Rh‐Catalyzed Hydrogenation of CO2 to Formic Acid in DMSO‐based Reaction Media: Solved and Unsolved Challenges for Process Development,Advanced Synthesis & Catalysis

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Rh‐Catalyzed Hydrogenation of CO2 to Formic Acid in DMSO‐based Reaction Media: Solved and Unsolved Challenges for Process Development
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2018-10-30 , DOI: 10.1002/adsc.201801098
Christian M. Jens ₁ , Martin Scott ₂ , Bastian Liebergesell ₁ , Christian G. Westhues ₂ , Pascal Schäfer ₁ , Giancarlo Franciò ₂ , Kai Leonhard ₁ , Walter Leitner _{2,

3} , André Bardow ₁

Affiliation

Process concepts have been conceived and evaluated for the amine‐free homogeneous catalyzed hydrogenation of CO₂ to formic acid (FA). Base‐free DMSO‐mediated production of FA has been shown to avoid the formation of stable intermediates and presumably the energy‐intensive FA recovery strategies. Here, we address the challenges in the development of an overall process: from catalyst immobilization to the FA isolation. The immobilization of the homogeneous catalyst was achieved using a multiphasic approach (n‐heptane/DMSO) ensuring high retention of the catalyst (>99%) and allowing facile separation of the catalyst‐free product phase. We show that the strong molecular interactions between DMSO and FA on the one hand shift the equilibrium towards the product side, on the other hand, lead to the formation of an azeotrope preventing a simple isolation step by distillation. Thus, we devised an isolation strategy based on the use of co‐solvents and computed the energy demands. Acetic acid was identified as best co‐solvent and its compatibility with the catalyst system was experimentally verified. Overall, the outlined process involving DMSO and acetic acid as co‐solvent has a computed energy demand on a par with state‐of‐the art amine‐based processes. However, the insufficient chemical stability of DMSO poses major limitations on processes based on this solvent.

中文翻译：

在基于DMSO的反应介质中Rh催化CO2加氢成甲酸：工艺开发中已解决和尚未解决的挑战

已经构思并评估了用于无胺均相催化CO ₂加氢成甲酸（FA）的工艺概念。已证明，无碱DMSO介导的FA生产可避免形成稳定的中间体，并避免能源密集的FA回收策略。在这里，我们解决了整个流程开发中的挑战：从催化剂固定化到FA分离。均相催化剂的固定化是采用多相方法（n庚烷/ DMSO）确保催化剂的高保留率（> 99％），并允许轻松分离无催化剂的产物相。我们表明，DMSO和FA之间的强大分子相互作用一方面使平衡向产物侧移动，另一方面导致形成共沸物，从而阻止了通过蒸馏的简单分离步骤。因此，我们基于共溶剂的使用设计了隔离策略，并计算了能源需求。乙酸被认为是最好的助溶剂，并通过实验验证了其与催化剂体系的相容性。总体而言，以DMSO和乙酸为助溶剂的工艺概述具有与最先进的基于胺的工艺相当的计算能量需求。然而，

更新日期：2018-10-30

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