Liquid-phase hydrogenation of methyl oleate on a Ni/α-Al2O3 catalyst: A study based on kinetic models describing extreme and intermediate adsorption regimes |
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Authors: | Maria I. Cabrera Ricardo J. Grau |
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Affiliation: | aINTEC, Institute de Desarrollo Tecnologico para la Industria Quimica. Universidad Nacional del Literal (U.N.L.) and Consejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET), Giiemes 3450, (3000) Santa Fe, Argentina |
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Abstract: | The kinetics of the hydrogenation of methyl oleate on a Ni/α-Al2O3 catalyst was studied in the absence of mass-transport limitation, at 398 ≤ T ≤ 443 K and 3.7 ≤ PH2 ≤ 6.5 bar. The kinetic modeling was performed on the basis of elementary step mechanisms involving different regimes of competition between hydrogen and methyl oleate. Admitting a distinction between occupied-sites and covered-sites by the large molecule of methyl oleate, a rigorous proposal was made to link the seemingly separate kinetic models corresponding to the extreme modes of competitive and non-competitive adsorption, without having to draw the common distinction between two types of surface sites. General rate equations were formulated without expressing opinion a priori on whether the adsorption regime is competitive or non-competitive. Then, typical LHHW rate equations for both extreme adsorption regimes were straightforwardly derived as special cases. Statistical results demonstrated the inadequacy of the models approaching non-competitive adsorption to describe the experimental data but results did not allow a definite discrimination between rival models with competitive and semi-competitive adsorption. A mechanistic model featuring dissociative adsorption of hydrogen, molecule of methyl oleate interacting with a single atom of Ni, and second insertion of hydrogen as RDS, proved to be the best candidate to describe the experimental data satisfactorily with physically reasonable parameters. As a distinctive feature, the model considering semi-competitive adsorption gave additional indication that the adsorbed molecule of methyl oleate could cover up to seven surface sites. From this finding, the semi-competitive model seems to be more realistic than the competitive one. |
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Keywords: | Hydrogenation Methyl oleate Kinetic models Competitive adsorption Semi-competitive adsorption Non-competitive adsorption |
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