Solution-processable polytriazoles from spirocyclic monomers for membrane-based hydrocarbon separations

NC Bruno and R Mathias and YJ Lee and GH Zhu and YH Ahn and ND Rangnekar and JR Johnson and S Hoy and I Bechis and A Tarzia and KE Jelfs and BA McCool and R Lively and MG Finn, NATURE MATERIALS (2023).

DOI: 10.1038/s41563-023-01682-2

The thermal distillation of crude oil mixtures is an energy-intensive process, accounting for nearly 1% of global energy consumption. Membrane-based separations are an appealing alternative or tandem process to distillation due to intrinsic energy efficiency advantages. We developed a family of spirocyclic polytriazoles from structurally diverse monomers for membrane applications. The resulting polymers were prepared by a convenient step-growth method using copper-catalysed azide-alkyne cycloaddition, providing very fast reaction rates, high molecular weights and solubilities in common organic solvents and non- interconnected microporosity. Fractionation of whole Arabian light crude oil and atmospheric tower bottom feeds using these materials enriched the low-boiling-point components and removed trace heteroatom and metal impurities (comparable performance with the lighter feed as the commercial polyimide, Matrimid), demonstrating opportunities to reduce the energy cost of crude oil distillation with tandem membrane processes. Membrane-based molecular separation under these demanding conditions is made possible by high thermal stability and a moderate level of dynamic chain mobility, leading to transient interconnections between micropores, as revealed by the calculations of static and swollen pore structures. Thermal fractionation of petroleum consumes large amounts of energy. Here stable microporous polymers are synthesized using click chemistry, which have similar performance to commercial polyimides for the fractionation of light crude oils and successful application to heavy feeds under realistic conditions.

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