Adsorption of C2−C8 n-Alkanes in Zeolites

Adsorption of n-alkanes has been studied in the industrially relevant zeolites H-FAU, H-BEA, H-MOR, and H-ZSM-5 combining QM−Pot(MP2//B3LYP) with statistical thermodynamics calculations and assuming a mobile adsorbate. In H-ZSM-5, adsorption at the intersection site with the hydrocarbon chain extending in the straight channel (SC+I) as well as in the zigzag channel (ZC+I) has been studied. In addition, differential heats of adsorption and adsorption isotherms at temperatures from 301 to 400 K of all C3−C6 n-alkane in H-ZSM-5 have been measured simultaneously via calorimetry and gravimetry. Calculated adsorption enthalpies are independent of temperature and are virtually identical to the adsorption energies. The adsorption strength increases in the order H-FAU < H-BEA < H-MOR < H-ZSM-5 (SC+I) < H-ZSM-5 (ZC+I) and varies linearly with the carbon number. As compared to experimental values, the calculated adsorption strength is overestimated by some 2 kJ mol−1/CH2 in FAU up to some 4 kJ mol−1/CH2 in H-ZSM-5 suggesting that the QM−Pot(MP2//B3LYP) calculations overestimate van der Waals stabilizing interactions and a correction term has been proposed. Adsorption entropy losses are independent of temperature and increase in the order H-FAU < H-BEA < H-MOR < H-ZSM-5 (SC+I) < H-ZSM-5 (ZC+I), according to the pore size of the zeolites. The calculated adsorption entropies agree nicely with available experimental results in all zeolites. QM−Pot(MP2//B3LYP) calculated adsorption equilibrium coefficients (using the corrected adsorption enthalpies) correspond relatively well to experimentally determined values. Comparison of relative turnover frequencies with relative adsorption equilibrium coefficients indicates that the variation of the equilibrium coefficient with the carbon number or with the zeolite can only partly explain the observed reactivity differences in monomolecular cracking of n-alkanes. In agreement with experimental observations, our results indicate that the difference in reactivity of the n-alkanes for monomolecular cracking in a given zeolite mainly originates from a difference in intrinsic monomolecular cracking rate coefficients.