328837 Continuous Hydroformylation With Nanofilterable Rh Catalyst Bound to Polysiloxane Ligands in a Stirred Membrane Reactor

Sunday, November 3, 2013: 4:15 PM
Continental 1 (Hilton)
Zhuanzhuan Xie1,2, Bibhas Sarkar1, Dupeng Liu1,2, R. V. Chaudhari1,2 and Bala Subramaniam3,4, (1)Center for Environmentally Beneficial Catalysis, University of Kansas, Lawrence, KS, (2)Department of Chemical & Petroleum Engineering, University of Kansas, Lawrence, KS, (3)Department of Chemical and Petroleum Engineering, Center for Environmentally Beneficial Catalysis, University of Kansas, Lawrence, KS, (4)Center for Environmentally Beneficial Catalysis, The University of Kansas, Lawrence, KS

Recently, we reported continuous 1-octene hydroformylation with bulky phosphite ligands1 in a stirred reactor equipped with nanofiltration membranes under either syngas pressure only2 or CO2-expanded liquids (CXLs).3 It was shown that the Rh leaching from these reactors is less than 1ppm, which easily exceeds the economic viability criterion.4  While JanaPhos ligand has many benefits, it involves tedious synthesis steps and is air- and moisture-sensitive, making cost-effective large-scale synthesis difficult. Rh complex catalysts bound to inexpensive soluble polysiloxanes ligands are investigated as alternatives for the hydroformylation of higher olefins (C5+). Polysiloxanes containing two different functional groups (amine- and phosphine-) were used for synthesis of Rh catalysts. Both types of Rh complexes show good chemoselectivity and stability when tested in batch and continuous hydroformylation experiments. The phosphine-functionalized ligand exhibited higher activity than the amine functionalized one. Continuous operation lasting several days was demonstrated in a stirred reactor equipped with nanofiltration membrane with steady hydroformylation activity (TOF = 193 h-1, cumulative TON after 120 hours was 12,240) and high chemoselectivity (> 91 %) towards the aldehydes. The Rh concentrations in the reactor effluent were less than a few ppm, which can be easily recovered by adsorption. In addition, the idea of using gas-expanded liquids to enhance H2/CO ratio and reduce CO inhibition during hydroformylation reactions catalyzed by Co-based complexes is also discussed.

1.            Jana R, Tunge JA. A Homogeneous, recyclable rhodium(I) catalyst for the hydroarylation of Michael acceptors. Org Lett. 2009;11:971-974.

2.            Fang J, Jana R, Tunge JA, Subramaniam B. Continuous homogeneous hydroformylation with bulky rhodium catalyst complexes retained by nano-filtration membranes. Appl Catal, A. 2011;393:294-301.

3.            Xie Z, Fang J, Maiti S, Snavely W, Tunge J, Subramaniam B. Enhanced Hydroformylation by Carbon Dioxide-Expanded Media with Soluble Rh Complexes in Nanofiltration Membrane Reactors. AIChE Journal. 2013;in press.

4.            Fang J, Jin H, Ruddy T, Pennybaker K, Fahey D, Subramaniam B. Economic and environmental impact analyses of catalytic olefin hydroformylation in CO2-expanded liquid (CXL) media. Ind Eng Chem Res. 2007;46:8687-8692.

 

 


Extended Abstract: File Not Uploaded
See more of this Session: Novel Catalytic Materials
See more of this Group/Topical: Catalysis and Reaction Engineering Division