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separation resulting in p-xylene yield leveling off with temperature decrease, due to diffusion limitations in the membrane substrate. Moreover, 100% selectivity to p-xylene was reported in the permeate-only mode, whereas the selectivity declined to nearly 48% when considering the retentate and permeate amounts. In a parallel study [163], the authors managed to synthesize higher quality membranes in terms of selectivity (p-xylene/o-xylene > 400). Accordingly, the membrane reactor outperformed the conventional one at the applied reaction temperature of 473 K. Furthermore, the same authors employed nanocomposite MFI-ceramic hollow fibre membranes for the xylene isomer separation, demonstrating nearly 30% p-xylene flux increase and reasonable selectivity [227]. Finally, the utilization of hollow fibre membranes in zeolite membrane reactors for the isomerization of xylene could offer the essential increase in the p-xylene permeation flux in order to overcome one of the considerable limitations of this reactor configuration in the competition with the existing technologies. 4.3. Selectivity Enhancement through Selective Distribution of Reactants or Removal of Intermediate Products As reviewed in the previous section, the performance of zeolite membranes packed with catalysts is widely evaluated in membrane reactor configurations either for the selective extraction of products in equilibrium limited reactions or for extraction of products inhibiting the catalyst activity. All the efforts were to improve the conversion of the reactions studied. Besides, zeolite membranes could play a further role which is based on upstream separation of a component from the feed mixture or removal of intermediate products. In this context, the principle of controlling reactants traffic from a feed mixture was demonstrated by Gora et al. [171]. In detail, the hydroisomerization of n-hexane was studied in single-pass operation with a membrane reactor combining silicalite-1/TiO2/stainless steel tubular membrane and Pt-chlorinated catalyst. The silicalite-1 membrane was able to selectively permeate n-hexane due to its preferential adsorption from a feed mixture comprising n-hexane and 2-methyl-pentane with a purity of ~99% to the reaction zone, thus revealing to some extent the advantages of this reactor configuration. The same working group proposed a concept for industrial scale heptane hydroisomerization process combining two reactors and a zeolite membrane. According to the simulation data a total feed amount of 907 metric ton per day (existing C5/C6 isomerization technologies operate between 600 and 1200 metric ton per day) is processed forming 220 metric ton per day product with improved research octane number from 57 up to 92 [228]. After economical evaluation, the authors concluded a total investment cost of 40 million euros being significantly higher than the state of the art C5/C6 hydroisomerization 34PDF Image | Zeolite Catalysis
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