Sustainable Separations of C(4)‐Hydrocarbons by Using Microporous Materials

Petrochemical refineries must separate hydrocarbon mixtures on a large scale for the production of fuels and chemicals. Typically, these hydrocarbons are separated by distillation, which is extremely energy intensive. This high energy cost can be mitigated by developing materials that can enable efficient adsorptive separation. In this critical review, the principles of adsorptive separation are outlined, and then the case for C(4) separations by using zeolites and metal–organic frameworks (MOFs) is examined. By analyzing both experimental and theoretical studies, the challenges and opportunities in C(4) separation are outlined, with a focus on the separation mechanisms and structure–selectivity correlations. Zeolites are commonly used as adsorbents and, in some cases, can separate C(4) mixtures well. The pore sizes of eight‐membered‐ring zeolites, for example, are in the order of the kinetic diameters of C(4) isomers. Although zeolites have the advantage of a rigid and highly stable structure, this is often difficult to functionalize. MOFs are attractive candidates for hydrocarbon separation because their pores can be tailored to optimize the adsorbate–adsorbent interactions. MOF‐5 and ZIF‐7 show promising results in separating all C(4) isomers, but breakthrough experiments under industrial conditions are needed to confirm these results. Moreover, the flexibility of the MOF structures could hamper their application under industrial conditions. Adsorptive separation is a promising viable alternative and it is likely to play an increasingly important role in tomorrow's refineries.