Abstract
A systematic study of the diffusion mechanism of CO2 in commercial 13X zeolite beads is presented. In order to gain a complete understanding of the diffusion process of CO2, kinetic measurements with a zero length column (ZLC) system and a volumetric apparatus have been carried out. The ZLC experiments were carried out on a single bead of zeolite 13X at 38 °C at a partial pressure of CO2 of 0.1 bar, conditions representative of post-combustion capture. Experiments with different carrier gases clearly show that the diffusion process is controlled by the transport inside the macropores. Volumetric measurements using a Quantachrome Autosorb system were carried out at different concentrations. These experiments are without a carrier gas and the low pressure measurements show clearly Knudsen diffusion control in both the uptake cell and the bead macropores. At increasing CO2 concentrations the transport mechanism shifts from Knudsen diffusion in the macropores to a completely heat limited process. Both sets of experiments are consistent with independent measurements of bead void fraction and tortuosity and confirm that under the range of conditions that are typical of a carbon capture process the system is controlled by macropore diffusion mechanisms.
Similar content being viewed by others
References
Ahn, H., Moon, J.H., Hyun, S.H., Lee, C.H.: Diffusion mechanism of carbon dioxide in zeolite 4A and CaX pellets. Adsorption 10, 111–128 (2004)
Bird, R.B., Stewart, W.E., Lightfoot, E.N.: Transport Phenomena, 2nd edn. Wiley, New York (2002)
Brandani, F., Ruthven, D.M., Coe, C.G.: Measurement of adsorption equilibrium by the zero length column (ZLC) technique Part 1: single-component systems. Ind. Eng. Chem. Res. 42, 1451–1461 (2003)
Brandani, S.: Analysis of the piezometric method for the study of diffusion in microporous solids: isothermal case. Adsorption 4, 17–24 (1998)
Brandani, S., Jama, M.A., Ruthven, D.M.: ZLC measurements under non-linear conditions. Chem. Eng. Sci. 55(7), 1205–1212 (2000)
Brandani, S., Ruthven, D.M.: Analysis of ZLC desorption curves for gaseous systems. Adsorption 2, 133–143 (1996)
Carniglia, S.C.: Construction of the tortuosity factor from porosimetry. J. Catal. 102, 401–418 (1986)
Cavenati, S., Grande, C.A., Rodrigues, A.E.: Adsorption equilibrium of methane, carbon dioxide, and nitrogen on zeolite 13X at high pressures. J. Chem. Eng. Data 49, 1095–1101 (2004)
Chou, C.T., Chen, C.Y.: Carbon dioxide recovery by vacuum swing adsorption. Sep. Purif. Technol. 39, 51–64 (2004)
Chue, K.T., Kim, J.N., Yoo, Y.J., Cho, S.H.: Comparison of activated carbon and zeolite 13X for CO2 recovery from flue gas by pressure swing adsorption. Ind. Eng. Chem. Res. 34, 591–598 (1995)
Crank, J.: The Mathematics of Diffusion. Oxford University Press, London (1956)
Cunnigham, R.E., Williams, R.J.J.: Diffusion in Gases and Porous Media. Plenum Press, New York (1980)
Dasgupta, S., Biswas, N., Aarti, Gode, N.G., Divekar, S., Nanoti, A., Goswami, A.N.: CO2 recovery from mixtures with nitrogen in a vacuum swing adsorber using metal organic framework adsorbent: a comparative study. Int. J. Greenh Gas Control 7, 225–229 (2012)
Duncan, W.L., Moller, K.P.: The effect of a crystal size distribution on ZLC experiments. Chem. Eng. Sci. 57(14), 2641–2652 (2002)
Ebner, A.D., Ritter, J.A.: State-of-the-art adsorption and membrane separation processes for carbon dioxide production from carbon dioxide emitting industries. Sep. Sci. Technol. 44, 1273–1421 (2009)
Eic, M., Ruthven, D.M.: A new experimental technique for measurement of intracrystalline diffusivity. Zeolites 8(1), 40–45 (1988)
Friedrich, D., Ferrari, M.C., Brandani, S.: Efficient simulation and acceleration of convergence for a dual piston pressure swing adsorption system. Ind. Eng. Chem. Res. (2013). doi:10.1021/ie3036349
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)
Gomes, V.G., Yee, K.W.K.: Pressure swing adsorption for carbon dioxide sequestration from exhaust gases. Sep. Purif. Technol. 28, 161–171 (2002)
Harlick, P.J.E., Tezel, F.H.: An experimental adsorbent screening study for CO2 removal from N2. Microporous Mesoporous Mater. 76, 71–79 (2004)
