Coupling Rhodium‐Catalyzed Hydroformylation of 10‐Undecenitrile with Organic Solvent Nanofiltration: Toluene Solution versus Solvent‐Free Processes

Abstract

Intensification of the rhodium‐catalyzed hydroformylation process to produce 12‐oxo‐dodecanenitrile from biosourced 10‐undecenitrile was performed by coupling the reaction with organic solvent nanofiltration (OSN) for the recycling of the expensive Rh catalyst and the ligands. Four phosphorus‐based ligands were compared with respect to their catalytic performance and rejection in OSN. Biphephos showed the best compromise and up to 3 reaction‐OSN cycles were performed in toluene. A good recycling of the catalytic system was evidenced arising from the OSN (up to 88 % rejection). In order to develop a greener process, a similar approach was achieved in bulk (i. e. solvent‐free medium), thus proving the catalyst recycling feasibility but also that the optimal OSN conditions are not the same as for toluene. Finally, integration of OSN in the overall production process is discussed, aiming at the proposal of a hybrid separation process involving a combination of OSN and distillation for an energy‐efficient separation step.

Organic Solvent Nanofiltration in Pharmaceutical Applications

“…The separation of homogeneous catalyst from the reaction mixture by OSN can be run at off-line or online mode. , In the off-line mode, OSN serves as a post-treatment step. The reaction is conducted separately in a batch reactor.…”

Recovery of Homogeneous Platinoid Catalysts from Pharmaceutical Media: Review on the Existing Treatments and the Perspectives of Membrane Processes

“…Starting from commercially available complexes, some modifications can be made by obtaining the desired characteristics without having to carry out a complete synthesis of a catalyst. Several studies are reported in the literature [ 115 , 116 ]. X. Bei et al [ 117 ] used the easily affordable Pd(dba) 2 and 4-tBu-C 6 H 4 Br.…”

In situ spectroscopic investigations on BiPhePhos modified rhodium complexes in alkene hydroformylation

“…[18][19][20][21][22][23] Novel separation techniques for molecular catalysts such as TMS (thermomorphic solvent systems) and organic solvent nanofiltration have been developed with the Rh/BiPhePhos catalysts. [24][25][26][27] The diphosphite ligand BiPhePhos was also applied in heterogenized catalysts on Scheme 1 Catalytic cycle of the chelate-ligand modified rhodium catalysed hydroformylation of alkenes based on a Wilkinson-type mechanism.…”

“…18–23 Novel separation techniques for molecular catalysts such as TMS (thermomorphic solvent systems) and organic solvent nanofiltration have been developed with the Rh/BiPhePhos catalysts. 24–27 The diphosphite ligand BiPhePhos was also applied in heterogenized catalysts on basis of the SILP (supported ionic liquid phase) and POL (porous organic ligand) concepts. 28–33…”