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[Display omitted] • A comprehensive study of naphtha separation by a series of adsorbents. • Influence of pore structure on the separation of real naphtha mixtures. • Influence of separation mechanism on the separation of naphtha mixtures. Naphtha separation is of significant importance for refineries to make full use of oil and to reduce the cost of refining. In the recent years, scientists have devoted great efforts to developing novel porous materials such as metal-organic frameworks (MOFs) for the separation of naphtha. However, previous investigations have been limited to single-component or 3- to 5-component model systems. Separation of full range hydrocarbon mixture such as naphtha has rarely been explored. In this work, we carry out a comprehensive study on the separation of alkane isomers as well as full range naphtha mixture by a series of robust microporous MOFs, e.g., Zr-abtc, Al-bttotb, Co-fa, in comparison with representative zeolite materials, e.g., ZSM-5 and zeolite 5A. We find that Al-bttotb and Co-fa, which can separate monobranched and dibranched alkanes through complete molecular exclusion, show superior separation performance for naphtha mixtures. This work may shed light on strategies for developing adsorbents with optimal performance for naphtha separation and ultimately realizing the industrialization of MOF-based separation technologies. [ABSTRACT FROM AUTHOR]

• The large-scale synthesis of H 4 abtc (180 g scale) and Y-abtc (100 g scale) in high yields. • Breakthrough experiments on binary mixtures of propane/propylene at the 100 g scale. • Polymer grade propylene purity achieved using Y-abtc at 100 g scale. • Retained performance of Y-abtc at large scale demonstrating its potential for real world applications. Olefin/Paraffin separation, especially propylene purification from propane, is of extreme commercial importance as it produces chemical feedstock for synthetic plastics such as polypropylene. As an alternative to cryogenic distillation commonly used to purify these mixtures, the use of solid porous materials for adsorptive separation offers a more energetically efficient route. Metal-Organic Frameworks (MOFs) have shown great promise as adsorptive separation candidates in recent years. However, reports of these materials for the purification of C3 hydrocarbons exclusively provide insight of their performance in small scale laboratory settings. Single component isotherms and breakthrough curves are typically tested in the milligrams to gram scale. Herein, we present a scale-up, one-pot synthesis of a robust MOF with high propylene/propane selectivity. The organic linker 3,3′,5,5′-azobenzene-tetracarboxylic acid (H 4 abtc) and its yttrium-based MOF, Y-abtc, are both synthesized at the hundred-gram scale. Furthermore, we perform large-scale breakthrough experiments at the same scale. Our results show that Y-abtc samples synthesized from the one-pot 100 g scale reactions retain high crystallinity and size-exclusion based mechanism for the separation of propane/propylene mixtures. The same polymer-grade purity of propylene (>99.5%) is achieved as in the case of small scale (∼1 g) experiments. [ABSTRACT FROM AUTHOR]