How reliable is the Real Adsorbed Solution Theory (RAST) for estimating ternary mixture equilibrium in microporous host materials?

• The tenets of the IAST are violated in several guest/host combinations of practical interest. • Models such as Wilson, NRTL need to be modified for adsorption equilibrium. • The activity coefficients in the adsorbed phase depend on both spreading pressure and composition. • CBMC simulations are used to test the reliability of the RAST for estimating ternary adsorption equilibrium. • The RAST for ternary mixtures requires inputs for constituent binary pairs. Microporous crystalline adsorbents such as zeolites, and metal-organic frameworks (MOFs) have potential use in a wide variety of separations applications. In applications such as CO 2 capture, the Ideal Adsorbed Solution Theory (IAST) often fails to provide a quantitative description of mixture adsorption equilibrium especially in cation-exchanged zeolites. The failure of the IAST is ascribable to non-compliance with one or more tenets mandated by the IAST such as (a) homogeneous distribution of adsorbates within the pore landscape, (b) no preferential location of guest species, and (c) absence of molecular clustering due to say hydrogen bonding. The focus of this article is on the reliability of the Real Adsorbed Solution Theory (RAST) models for quantitative estimation of adsorption equilibrium. Configurational-Bias Monte Carlo (CBMC) simulations are undertaken to determine the adsorption equilibrium for ternary CO 2 /CH 4 /N 2 , CO 2 /CH 4 /C 3 H 8 , CO 2 /CH 4 /H 2 , and water/methanol/ethanol mixtures in NaX, LTA-4A, CHA, DDR, and MFI zeolites. Additionally, CBMC simulations of the constituent binary pairs are used to determine the Wilson or NRTL parameters, taking due account of the dependence of the activity coefficients on the spreading pressure. Use of the binary pair Wilson or NRTL parameters allows the estimation of ternary mixture adsorption equilibrium, that is tested against the CBMC data on component loadings. In all investigated guest/host combinations, the RAST provides a good estimation of ternary mixture adsorption equilibrium.