Continuous hydroformylation of 1-decene in an aqueous biphasic system enabled by methylated cyclodextrins. Issue 12 (29th April 2020)

• Record Type: Journal Article
• Authors: Künnemann, K. U.; Schurm, L.; Lange, D.; Seidensticker, T.; Tilloy, S.; Monflier, E.; Vogt, D.; Dreimann, J. M.
• Is Part Of: Green chemistry. Volume 22:Issue 12(2020)
• Page Start: 3809
• Page End: 3819
• Publication Date: 2020-04-29
• Subjects: Environmental chemistry -- Industrial applications -- Periodicals; Environmental management -- Periodicals; 660
• DOI: 10.1039/d0gc00820f
• Languages: English
• ISSNs: 1463-9262

Abstract

Abstract : Long-term applications of cyclodextrins in the aqueous biphasic hydroformylation of higher olefins with high selectivities and simultaneous catalyst recycling. Abstract : For the first time, randomly methylated β-cyclodextrin was applied as the mass transfer agent in a continuous process. Considering the example of the Rh-catalyzed hydroformylation of 1-decene, process development was shown, where cyclodextrin was used together with a catalyst system that was continuously recovered and recycled using an aqueous biphasic system. In initial experiments, water-soluble and commercially available Rh/TPPTS and Rh/sulfoxantphos catalyst systems were scaled up from 50 ml into 1000 ml high-pressure autoclave systems to demonstrate their scalability. Both these systems were compared, and they afforded excellent chemoselectivity (>99%) toward the desired linear aldehyde product. In particular, higher regioselectivity (up to 31) was achieved for the Rh/sulfoxantphos system. Investigations regarding the long-term stability of the mass transfer agent and both catalyst systems were carried out in a continuously operated miniplant process. It was shown that the process could be successfully operated under the steady state for over 200 h with chemoselectivity of >97% toward the desired aldehyde product. Simultaneously, extremely low Rh leaching (total: 0.59%) was observed over the entire period of 200 h.