Hydroformylation of 1-hexene in supercritical carbon dioxide: characterization, activity, and regioselectivity studies.
The hydroformylation of alkenes is a major commercial process used for the production of oxygenated organic compounds. When the hydroformylation reaction is performed using a homogeneous catalyst, an organic or aqueous solvent is employed, and a significant effort must be expended to recover the catalyst so it can be recycled. Development of a selective heterogeneous catalyst would allow simplification of the process design in an integrated system that minimizes waste generation. Recent studies have shown that supercritical carbon dioxide (scCO2) as a reaction solvent offers optimal environmental performance and presents advantages for ease of product separation. In particular, we have considered the conversion of 1-hexene to heptanal using rhodium- and platinum-phosphine catalysts tethered to supports insoluble in scCO2 to demonstrate the advantages and to understand the limitations of a solid-catalyzed process. One of the historical limitations of supported catalysts is the inability to control product regioselectivity. To address this concern, we have developed tethered catalysts with phosphinated silica and controlled pore size MCM-41 and MCM-20 supports that provide improved regioselectivity and conversion relative to their nonporous equivalents. Platinum catalysts supported on MCM-type supports were the most regioselective whereas the analogous rhodium catalysts were the most active for hydroformylation of 1-hexene in scCO2.
Marteel
Anne E
AE
Department of Chemistry, The University of Toledo, Toledo, Ohio 43606, USA.
Tack
Timothy T
TT
Bektesevic
Selma
S
Davies
Julian A
JA
Mason
Mark R
MR
Abraham
Martin A
MA
D000475:Alkenes / Q000032:analysis / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D002617:Chemical Industry; D003246:Conservation of Energy Resources; D004787:Environmental Pollution / Q000517:prevention & control; D016062:Porosity; D014867:Water / Q000737:chemistry
D000475:Alkenes; D014867:Water; D002245:Carbon Dioxide; C117224:1-hexene