Abstract
A conversion of stearic acid into hydrocarbons in the presence of palladium on alumina has been studied. It has been shown that heptadecane and carbon monoxide are formed as the main products, diheptadecylketone is formed as a by-product, and the contribution of the decarbonylation reaction increases as compared to decarboxylation in the presence of hydrogen with an increase in its pressure. The formation of heptadecene and formic acid as intermediate products has allowed the conclusion that the cleavage of the carbon-carbon bond in the stearic acid molecule R-COOH takes place in the Pd coordination sphere, resulting in the formation of formic acid (or its fragment associated with palladium) and the corresponding olefinic product. Depending on the reaction conditions, formic acid and/or its fragment decompose, yielding CO and H2O or CO2 and H2. The main routes of the reaction have been simulated using quantum-chemical methods, and it has been shown that the reaction rate-limiting stage is the cleavage of C-C bond in the acid molecule.
Similar content being viewed by others
References
A. S. Berenblyum, V. Ya. Danyushevsky, E. A. Katsman, et al., Neftekhimiya 50, 17 (2010) [Pet. Chem. 50, 305 (2010)].
B. Smith, H. C. Greenwell, and A. Whiting, Energy Environ. Sci. 2, 262 (2009).
T. Kalnes, T. Marker, and D. R. Shonnard, Int. J. Chem. Reactor Eng., Article A 48 (2007).
P. M. Schenk, S. R. Thomas-Hall, E. Stephens, et al., Bioenerg. Res., No. 1, 20 (2008).
I. Kubičková, M. Snåre, K. Eränen,et al., Catal. Today 106, 197 (2005).
J. G. Immer, M. J. Kelly, and H. H. Lamb, Appl. Catal. A: Gen. 375, 134 (2010).
J. G. Immer, PhD Dissertation, North Carolina State University (2010).
L. Boda, G. Onyestyák, H. Solt, et al., Appl. Catal. A: Gen. 374, 158 (2010).
Yizhi Xiang, Xiaonian Li, Chunshan Lu, et al. Appl. Catal. A: Gen. 375, 289 (2010).
D. N. Laikov, Chem. Phys. Lett. 281, 151 (1997).
J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett 77, 3865 (1996).
D. N. Laikov, Chem. Phys. Lett. 416, 116 (2005).
J. Cizek, Adv. Chem. Phys. 14, 35 (1969).
The Aldrich Library of 13C and 1H FT NMR Spectra (Aldrich Chemical Company, Milwaukee, 1993).
P. T. Do, M. Chiappero, L. L. Lobban, and D. E. Resasco, Catal. Lett. 130, 9 (2009).
M. Snåre, I. Kubičková, P. Mäki-Arvela, et al., Ind. Eng. Chem. Res. 45, 5708 (2006).
E. Stern and C. Timmons, Gillam and Stern’s Introduction to Electronic Absorption Spectroscopy in Organic Chemistry (Edward Arnold, London, 1970).
B. Donnis, R. G. Egeberg, P. Blom, and K. G. Knudsen, Top. Catal. 52, 229 (2009).
M. Snåe, P. Mäki-Arvela, I. L. Simakova, et al., Russ. J. Phys. Chem. B 3, 1035 (2009).
J. R. Rostrup-Nilsen, J. Sehested, and J. K. Norskov, Hydrogen and Synthesis Gas by Steam and CO2 Reforming (Academic, 2002).
G. Patermarakis, Appl. Catal. A: Gen. 252, 231 (2003).
I. S. Kolomnikov, M. B. Erman, V. P. Kukolev, and M. E. Vol’pin, Kinet. Katal. 13, 252 (1979).
G. Henrici-Olive and S. Olive, Coordination and Catalysis, (Verlag Chemie, Weinheim, 1977).
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © A.S. Berenblyum, T.A. Podoplelova, R.S. Shamsiev, E.A. Katsman, V.Ya. Danyushevsky, 2011, published in Neftekhimiya, 2011, Vol. 51, No. 5, pp. 342–347.
Rights and permissions
About this article
Cite this article
Berenblyum, A.S., Podoplelova, T.A., Shamsiev, R.S. et al. On the mechanism of catalytic conversion of fatty acids into hydrocarbons in the presence of palladium catalysts on alumina. Pet. Chem. 51, 336–341 (2011). https://doi.org/10.1134/S0965544111050069
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0965544111050069