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Effect of Compressed Gas Addition On H2/CO Tunability and Hydroformylation Catalysis In Gas-Expanded Liquids (GXLs)

Thursday, October 20, 2011: 12:35 PM
200 H (Minneapolis Convention Center)
Zhuanzhuan Xie, Chemical & Petroleum Engineering, University of Kansas, Lawrence, KS, Kirk Snavely, Cebc, University of Kansas, Lawrence, KS, Swarup Maiti, Center for Environmentally Beneficial Catalysis, University of Kansas, Lawrence, KS, Jon Tunge, Chemistry, Univ. Kansas, Lawrence, KS and Bala Subramaniam, Chemical and Petroleum Engineering, Center for Environmentally Beneficial Catalysis, University of Kansas, Lawrence, KS

Previously, we had reported on the beneficial effects of carbon dioxide expanded liquids for hydroformylation1, 2. In this talk, we present systematic investigations of the comparative effects of compressed gases (CO2 and light alkanes) on the relative miscibilities of CO and H2 in GXLs and also the corresponding effects on Rh-based hydroformylation catalysis with monodendate (triphenylphosphine) and bidendate ligands. It is shown that the H2/CO ratio in the gas-expanded liquid phase (containing substrate and dissolved catalyst complex), a key determinant of the turnover frequency and regioselectivity, can be easily tuned with GXLs to optimize these performance measures at relatively mild pressures3. Continuous hydroformylation with bulky phosphite ligands is demonstrated in a GXL-based stirred reactor equipped with nanofiltration membranes.  It is shown that the Rh leaching from these reactors is on the order of a few tens of ppb, which easily exceeds the economic viability criterion4, 5.     

1.      H. Jin, A. Ghosh, J. A. Tunge and B. Subramaniam, AIChE Journal, 52(7), 2575-2591 (2006)

2.      H. Jin and B. Subramaniam, Chem. Eng. Sci., 59, 4887, (2004)

3.      Z. Xie, W. Snavely, A. Scurto, and B. Subramaniam, J. Chem. Eng. Data, 54 (5), 1633, (2009)

4.      J. Fang, H. Jin, T. Ruddy, K. Pennybaker, D. Fahey and B. Subramaniam, Industrial and Engineering Chemistry Research, 46, 8687-8692 (2007)

5.      J. Fang, R. Jana, J. Tunge, B. Subramaniam, Applied Catalysis, A: General, 393(1-2), 294-301 (2011)


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See more of this Session: Reactions In near-Critical and Supercritical Fluids
See more of this Group/Topical: Catalysis and Reaction Engineering Division