Single- and Multicomponent Fixed Bed Adsorption of CO2, CH4, and N2 in Binder-Free Beads of 4A Zeolite
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Single- and multicomponent adsorption fixed bed breakthrough experiments of carbon dioxide (CO 2 ), methane (CH 4 ), and nitrogen (N 2 ) on commercial binder-free beads of 4A zeolite have been studied at 313, 373, and 423 K and a total pressure of up to 5 bar. The ternary experiments (CO 2 /CH 4 /N 2 ) show a practically complete separation of CO 2 from CH 4 /N 2 at all the temperatures studied, with selectivity at 313 K of CO 2 around 24 over CH 4 and 50 over N 2 . The adsorption equilibrium data measured from the breakthrough experiments were modeled by the dual-site Langmuir isotherm, and the breakthrough results were simulated with a fixed bed adsorption model taking into account axial dispersion, mass-transfer resistances, and heat effects. The mathematical model predicts with a good accuracy the systematic behavior of the single- and multicomponent breakthrough results based on the independent parameters calculated from well-established correlations and intracrystalline diffusivities for zeolite 4A available in the literature. The results showed in the present work evidence that the binder-free beads of zeolite 4A can be employed to efficiently separate CO 2 from CO 2 /CH 4 /N 2 mixtures by fixed bed adsorption.
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Foo, K. Y., & Hameed, B. H. (2010) · Chemical Engineering Journal · doi:10.1016/j.cej.2009.09.013 · Cited by 8,479 · see citing works
Shampine, L. F., & Reichelt, M. W. (1997) · SIAM Journal on Scientific Computing · doi:10.1137/s1064827594276424 · Cited by 3,628 · see citing works
Adsorbent Materials for Carbon Dioxide Capture from Large Anthropogenic Point Sources
Choi, S., Drese, J. H., & Jones, C. W. (2009) · ChemSusChem · doi:10.1002/cssc.200900036 · Cited by 2,602 · see citing works
Principles of adsorption and adsorption processes
Klein, G. (1985) · Reactive Polymers Ion Exchangers Sorbents · doi:10.1016/0167-6989(85)90037-6 · Cited by 2,122 · see citing works
Adsorption Analysis: Equilibria and Kinetics
Do, D. D. (1998) · Series on chemical engineering · doi:10.1142/p111 · Cited by 1,928 · see citing works
Solution of differential equation models by polynomial approximation
Villadsen, J., & Michelsen, M. L. (1978) · Prentice Hall eBooks · Cited by 1,286 · see citing works
Handbook of zeolite science and technology
Auerbach, S. M. (2004) · Focus on Catalysts · doi:10.1016/s1351-4180(04)00164-3 · Cited by 1,023 · see citing works
Lapidus, L., & Amundson, N. R. (1952) · The Journal of Physical Chemistry · doi:10.1021/j150500a014 · Cited by 947 · see citing works
Sun, Q., Li, H., Yan, J., Liu, L., Yu, Z., & Yu, X. (2015) · Renewable and Sustainable Energy Reviews · doi:10.1016/j.rser.2015.06.029 · Cited by 924 · see citing works
Theory of chromatography. Part 9. The “theoretical plate” concept in column separations
Glueckauf, E. (1955) · Trans. Faraday Soc. · doi:10.1039/tf9555100034 · Cited by 464 · see citing works
A Microporous Metal−Organic Framework for Separation of CO2/N2 and CO2/CH4 by Fixed-Bed Adsorption
Bastin, L., Bárcia, P. S., Hurtado, E. J., Silva, J. A. C., Rodrigues, A. E., & Chen, B. (2008) · The Journal of Physical Chemistry C · doi:10.1021/jp077618g · Cited by 442 · see citing works
Self-citationA Compendium of Partial Differential Equation Models
Schiesser, W. E., & Griffiths, G. W. (2009) · Cambridge University Press eBooks · doi:10.1017/cbo9780511576270 · Cited by 266 · see citing works
Habgood, H. W. (1958) · Canadian Journal of Chemistry · doi:10.1139/v58-204 · Cited by 211 · see citing works
Wankat, P. C. (1990) · Springer eBooks · doi:10.1007/978-94-010-9724-6 · Cited by 189 · see citing works
Akten, E. D., Siriwardane, R. V., & Sholl, D. S. (2003) · Energy & Fuels · doi:10.1021/ef0300038 · Cited by 178 · see citing works
Himeno, S., Tomita, T., Suzuki, K., & Yoshida, S. (2006) · Microporous and Mesoporous Materials · doi:10.1016/j.micromeso.2006.05.018 · Cited by 173 · see citing works
CO2, CH4 and N2 separation with a 3DFD-printed ZSM-5 monolith