IEA.: Energy Technology Transitions for Industry: Strategies for the Next Industrial Revolution. International Energy Agency, Paris (2009)
Ishibashi, M., Ota, H., Akutsu, N., Umeda, S., Tajika, M., Izumi, J., Yasutake, A., Kabata, T., Kageyama, Y.: Technology for removing carbon dioxide from power plant flue gas by the physical adsorption method. Energy Convers. Manag. 37, 929–933 (1996)
Kaerger, J., Ruthven, D.M., Theodorou, D.N.: Diffusion in Nanoporous Materials. Weinheim, Germany (2012)
Kikkinides, E.S., Yang, R.T., Cho, S.H.: Concentration and recovery of CO2 from flue gas by pressure swing adsorption. Ind. Eng. Chem. Res. 32, 2714–2720 (1993)
Kočiřík, 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. Faraday Trans. 1(80), 2167–2174 (1984)
Kuramochi, T., Ramírez, A., Turkenburg, W., Faaij, A.: Comparative assessment of CO2 capture technologies for carbon-intensive industrial processes. Prog. Energy Combust. Sci. 38, 87–112 (2012)
Lee, L.-K., Ruthven, D.M.: Analysis of thermal effects in adsorption rate measurements. J. Chem. Soc. Faraday Trans. 1 75, 2406–2422 (1979)
Levitz, P.: Knudsen diffusion and excitation transfer in random porous media. J. Phys. Chem. 97, 3813–3818 (1993)
Li, G., Xiao, P., Webley, P., Zhang, J., Singh, R., Marshall, M.: Capture of CO2 from high humidity flue gas by vacuum swing adsorption with zeolite 13X. Adsorption 14, 415–422 (2008)
Luis, P., Van Gerven, T., Van der Bruggen, B.: Recent developments in membrane-based technologies for CO2 capture. Prog. Energ. Combust. 38, 419–448 (2012)
Onyestyák, G.: Comparison of dinitrogen, methane, carbon monoxide, and carbon dioxide mass-transport dynamics in carbon and zeolite molecular sieves. Helv. Chim. Acta 94, 206–217 (2011)
Onyestyák, G., Rees, L.V.C.: Frequency response study of adsorbate mobilities of different character in various commercial adsorbents. J. Phys. Chem. B 103, 7469–7479 (1999)
Onyestyák, G., Shen, D., Rees, L.V.C.: Frequency-response study of micro- and macro-pore diffusion in manufactured zeolite pellets. J. Chem. Soc. Faraday Trans. 91, 1399–1405 (1995)
Papadopoulos, G.K., Theodorou, D.N., Vasenkov, S., Kaerger, J.: Mesoscopic simulations of the diffusivity of ethane in beds of NaX zeolite crystals: comparison with pulsed field gradient NMR measurements. J. Chem. Phys. 126(094702), 1–8 (2007)
Ruthven, D.M.: Principles of Adsorption and Adsorption Processes. Wiley, New York (1984)
Ruthven, D.M., Lee, L.-K., Yucel, H.: Kinetics of non-isothermal sorption in molecular sieve crystals. AIChE J. 26(1), 16–23 (1980)
Ruthven, D.M., Xu, Z.: Diffusion of oxygen and nitrogen in 5A zeolite crystals and commercial 5A pellets. Chem. Eng. Sci. 48(18), 3307–3312 (1993)
Schumacher, R., Ehrhardt, K., Karge, H.G.: Determination of diffusion coefficients from sorption kinetic measurements considering the influence of nonideal gas expansion. Langmuir 15, 3965–3971 (1999)
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)
Siriwardane, R.V., Shen, M.S., Fisher, E.P.: Adsorption of CO2, N2, and O2 on natural zeolites. Energy Fuels 17, 571–576 (2003)
Xiao, P., Zhang, J., Webley, P., Li, G., Singh, R., Todd, R.: Capture of CO2 from flue gas streams with zeolite 13X by vacuum-pressure swing adsorption. Adsorption 14, 575–582 (2008)
Zalc, J.M., Reyes, S.C., Iglesia, E.: The effects of diffusion mechanism and void structure on transport rates and tortuosity factors in complex porous structures. Chem. Eng. Sci. 59, 2947–2960 (2004)
Acknowledgments
The authors would like to dedicate this paper to Fred Leavitt, who is a pioneer in adsorption technology. We hope that he will enjoy this study of the fundamentals of mass transport in commercial beads, linked to an industrially relevant adsorption separation process. We would also like to thank the anonymous reviewer for pointing out the need to correct the Knudsen diffusivity using Derjaguin’s approach. Financial support from the EPSRC through Grants EP/F034520/1; EP/G062129/1 and EP/I010939/1 is gratefully acknowledged.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Hu, X., Mangano, E., Friedrich, D. et al. Diffusion mechanism of CO2 in 13X zeolite beads. Adsorption 20, 121–135 (2014). https://doi.org/10.1007/s10450-013-9554-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10450-013-9554-z