Continuously Operated Hydroamination – Toward High Catalytic Performance via Organic Solvent Nanofiltration in a Membrane Reactor

• Published in: Industrial & engineering chemistry research 2017-11, Vol.56 (46), p.13634-13641
• Main Authors: Vogelsang, Dennis, Dreimann, Jens M, Wenzel, Dominik, Peeva, Ludmila, da Silva Burgal, João, Livingston, Andrew G, Behr, Arno, Vorholt, Andreas J
• Format: Article
• Language: English
• ISSN: 0888-5885; 1520-5045
• DOI: 10.1021/acs.iecr.7b03770

Still, the hydroamination of dienes to form allylic amines is a challenging task in a continuous operation. Herein, we present the performance of a membrane reactor by the implementation of a continuously operated hydroamination reaction of β-myrcene with morpholine. Via application of a poly ether–ether–ketone (PEEK) membrane, operation at elevated temperatures was possible in an integrated reaction/separation unit. First, the kinetics of the hydroamination reaction and relevant membrane characteristics were determined under optimized reaction conditions. Afterward, these results were incorporated in a reactor/separator model to predict the process behavior. With this, catalyst replenishment was adjusted resulting in stable continuous operation. In the end an increase of the turnover number from 460 to 5135 compared to a batch process was achieved. The desired geranyl amines were obtained in very good yields higher than 80%, while an excellent conversion of β-myrcene above 93% was reached in a long-time stable process.