Couck, S., Lefevere, J., Mullens, S., Protasova, L. N., Meynen, V., Desmet, G., Baron, G. V., & Denayer, J. F. M. (2016) · Chemical Engineering Journal · doi:10.1016/j.cej.2016.09.046 · Cited by 165 · see citing works
Palomino, M., Corma, A., Jordá, J. L., Rey, F., & Valencia, S. (2012) · Chem. Commun. · doi:10.1039/c1cc16320e · Cited by 161 · see citing works
Sorption and kinetics of CO2 and CH4 in binderless beads of 13X zeolite
Silva, J. A. C., Schumann, K., & Rodrigues, A. E. (2012) · Microporous and Mesoporous Materials · doi:10.1016/j.micromeso.2012.03.042 · Cited by 131 · see citing works
Self-citationPressure Swing Adsorption for Biogas Upgrading with Carbon Molecular Sieve
Canevesi, R. L. S., Andreassen, K. A., da Silva, E. A., Borba, C. E., & Grande, C. A. (2018) · Industrial & Engineering Chemistry Research · doi:10.1021/acs.iecr.8b00996 · Cited by 122 · see citing works
Santos, M. P. S., Grande, C. A., & Rodrigues, A. E. (2011) · Industrial & Engineering Chemistry Research · doi:10.1021/ie100757u · Cited by 116 · see citing works
Self-citationThe Infrared Spectra of Carbon Dioxide Adsorbed on Zeolite X
Ward, J. W., & Habgood, H. W. (1966) · The Journal of Physical Chemistry · doi:10.1021/j100876a034 · Cited by 114 · see citing works
Kinetics of hydrocarbon adsorption on activated carbon and silica gel
Malek, A., & Farooq, S. (1997) · AIChE Journal · doi:10.1002/aic.690430321 · Cited by 104 · see citing works
Ruthven, D. M. (1976) · AIChE Journal · doi:10.1002/aic.690220419 · Cited by 90 · see citing works
Delgado, J. A., Uguina, M. A., Gómez, J. M., & Ortega, L. M. (2005) · Separation and Purification Technology · doi:10.1016/j.seppur.2005.07.027 · Cited by 90 · see citing works
Diffusion in 4A zeolite. Study of the effect of crystal size
Yücel, H., & Ruthven, D. M. (1980) · Journal of the Chemical Society Faraday Transactions 1 Physical Chemistry in Condensed Phases · doi:10.1039/f19807600060 · Cited by 86 · see citing works
Diffusion Mechanism of Carbon Dioxide in Zeolite 4A and CaX Pellets
Ahn, H., Moon, J.-H., Hyun, S., & Lee, C. (2004) · Adsorption · doi:10.1023/b:adso.0000039867.14756.ac · Cited by 84 · see citing works
Diffusion of CO2 in 4A and 5A zeolite crystals
Yücel, H., & Ruthven, D. M. (1980) · Journal of Colloid and Interface Science · doi:10.1016/0021-9797(80)90182-4 · Cited by 84 · see citing works
Upgrading biogas by a low-temperature CO2 removal technique
Yousef, A. M. I., Eldrainy, Y. A., El-Maghlany, W. M., & Attia, A. E. (2016) · Alexandria Engineering Journal · doi:10.1016/j.aej.2016.03.026 · Cited by 82 · see citing works
Binary adsorption of CO2/CH4 in binderless beads of 13X zeolite
Silva, J. A. C., Cunha, A. F., Schumann, K., & Rodrigues, A. E. (2013) · Microporous and Mesoporous Materials · doi:10.1016/j.micromeso.2013.12.017 · Cited by 74 · see citing works
Self-citationSeabra, R., Ribeiro, A. M., Gleichmann, K., Ferreira, A. F. P., & Rodrigues, A. E. (2018) · Microporous and Mesoporous Materials · doi:10.1016/j.micromeso.2018.10.024 · Cited by 70 · see citing works
Self-citationAssessment of CO2 desorption from 13X zeolite for a prospective TSA process
Morales-Ospino, R., Santiago, R. G., Siqueira, R. M., Azevedo, D. C. S., & Bastos-Neto, M. (2019) · Adsorption · doi:10.1007/s10450-019-00192-5 · Cited by 61 · see citing works
Mohr, R., Vorkapić, D., Rao, M. B., & Sircar, S. (1999) · Adsorption · doi:10.1023/a:1008917308002 · Cited by 55 · see citing works
Ruthven, D. M., & Kumar, R. (1979) · The Canadian Journal of Chemical Engineering · doi:10.1002/cjce.5450570316 · Cited by 51 · see citing works
Silva, J. A. C., Ferreira, A. F. P., Mendes, P. A. P., Cunha, A. F., Gleichmann, K., & Rodrigues, A. E. (2015) · Industrial & Engineering Chemistry Research · doi:10.1021/acs.iecr.5b01608 · Cited by 44 · see citing works
Self-citationKinetics and equilibrium of adsorption on 4A zeolite
Eagan, J. D., & ANDERSON, R. B. (1975) · Journal of Colloid and Interface Science · doi:10.1016/0021-9797(75)90165-4 · Cited by 42 · see citing works
A chromatographic study of sorption and diffusion in 5A zeolite
Haq, N., & Ruthven, D. M. (1986) · Journal of Colloid and Interface Science · doi:10.1016/0021-9797(86)90078-0 · Cited by 42 · see citing works
