apparatus. Adsorption 19, 1165–1180 (2013)

    Article  CAS  Google Scholar 

  • Saleman, T.L., Li, G., Rufford, T.E., Stanwix, P.L., Chan, K.I., Huang, S.H., May, E.F.: Capture of low grade methane from nitrogen gas using dual-reflux pressure swing adsorption. Chem. Eng. J. 281, 739–748 (2015)

    Article  CAS  Google Scholar 

  • Samanta, A., Zhao, A., Shimizu, G.K.H., Sarkar, P., Gupta, R.: Post-combustion CO2 capture using solid sorbents: a review. Ind. Eng. Chem. Res. 51, 1438–1463 (2011)

    Article  Google Scholar 

  • Setzmann, U., Wagner, W.: A new equation of state and tables of thermodynamic properties for methane covering the range from the melting line to 625 K at pressures up to 100 MPa. J. Phys. Chem. Ref. Data 20, 1061–1155 (1991)

    Article  CAS  Google Scholar 

  • Shafeeyan, M.S., Wan Daud, W.M.A., Shamiri, A.: A review of mathematical modeling of fixed-bed columns for carbon dioxide adsorption. Chem. Eng. Res. Des. 92, 961–988 (2014)

    Article  CAS  Google Scholar 

  • Sheikh, M.A., Hassan, M.M., Loughlin, K.F.: Adsorption equilibria and rate parameters for nitrogen and methane on Maxsorb activated carbon. Gas Sep. Purif. 10, 161–168 (1996)

    Article  CAS  Google Scholar 

  • Silva, J.A.C., Schumann, K., Rodrigues, A.E.: Sorption and kinetics of CO2 and CH4 in binderless beads of 13X zeolite. Microporous Mesoporous Mater. 158, 219–228 (2012)

    Article  CAS  Google Scholar 

  • Sircar, S.: Air fractionation by adsorption. Sep. Sci. Technol. 23, 2379–2396 (1988)

    Article  Google Scholar 

  • Sircar, S., Hufton, J.R.: Why does the linear driving force model for adsorption kinetics work? Adsorption 6, 137–147 (2000)

    Article  CAS  Google Scholar 

  • Span, R., Lemmon, E.W., Jacobsen, R.T., Wagner, W.: A reference quality equation of state for nitrogen. Int. J. Thermophys. 19, 1121–1132 (1998)

    Article  CAS  Google Scholar 

  • Spoorthi, G., Thakur, R.S., Kaistha, N., Rao, D.P.: Process intensification in PSA processes for upgrading synthetic landfill and lean natural gases. Adsorption 17, 121–133 (2011)

    Article  CAS  Google Scholar 

  • Taylor, B.N., Kuyatt, C.E.: Guidelines for evaluating and expressing the uncertainty of NIST measurement results. National Institute of Standards and Technology, Washington, DC (1994)

    Book  Google Scholar 

  • Xiao, G., Singh, R., Chaffee, A., Webley, P.: Advanced adsorbents based on MgO and K2CO3 for capture of CO2 at elevated temperatures. Int. J. Greenh. Gas Control 5, 634–639 (2011)

    Article  CAS  Google Scholar 

  • Xiao, G., Xiao, P., Lee, S., Webley, P.A.: CO2 capture at elevated temperatures by cyclic adsorption processes. RSC Adv. 2, 5291–5297 (2012)

    Article  CAS  Google Scholar 

  • Yang, J., Lee, C.-H., Chang, J.-W.: Separation of hydrogen mixtures by a two-bed pressure swing adsorption process using zeolite 5A. Ind. Eng. Chem. Res. 36, 2789–2798 (1997)

    Article  CAS  Google Scholar 

  • Yang, Y., Ribeiro, A.M., Li, P., Yu, J.-G., Rodrigues, A.E.: Adsorption equilibrium and kinetics of methane and nitrogen on carbon molecular sieve. Ind. Eng. Chem. Res. 53, 16840–16850 (2014)

    Article  CAS  Google Scholar 

  • Yu, M., Primera-Pedrozo, J.N., Marcano-González, M.E., Hernández-Maldonado, A.J.: Selective adsorption of N2 over CH4 in flexible Sr2+- and Ba2+-UPRM-5 (TEA) titanium silicates: effect of activation temperature. Chem. Eng. J. 252, 311–319 (2014)

    Article  CAS  Google Scholar 

  • Zhang, Z., Zhang, W., Chen, X., Xia, Q., Li, Z.: Adsorption of CO2 on zeolite 13X and activated carbon with higher surface area. Sep. Sci. Technol. 45, 710–719 (2010)

    Article  CAS  Google Scholar 

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Acknowledgements

The research was funded by the Australian Research Council Industrial Transformation Training Centre for LNG Futures (Project IC150100019).

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Correspondence to Eric F. May.

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Xiao, G., Li, Z., Saleman, T.L. et al. Adsorption equilibria and kinetics of CH4 and N2 on commercial zeolites and carbons. Adsorption 23, 131–147 (2017). https://doi.org/10.1007/s10450-016-9840-7

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  • DOI: https://doi.org/10.1007/s10450-016-9840-7

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