(701a) Heterogeneous, Carbon-Supported Cobalt Oxide Catalysts for the Oligomerization of Light Olefins (C2-C4) into Linear Olefins

Authors: 
Chada, J. P., University of Wisconsin-Madison
Xu, Z., University of Wisconsin-Madison
Zhao, D., University of Wisconsin-Madison
Rosenfeld, D. C., The Dow Chemical Company
Rogers, J., The Dow Chemical Company
Hermans, I., University of Wisconsin-Madison
Huber, G. W., University of Wisconsin-Madison
Olefin oligomerization is a useful reaction to upgrade abundant, light hydrocarbons stemming from natural gas and petroleum manufacturing to higher-valued, longer-chain derivatives. Despite its commercial relevance, olefin oligomerization is one of the few industrial processes still dominated by homogeneous catalyst systems, which require an activator such as MAO. An early publication by Shultz et al. identified carbon-supported cobalt oxide as a particularly selective heterogeneous catalyst for linear oligomerization of C2-C6 alpha-olefins into linear olefins. [1] Recent work from our research group has expanded upon the original work of Shultz et al. to provide rational for the exceptional selectivity of this system and highlight the sensitivity of catalytic activity which can be improved by making variations to the synthesis procedures. [2] Here, we will report our most recent efforts to optimize these carbon-supported, cobalt oxide-based systems for the oligomerization of ethylene to 1-butene with selectivities as high as 82%. The influence of the carbon support on the final state of the active catalyst will be presented. We will suggest reasons for the inactivity of similarly synthesized materials on SiO2 and Al2O3 supports. Finally, we will demonstrate the potential industrial application of this system by showing that the less-valuable linear internal oligomers can be fed directly to a hydroformylation catalyst to form linear aldehydes.

[1] (a) Schultz, R. G.; Schuck, J.; Wildi, B. J. Catal. 1966, 6, 385−396. (b) Schultz, R. G.; Engelbrecht, R. M.; Moore, R. N.; Wolford, L. T. J. Catal. 1966, 6, 419−424.

[2] Zhuoran Xu, Joseph P. Chada, Dongting Zhao, Carlos A. Carrero, Yong Tae Kim, Devon C. Rosenfeld, Jessica L. Rogers, Steven J. Rozeveld, Ive Hermans, and George W. Huber. ACS Catalysis 2016 6 (6), 3815-3825