Olefins Fischer-Tropsch catalysis

Fig. 5 Olefin/paraffin ratio as a function of TOS for C2-C6 components for 12% Co/Si02. Step changes in olefin/paraffin ratio are due to increased GHSV at 23 h, as 20% water addition at 50 h, 33% water addition at 70 h and back to the dry feed at 95 h. H2/CO = 2.1, P - 20 bar, T = 483 K.19 Reprinted from Journal of Catalysis, Vol. 231, S. Storsaeter, 0. Borg, E. A. Blekkan and A. Holmen, Study of the effect of water on Fischer-Tropsch synthesis over supported cobalt catalysts, pp. 405 119. Copyright (2005), with permission from Elsevier. 

Transition metal carbonyls and their derivatives are remarkably effective and varied in their ability to catalyze reactions between unsaturated molecules (e.g., CO and olefinic compounds) or between certain saturated and unsaturated molecules (e.g., olefins and H2 or H20). The carbonyl derivatives of cobalt are particularly active catalysts for such reactions and have been put to use in the industrial synthesis of higher aliphatic alcohols. In fact, much of the growth in knowledge concerning catalysis by metal carbonyls has been stimulated by the industrial importance of the Fischer-Tropsch synthesis, and by the economically less important, but chemically more tractable, hydroformylation reaction. 

The reaction of olefins with carbon monoxide and hydrogen in the presence of cobalt carbonyl catalysis affords inter alia aldehydes, ketones, and alcohols. These reactions are of considerable industrial importance. The industrial reactions were originally called the Fischer-Tropsch or Oxo syntheses but now are described under the general title of hydro-formylation reactions 3, 224). 

H. Schulz, H. Gokcebay, Fischer-Tropsch CO-hydrogenation as a means for linear olefins production, in Catalysis of Organic Reactions , Ed. J. Kosak, M. Dekker, New York (1984) 153... 

The hydroformylation or oxo reaction, or oxo synthesis discovered by Otto Roelen and patented in 1938 (1) is the addition of carbon monoxide and dihydrogen to an olefin double bond in the presence of a transition metal complex as the catalyst. The discovery of the reaction regarding the cobalt catalyzed Fischer-Tropsch reactions. Roelen s observation that ethylene, H2, and CO were converted into propanal, and at higher pressures, diethyl ketone, marked the beginning of hydroformylation catalysis (2). The term of hydroformylation relates to the formal addition of hydrogen and a formyl group to the olefin substrate. 

J. Barrault, C. Forquy, and V. Perrichon, Effects of manganese oxide and sulphate on olefin selectivity of iron supported catalysts in the Fischer-Tropsch reaction, Applied Catalysis, vol. 5, no. 1, pp. 119—125, 1983. 

Dupain, X., Krul, R.A., Schaverien, C.J., Makkee, M., Mouhjn, J.A., 2006. Production of clean transportation fuels and lower olefins from Fischer—Tropsch synthesis waxes under fluid catalytic cracking conditions. The potential of highly paraffinic feedstocks for FCC. Applied Catalysis B 63, 277—295. 

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