Zeolites for CO2–CO–O2 Separation to Obtain CO2-Neutral Fuels
Perez-Carbajo, J., Matito-Martos, I., Balestra, S. R. G., Tsampas, M. N., van de Sanden, M. C. M., Delgado, J. A., Águeda, V. I., Merkling, P. J., & Calero, S. (2018) · ACS Applied Materials & Interfaces · doi:10.1021/acsami.8b04507 · Cited by 39 · see citing works
Modeling adsorption equilibria of xylene isomers in a microporous metal–organic framework
Bárcia, P. S., Nicolau, M. P. M., Gallegos, J. M., Chen, B., Rodrigues, A. E., & Silva, J. A. C. (2012) · Microporous and Mesoporous Materials · doi:10.1016/j.micromeso.2012.01.033 · Cited by 34 · see citing works
Self-citationIndustrial Zeolite Molecular Sieves
Gleichmann, K., Unger, B., & Brandt, A. (2016) · InTech eBooks · doi:10.5772/63442 · Cited by 34 · see citing works
Separation of Hexane Isomers in ZIF-8 by Fixed Bed Adsorption
Henrique, A., Rodrigues, A. E., & Silva, J. A. C. (2018) · Industrial & Engineering Chemistry Research · doi:10.1021/acs.iecr.8b05126 · Cited by 30 · see citing works
Self-citationGrained binder-free zeolites: Synthesis and properties
Павлов, М. Л., Travkina, O. S., & Kutepov, B. I. (2012) · Catalysis in Industry · doi:10.1134/s2070050412010096 · Cited by 19 · see citing works
Short Communication: Diffusion of Simple Molecules in 4A Zeolite
Ruthven, D. M. (2001) · Adsorption · doi:10.1023/a:1013173817592 · Cited by 13 · see citing works
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Self-citationLiu, R.-S., Shi, X., Wang, C., Gao, Y., Xu, S. H., Hao, G., Chen, S., & Lu, A. (2021) · ChemSusChem · doi:10.1002/cssc.202002677 · Cited by 196 · see citing works
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Zhang, Y., Josien, L., Vaulot, C., Simon‐Masseron, A., & Lalevée, J. (2023) · Advanced Materials Technologies · doi:10.1002/admt.202300699 · Cited by 4 · see citing works
Devi, V. G., Aravamudan, K., Yadav, D., Dhorajiya, P. B., Bhattacharya, R. P., & Sircar, A. (2024) · Microporous and Mesoporous Materials · doi:10.1016/j.micromeso.2024.113464 · Cited by 2 · see citing works
Zhang, Z., & Shu, Y. (2025) · Chemical Engineering Journal Advances · doi:10.1016/j.ceja.2025.100926 · Cited by 2 · see citing works
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Henrique, A., Dutta, P., Gupta, M., Mouchaham, G., Magnin, Y., Serre, C., Maurin, G., & da Silva, J. A. C. (2026) · Journal of Materials Chemistry A · doi:10.1039/d6ta01917j · Cited by 2 · see citing works
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- Authors
- Zafanelli, L. F. A. S., Henrique, A., Karimi, M., Rodrigues, A. E., & Silva, J. A. C.
- Affiliations
- Universidade Politécnica de Bragança (PT)
- Universidade do Porto (PT)
- Corresponding author
- Zafanelli, Lucas F. A. S.
- Silva, José A. C.
- Venue
- Industrial & Engineering Chemistry Research
- Publisher
- American Chemical Society (ACS)
- Published
- 2020-06-30
- Volume
- 59
- Issue
- 30
- Pages
- 13724-13734
- ISSN
- 0888-5885 (ISSN-L)
- 1520-5045
- OpenAlex
- W3039153555
- Cited by
- 33
- References
- 43
- Citations by year
- 2026: 3 · 2025: 8 · 2024: 8 · 2023: 6 · 2022: 3 · 2021: 5
- FWCI
- 1.72
- Type
- journal article
- Language
- en
- Open access
- green
- hdl.handle.net
- Licence
- Locations
- Industrial & Engineering Chemistry Research (publishedVersion)
- Portuguese National Funding Agency for Science, Research and Technology (RCAAP Project by FCT) (submittedVersion, other-oa)
- Funders
- European Regional Development Fund (POCI-01-0145-FEDER006984, UID/AGR/00690/2019)
- Funda??o para a Ci?ncia e a Tecnologia (SFRH/BD/140550/2018, UID/AGR/00690/2019)
- Topics
- Physical Sciences › Engineering › Mechanical Engineering › Carbon Dioxide Capture Technologies
- Physical Sciences › Chemistry › Inorganic Chemistry › Zeolite Catalysis and Synthesis
- Physical Sciences › Engineering › Mechanical Engineering › Membrane Separation and Gas Transport
- Keywords
- 4A zeolite, fixed-bed adsorption, breakthrough experiments, adsorption equilibrium modeling, axial dispersion, mass transfer resistance, thermal effects, intracrystalline diffusion, CO2 capture
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