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Moreover, the heat of adsorption at zero coverage Qst were obtained from 1/T dependence of ln(KH) in terms of van’t Hoff expression [30,31]: lnKH = −Qst + C (4) RT The results are listed in Table 4. It is seen that Henry’s constants and the initial heats of adsorption for three xylene isomers in the four samples follow the same order of Beta-3 < Beta-2 < Beta-1 < Beta-0, indicating the weaker interaction between the adsorbate and adsorbent in mesoporous Beta zeolites. The difference in values of KH between microporous Beta-0 and mesoporous Beta-1,-2,-3 seems to be remarkable, corresponding to the variation of b-values and b1-values discussed above. The initial heats of adsorption for three xylene isomers in Beta-0, ranging from 55.5 kJ/moL for p-xylene to 69.5 kJ/moL for o-xylene, were higher than the values of 53.6 kJ/moL for 2,2-dimethylbutane and 63.4 kJ/moL for n-hexane in Beta zeolite [32]. The values of Henry’s constants and the initial heats of adsorption for three xylene isomers go in order of p-xylene < m-xylene < o-xylene, which is accordance with the results of b and b1. This can be explained by the dipole moment (D) of p-xylene, m-xylene and o-xylene, which are 0, 0.33 and 0.62, respectively. The non-polar and the smallest molecule kinetic diameter of p-xylene result in the smallest Henry’s constant value among three xylene isomers. 2.3. Diffusion Results ZLC diffusion experiments of xylene isomers (p-xylene, m-xylene and o-xylene) on the four Beta zeolites with different mesoporosity were carried out at the high flow rate of 80 mL/min and temperatures from 333 K to 373 K. The partial pressure of three xylene isomers was maintained at 0.04 mbar, which are low enough to ensure the experiments were carried out within the Henry’s law region. The fact that the system is controlled by kinetics was verified by measuring ZLC desorption curves of xylene isomers at two different flow rates under the same conditions. It turned out that two desorption curves have similar long time slopes, i.e., they are nearly parallel to each other in the tails [33]. The experimental desorption plots were fitted using Equations (5)–(7) to obtain the fitting parameters, L, β and Deff/R2. Representative experimental and theoretical ZLC curves of xylene isomers are showed in Figure 5. A good agreement is observed between the symbols represented experimental data and the solid lines obtained from fitting ZLC theoretical model with the goodness of fit R2 > 0.98. The correctness and effectiveness of the method was demonstrated by the above points. 247PDF Image | Zeolite Catalysis
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