Continuous Gas‐Phase Hydroformylation of 1‐Butene using Supported Ionic Liquid Phase (SILP) Catalysts

Abstract

Abstract:The concept of supported ionic liquid phase (SILP) catalysis has been extended to 1-butene hydroformylation. A rhodium-sulfoxantphos complex was dissolved in [BMIM][n-C 8 H 17 OSO 3 ] and this solution was highly dispersed on silica. Continuous gas-phase experiments in a fixed-bed reactor revealed these SILP catalysts to be highly active, selective and long-term stable. Kinetic data have been acquired by variation of temperature, pressure, syngas composition, substrate and catalyst concentration. A linear dependency in rhodium concentration could be established over a large concentration range giving another excellent hint for truly homogeneous catalysis in the SILP system. Compared to former studies using propene, the SILP system showed significantly higher activity and selectivity with 1-butene as feedstock. These findings could be elucidated by solubility measurements using a magnetic microbalance.

Recent Advances in Continuous Rhodium-Catalyzed Hydroformylation

“…Haumann and coworkers continued this work by extending the method to the continuous hydroformylation of 1-butene [47]. With [BMIM] [n-C 8 H 17 OSO 3 ] and Rh-SulfoXantPhos, the catalytic activity was found to be much higher than that in the hydroformylation of propene.…”

Metal Nanoparticles/Ionic Liquid/Cellulose: Polymeric Membrane for Hydrogenation Reactions

“…In comparison to traditional liquid-liquid biphasic systems, higher catalytic activity and lower metal leaching can be achieved by appropriately tuning the experimental conditions [15,[18][19][20][21][22] . These materials are prepared by the covalent attachment of IL to the support surface or by simply depositing the IL phases containing catalytically active species, usually transition metal complexes [20] or, more rarely, metal nanoparticles [23,24] on the surface of the support, which is usually a silica or polymeric material.…”

Rhodium–Phosphite SILP Catalysis for the Highly Selective Hydroformylation of Mixed C4 Feedstocks

“…During catalysis the immobilized catalytic ionic liquid film comes into contact solely with gaseous reactants and products. For the continuous gas-phase hydroformylation of pure 1-alkene feedstock, such as, propene and 1-butene, this concept has been demonstrated quite successfully with good catalytic activity (turnover frequencies (TOFs) up to 500 h À1 in the case of propene [10] and 564 h À1 in the case of 1-butene [11] ) and excellent catalyst stability (up to 200 h time-on-stream in the case of propene [10] and 120 h in the case of 1-butene [12] ) as was demonstrated using a Rh-SILP catalyst modified with the sulfonated phosphine ligand sulfoxantphos (1). The sulfoxantphos-rhodium catalyst is, however, unable to react with internal alkenes such as 2-butenes in either hydroformylation or isomerization.…”