B.A. Rodriguez, W.J. Tenn III / Applied Catalysis A: General 421–422 (2012) 161–163
163
2
1.5
1
rhodium–rhodium dimers, resulting in deactivation. By increasing
the excess of hydrogen to a ratio of 8:1:1 this dimer formation
can be overcome. As previously mentioned, this impacted product
selectivity, and as a result of the buildup of ethane, inhibited the
amount of makeup feed gas to be introduced which is represented
in a slight decrease in rate proportional to ethane formed.
Equally significant is the ability to perform this process under
low ethylene pressures – far lower than what has been explored
in any industrial process, thus demonstrating that ethylene other-
wise used as fuel could potentially be converted directly to alcohol.
This direct method provides a substantial economic incentive by
eliminating the need for the aldehyde hydrogenation. And while
it is expected that a more realistic gas stream other than syngas
diluted in nitrogen will provide hurdles in the future, this work
provides a proof of concept and ‘base-case’ scenario for evaluation
of an industrially significant chemical process.
0.5
0
0
1
2
3
4
5
time (h)
Fig. 2. Product formation with 4 wt. % Tri-n-hexylphosphine, 0.7 atm ethylene,
8:1:1. Triangles = propanol, diamonds = propionaldehyde, circles = pentanol.
1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
Acknowledgements
We gratefully acknowledge Luis Bollmann, Susan Domke, Rick
Wehmeyer, Kurt Olson, Howard Clark, and Mark Kaminsky for help-
ful suggestions.
References
0
1
2
3
4
5
6
7
time (h)
[1] (a) L. Xu, J. Liu, Q. Wang, S. Liu, W. Xin, Y. Xu, Appl. Catal. A 258 (2004) 47–53;
(b) S. Wang, B. Shen, L. Qu, Catal. Today 98 (2004) 339–342;
(c) W. Tenn, R. Singley, B. Rodriguez, Dellamea, J. Catal. Comm. 12 (2011)
1323–1327;
Fig. 3. Product formation with 4 wt. % Triphenylphosphine, 0.7 atm ethylene, 8:1:1.
Triangles = propanol, diamonds = propionaldehyde, circle = pentanol.
(d) L. Ropartz, D.F. Foster, R.E. Morris, A.M.Z. Slawin, D.J. Cole-Hamilton, J. Chem.
Soc. 9 (2002), 1997–2008 and references therein.
4. Discussion
[2] A rhodium catalyst immobilized on a phosphinated resin is utilized in the com-
mercial Acetica Process developed by Chiyoda/UOP for the carbonylation of
methanol;
From this study we find that the hydroformylation capability of
try and academia have focused more on converting ethylene to
propanol utilizing triphenylphosphine to reach an aldehyde inter-
mediate, [6,7] a direct method is readily available even at dilute
feed streams. As shown in Figs. 2 and 3, a preference for propanol
or propanal can be decided merely via the addition of the free lig-
and prior to reactor startup and in situ generation of the catalyst.
While TPP and the other bulky, phosphine ligands heavily favor
was previously proposed that this effect is highly correlated to the
cone angle of the phosphine ligands, [8] wherein all three of the
bulkiest ligands almost exclusively produce propanal. As demon-
strated from Table 1, significant selectivity behaviors are affected
by feed gas conditions. At a 2:1:1 excess of hydrogen over carbon
monoxide and ethylene at 3.4 atm, ethane formation remains low
for the linear alkyl phosphines. However as the feed gas becomes
further diluted, this increases ethane formation by as much as
a factor of ten. This is likely the result of less hydrogen being
available to regenerate the rhodium catalyst, and to break up any
(a) N. Yoneda, T. Minami, J. Weiszmann, B. Spehlmann, The Chiyoda/UOP
AceticaTM process: a novel acetic acid technology, in: H. Hattori, K. Otsuka (Eds.),
Surface Science and Catalysis, vol. 121, Kodansha, Tokyo, 1999, pp. 93–98;
(b) N. Yoneda, Y. Shiroto, K. Hamato, S. Asaoka, T. Maekima, U.S. Patent 5,334,755
(1994).;
(c) N. Yoneda, T. Minami, K. Hamato, Y. Shiroto, Y.J. Hosono, Jpn. Petrol. Inst. 46
(2003) 229–231. A plant design and feasibility study of a process for the hydro-
formylation of 1-octene to nonanal utilizing a rhodium catalyst on immobilized
on phosphinated silica has been reported: H. van den Berg and A.G.J. van der
Ham, University of Twente, Department of Science and Technology, 2004 and
discussed in Reek, J.N.H., van Leeuwen, P.W.N.M., van der Ham, A.G.J., De Haan,
A.B. “Immobilization of Tailor-made Homogeneous Catalysts” in Catalyst Separa-
tion, Recovery, and Recycling, In: D.J. Cole-Hamilton, R.P. Tooze (Eds.), Springer,
The Netherlands, 2006.
[3] (a) Tjeerd Jongsma Polymer-Bound Rhodium Hydroformylation Catalysts The-
sis, Rijksuniversiteit Groningen, 1992;
(b) Chapter 10 P.W.N.M. van Leeuwen, C. Claver (Eds.), Rhodium Catalyzed
Hydroformylation, Kluwer Academic Publishers, Dordecht, The Netherlands,
2000.
[4] A.S.C. Chan, H. Shieh, J.R. Hill, Chem. Commun. (1983) 688–689.
[5] G. Kiss, E.J. Mozeleski, K.C. Nadler, E. VanDriessche, C. DeRoover, J. Mol. Catal.
138 (1999) 155–176.
[6] R.H. Grubbs, C. Gibbons, L.C. Kroll, W.D. Bonds, C.H. Brubaker, J. Am. Chem. Soc.
95 (1973) 2373–2375, and references therein.
[7] J.P. Collman, L.S. Hegedus, M.P. Cooke, J.R. Norton, G. Dolcetti, D.N. Marquardt, J.
Am. Chem. Soc. 94 (1972) 1789–1790, and references therein.
[8] C.A. Tolman, Chem. Rev. 77 (1977) 313.