Rhodium-Catalyzed Hydroformylation of Long-Chain Olefins in Aqueous Multiphase Systems in a Continuously Operated Miniplant

Abstract

We investigate aqueous multiphase systems for catalytic gas/liquid reactions, namely, the rhodium-catalyzed hydroformylation of the long-chain olefin 1-dodecene. The multiphase system was formulated from 1-dodecene, water, and a nonionic surfactant, which increases the solubility between the two nonmiscible liquid phases. On the basis of these systems, we present in this paper a transfer of lab experiments (semibatch) to a successful operation of a miniplant in continuous mode. Under optimized conditions, the reaction showed turnover frequencies of ∼200 h–1 and high selectivity of 98:2 to the desired linear aldehyde. The miniplant was operated continuously for a total of 130 h. The control of the phase separation and catalyst recycling for product isolation for a long time period appeared to be challenging. Nevertheless, the separation was kept stable for over 24 h. The organic components in the product phase amounted to desired values between 95 and 99 wt %. The desired 99.99% of the catalyst remained in the aqueous catalyst phase.

Microemulsion Systems as Switchable Reaction Media for the Catalytic Upgrading of Long‐Chain Alkenes

“…2) is investigated by our research group for several years [7,10,11]. 2) is investigated by our research group for several years [7,10,11].…”

“…A more detailed description of experimental set-up and reaction procedure can be found in [7]. The typical reaction conditions for the hydroformylation were 15 bar of synthesis gas (1:1 mixture, purity 2.1), an internal reactor temperature of 65 -110°C, and a stirring speed of 1200 rpm.…”

Characteristics of Stable Pickering Emulsions under Process Conditions

“…A lot of parameters are crucial to find the optimal reaction setup [26]. A lot of parameters are crucial to find the optimal reaction setup [26].…”

Recycling Homogeneous Catalysts Simply by Organic Solvent Nanofiltration: New Ways to Efficient Catalysis

“…Unfortunately, this process is limited to short‐chain olefins (C 3 and C 4 ). A variety of approaches have been presented in the literature for making long‐chain olefins accessible to highly selective hydroformylation and even for recycling the homogeneous catalyst, namely: i) the design of sophisticated catalyst complexes, ii) design of advanced solvent systems such as thermomorphic solvent systems or ionic liquid catalyst phases, and iii) the application of additives . Unfortunately, these approaches are often designed to suit specific, narrow applications or are unable to simultaneously fulfill multiple critical process demands such as reactivity, stability and recovery…”