Zhou Lin, Brântuas Pedro, Henrique Adriano, Reinsch Helge, Wahiduzzaman Mohammad, Grenèche Jean-Marc, Rodrigues Alírio E, Silva José A C, Maurin Guillaume, Serre Christian
Institut des Matériaux Poreux de Paris, ESPCI Paris, Ecole Normale Supérieure, CNRS, PSL University, 75005, Paris, France.
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, 310027, Hangzhou, China.
Angew Chem Int Ed Engl. 2024 Apr 8;63(15):e202320008. doi: 10.1002/anie.202320008. Epub 2024 Mar 4.
The improvement of the Total Isomerization Process (TIP) for the production of high-quality gasoline with the ultimate goal of reaching a Research Octane Number (RON) higher than 92 requires the use of specific sorbents to separate pentane and hexane isomers into classes of linear, mono- and di-branched isomers. Herein we report the design of a new multi-cage microporous Fe(III)-MOF (referred to as MIP-214, MIP stands for materials of the Institute of Porous Materials of Paris) with a flu-e topology, incorporating an asymmetric heterofunctional ditopic ligand, 4-pyrazolecarboxylic acid, that exhibits an appropriate microporous structure for a thermodynamic-controlled separation of hydrocarbon isomers. This MOF produced via a direct, scalable, and mild synthesis route was proven to encompass a unique separation of C5/C6 isomers by classes of low RON over high RON alkanes with a sorption hierarchy: (n-hexane≫n-pentane≈2-methylpentane>3-methylpentane)≫(2,3-dimethylbutane≈i-pentane≈2,2-dimethylbutane) following the adsorption enthalpy sequence. We reveal for the first time that a single sorbent can efficiently separate such a complex mixture of high RON di-branched hexane and mono-branched pentane isomers from their low RON counterparts, which is a major achievement reported so far.
以生产研究法辛烷值（RON）高于92的高品质汽油为最终目标的全异构化工艺（TIP）的改进，需要使用特定的吸附剂将戊烷和己烷异构体分离成直链、单支链和双支链异构体类别。在此，我们报道了一种具有flu-e拓扑结构的新型多笼微孔铁（III）-金属有机框架（称为MIP-214，MIP代表巴黎多孔材料研究所的材料）的设计，该框架包含一种不对称的异功能双齿配体4-吡唑羧酸，其具有适合于烃类异构体热力学控制分离的微孔结构。通过直接、可扩展且温和的合成路线制备的这种金属有机框架被证明能够通过吸附层级以低RON烷烃相对于高RON烷烃的类别对C5/C6异构体进行独特的分离：（正己烷≫正戊烷≈2-甲基戊烷>3-甲基戊烷）≫（2,3-二甲基丁烷≈异戊烷≈2,2-二甲基丁烷），遵循吸附焓序列。我们首次揭示，单一吸附剂能够有效地从低RON对应物中分离出如此复杂的高RON双支链己烷和单支链戊烷异构体混合物，这是迄今为止报道的一项重大成就。
