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

Abstract

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.

Recycled Poly(ethylene terephthalate) for High Temperature Solvent Resistant Membranes

“…DMF is a commonly used solvent in synthetic organic chemistry. Other potential applications requiring solvent-resistant membranes are the optimization of chemical processes by coupling reactors with membrane systems. , An interesting example is the membrane enhanced peptide synthesis …”

“…Other potential applications requiring solvent-resistant membranes are the optimization of chemical processes by coupling reactors with membrane systems. 52,53 An interesting example is the membrane enhanced peptide synthesis. 54 The measurement of the DMF flux as a function of pressure for PET membranes at room temperature, shown in Figure S9, demonstrates that the membranes suffer only compaction around 10% when the pressure is increased from 1 to 10 bar.…”

Homogeneously Catalyzed 1,3‐Diene Functionalization – A Success Story from Laboratory to Miniplant Scale

“…Recently, our group presented an appropriate solution to that problem in combination with a drastic increase of productivity of the palladium catalyst. By implementation of a continuously operated membrane reactor, the turnover number (TON) of the palladium catalyst was increased from 460 (batchwise) to 5135 (continuously) …”

Facile catalyst recycling by thermomorphic behaviour avoiding organic solvents: a reactive ionic liquid in the homogeneous Pd-catalysed telomerisation of the renewable β-myrcene

“…β-Myrcene as a renewable raw material 22,23 has been investigated in telomerisation. 24,25 Additionally, it has been used in several amination reactions, such as hydroaminomethylation 26 and hydroamination, [27][28][29] and in other homogeneously catalysed functionalization reactions such as hydroformylation. 30,31 However, its telomerisation was never carried out with dimethylamine and recycling of the homogeneous palladium/phosphorus catalyst was considered but never executed.…”