Improving Aqueous Biphasic Hydroformylation of Unsaturated Oleochemicals Using a Jet‐Loop‐Reactor

Abstract

In two case studies, the reaction performance of the aqueous biphasic hydroformylation of two industrially relevant oleochemicals, namely methyl 10-undecenoate (case 1) and methyl oleate (case 2), is significantly improved by the use of a Jet-Loop Reactor concept. Based on previously reported studies, only the two green and benign co-solvents, 1-butanol and isopropanol are applied, respectively, in the absence of any additional auxiliary. Both reactions benefit highly from using this special piece of equipment, specifically designed for improving gas-liquid-liquid mixing to create large interfacial areas with no moving internals. In case 1, the loading of the co-solvent 1-butanol is successfully reduced. For the first time significant yields (>40% after 1 h) are obtained in the absence of any co-solvent, which is very beneficial, since aldehyde products and substrate form a pure product phase enabling straightforward separation. In case 2, the loading of the substrate methyl oleate is successfully increased from 6 to 30 wt% still showing satisfying productivity. At 15 wt%, the yield of the desired internal aldehydes in the jet-loop reactor is increased by a factor of five compared to a stirred tank reactor after 3 h. Practical Applications: The production of aldehydes from hydroformylation of olefins is highly relevant for the chemical industry, since these can undergo numerous subsequent reactions, to form for instance alcohols, amines, and carboxylic acids. Generally, aldehydes from oleochemicals can serve as platform chemicals for gaining access to bifunctional molecules, which are interesting as polymer precursors. Performing hydroformylation with a water-based solvent system enables efficient product separation from the aqueous catalyst phase for the realzation of more sustainable processes. By using the Jet-Loop Reactor, the performance of the reaction system can be greatly improved addressing its practical relevance.

Rhodium‐Catalysed Reductive Amination for the Synthesis of Tertiary Amines

“…1 j is synthesised by hydroformylation of methyl 10-undecenoate, which is made from castor oil. [24,25] This is a promising result for the conversion of other bifunctional aldehydes.…”

Reusable Catalysts for Hydroformylation‐Based Reactions

“…However, after the first run, the conversion decreases to around 50 % and remained almost constant for nine additional runs. The same authors [106] extended this study for the valorization of methyl 10‐undecenoate using a jet‐loop reactor (JLR) for this biphasic system, in which intensive mixing was achieved to overcome the solubility limitations [107] …”

“…The same authors [106] extended this study for the valorization of methyl 10-undecenoate using a jet-loop reactor (JLR) for this biphasic system, in which intensive mixing was achieved to overcome the solubility limitations. [107] The low solubility of long-chain olefins in water often result in low olefin conversion in the biphasic hydroformylation reactions. Attempting to improve their conversion under Scheme 10.…”

Fettsäuren und Fettsäurederivate als nachwachsende Plattformmoleküle für die chemische Industrie

“…[75] Von hohem Interesse sind auch neuartige Entwicklungen im Aufbau der Reaktoren, die für Gas-flüssig-flüssig-Multiphasen-Katalyse eingesetzt werden, beispielsweise die Verwendung eines Jet-Loop-Reaktors für die Verbesserung der wässrigen, biphasischen Hydroformylierung von 17 b und 2 b. [76] Bis-Hydroaminoalkylierung von 17 b beziehungsweise 17 d mit Piperazin gibt den langkettigen linearen Diester 36 b und Diol 36 d, interessante Substrate für Polyester (Schema 15). Der Schlüssel zum Erfolg war hierbei die selektive Kristallisation des Produktes aus der Reaktionsmischung in einer Reinheit von > 98 %.…”