Assessment of the new kinetically limited linear driving force model for predicting diffusion limited adsorption breakthrough curves

• Published in: Adsorption : journal of the International Adsorption Society 2024, Vol.30 (1), p.57-77
• Main Authors: Adegunju, Sulaimon A., Amalraj, Pravin B. C. A., Holland, Charles E., Nicholson, Marjorie A., Ebner, Armin D., Ritter, James A.
• Format: Article
• Language: English
• Subjects: Adsorption; Ambient temperature; Carbon dioxide; Chemistry; Chemistry and Materials Science; Diffusion; Engineering Thermodynamics; Equilibrium; Heat and Mass Transfer; Industrial Chemistry/Chemical Engineering; Mass transfer; Molecular sieves; Partial pressure; Surfaces and Interfaces; Thin Films; Vapor phases
• ISSN: 0929-5607; 1572-8757
• DOI: 10.1007/s10450-023-00434-7

The new kinetically limited linear driving force (KLLDF) model was assessed against the traditional LDF model in the prediction of twelve different ternary and quaternary experimental breakthrough curves. These breakthrough curves comprised mixtures of CO 2 , N 2 and CH 4 in He adsorbed on carbon molecular sieve MSC 3 K 172 and were conducted at various pressures (30, 50 and 100 psia) and at ambient temperature. The LDF and KLLDF models were implemented in the dynamic adsorption process simulator (DAPS) with the loading dependent LDF mass transfer coefficients and the single gas equilibrium adsorption isotherms measured independently with gravimetric uptake experiments. To make the comparison between the LDF and the KLLDF models as fair as possible, they utilized the same set of thermodynamic and kinetic parameters in DAPS, with no adjustments to any of them. Both the LDF and KLLDF models provided reasonable predictions of the experimental breakthrough curves and in-bed temperature histories, with general trends of no CH 4 uptake, gradual N 2 uptake and fast CO 2 uptake. However, the KLLDF model always provided better predictions, especially when CO 2 was present. The results revealed that the traditional LDF model led to depressed adsorbed phase loadings of CO 2 , thereby underpredicting its breakthrough time in all cases. This depression stemmed from the equilibrium loading in the LDF driving force of the LDF model depending on the gas phase partial pressure of each component outside the pore structure. In contrast, the KLLDF model corrects this issue by making the equilibrium loading in its LDF driving force dependent on the actual loading of each component inside the pore structure. In conjunction with the mixed gas extended Langmuir model, the KLLDF model is perhaps the more appropriate model to use instead of the LDF model for any multicomponent adsorbate-adsorbent systems, whether diffusion limited or not, since it reduces to the LDF model for systems that do not exhibit significant diffusional limitations.