Curse and Blessing–The Role of Water in the Homogeneously Ru-Catalyzed Epoxidation of Technical Grade Methyl Oleate,ACS Sustainable Chemistry & Engineering

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Curse and Blessing–The Role of Water in the Homogeneously Ru-Catalyzed Epoxidation of Technical Grade Methyl Oleate
ACS Sustainable Chemistry & Engineering ( IF 7.1 ) Pub Date : 2021-08-19 , DOI: 10.1021/acssuschemeng.1c03573
Johanna Vondran ₁ , Jerzy Pela _{2,

3} , Dennis Palczewski ₁ , Mirko Skiborowski ₄ , Thomas Seidensticker ₁

Affiliation

A homogeneous Ru-catalyst was investigated toward its potential recycling in methyl oleate epoxidation under mild conditions using hydrogen peroxide as a green oxidant. The literature-known catalyst complex, in situ formed from ruthenium acetylacetonate and dipicolinic acid, offers excellent selectivity toward epoxidation of technical grade (91.5%) methyl oleate. The resulting product methyl 9,10-epoxy stearate exhibits versatile applications. It is used industrially as a biobased epoxide for plasticizers and lubricants, or it can be further processed into polyurethanes. In this work, we first report a concept for homogeneous catalyst recycling, including extraction of the epoxide into an organic phase. Particular emphasis was on the effect of water, as it would accumulate due to recycling of the aqueous catalyst phase and replenishment of hydrogen peroxide prior to each recycling run. Consequently, mass transfer limitations needed to be addressed. By a combined extraction-distillation technique, we report the first sufficient homogeneous catalyst recycling strategy for Ru-catalyzed epoxidation of methyl oleate. Removal of water and separation of epoxide allowed for a ∑TON of 1243 after seven recycling runs with 97% selectivity toward epoxide and a TTON of 1384 after 13 runs, respectively, while catalyst leaching into the product phase was negligibly small. Moreover, pervaporation using a poly(vinyl alcohol) membrane was investigated as a promising technique for both removal of water and retention of the catalyst showing very promising results.

中文翻译：

诅咒与祝福——水在工业级油酸甲酯均相 Ru 催化环氧化中的作用

在温和条件下，使用过氧化氢作为绿色氧化剂，研究了均相 Ru 催化剂在油酸甲酯环氧化中的潜在回收利用。文献已知的催化剂配合物，原位由乙酰丙酮钌和吡啶二羧酸形成，对工业级 (91.5%) 油酸甲酯的环氧化具有出色的选择性。所得产品 9,10-环氧硬脂酸甲酯具有多种应用。它在工业上用作增塑剂和润滑剂的生物基环氧化物，或者可以进一步加工成聚氨酯。在这项工作中，我们首先报告了均相催化剂回收的概念，包括将环氧化物萃取到有机相中。特别强调水的影响，因为在每次循环运行之前，水会因含水催化剂相的循环和过氧化氢的补充而积聚。因此，需要解决传质限制。采用萃取-蒸馏联合技术，我们报告了第一个用于 Ru 催化油酸甲酯环氧化的充分均相催化剂回收策略。除去水和分离环氧化物使得在七次循环运行后 ∑TON 为 1243，环氧化物选择性分别为 97% 和 13 次运行后 TTON 为 1384，而浸出到产物相中的催化剂很少。此外，使用聚乙烯醇膜的渗透蒸发被研究为一种有前途的技术，用于去除水和保留催化剂，显示出非常有希望的结果。而浸出到产物相中的催化剂很少。此外，使用聚乙烯醇膜的渗透蒸发被研究为一种有前途的技术，用于去除水和保留催化剂，显示出非常有希望的结果。而浸出到产物相中的催化剂很少。此外，使用聚乙烯醇膜的渗透蒸发被研究为一种有前途的技术，用于去除水和保留催化剂，显示出非常有希望的结果。

更新日期：2021-08-30

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