The doctoral dissertations of the former Helsinki University of Technology (TKK) and Aalto University Schools of Technology (CHEM, ELEC, ENG, SCI) published in electronic format are available in the electronic publications archive of Aalto University - Aaltodoc.
Aalto

Kinetic Modeling of Liquid-Phase Hydrogenation Reactions

Mikko Lylykangas

Dissertation for the degree of Doctor of Science in Technology to be presented with due permission of the Department of Chemical Technology for public examination and debate in Auditorium KE 2 (Komppa Auditorium) at Helsinki University of Technology (Espoo, Finland) on the 13th of February, 2004, at 12 o'clock noon.

Overview in PDF format (ISBN 951-22-6913-9)   [459 KB]
Dissertation is also available in print (ISBN 951-22-6912-0)

Abstract

Kinetic models are an essential part of modern computer simulation based process design. The goal of the work presented here was to develop models for two types of industrially important hydrogenation reactions, namely the hydrogenation of mono- and diaromatic compounds and the hydrogenation of isooctenes. The studied reactions are important in the production of new, environmentally friendly fuels. Saturation of aromatics is needed to limit the undesired particle emissions in the exhaust gases of diesel engines, and isooctane could be used to replace methyl-tert-butyl ether (MTBE) in gasoline as an octane rating increasing component.

The hydrogenation of aromatics was studied on a commercial Ni/Al2O3 catalyst using three model compounds: toluene, 1,2,3,4-tetrahydronaphthalene (tetralin), and naphthalene. The results showed that the first ring of the diaromatic compound (naphthalene) is considerably more reactive than the second, whereas the hydrogenation rate of the monoaromatic compounds (toluene and tetralin) is only slightly affected by the structure of the substituent. In addition, an inhibition effect induced by competitive adsorption was observed in the hydrogenation of multicomponent mixtures. The most reactive compound adsorbs most strongly on the catalyst and inhibits the other reactions. Hydrogenation was assumed to proceed by a mechanism of stepwise addition of dissociatively adsorbed hydrogen. Langmuir–Hinshelwood type rate equations were able to describe the reaction kinetics successfully, including the inhibition effect. The estimated adsorption parameters in the mixtures increased with reactivity (Ktoluene = 1.0 × 10−3 m3/mol, Ktetralin = 4.4 × 10−3 m3/mol, Knaphthalene = 7.8 × 10−3 m3/mol). Additionally, the estimated activation energies were in the physically meaningful range of 26-59 kJ/mol.

The hydrogenation of the isooctenes 2,4,4-trimethyl-1-pentene (TMP-1) and 2,4,4-trimethyl-2-pentene (TMP-2) to "isooctane" (IO; 2,2,4-trimethylpentane) was examined on commercial Ni/Al2O3, Co/SiO2, and Pt/Al2O3 catalysts. Qualitatively, the hydrogenation proceeded in the same way on the different catalysts in that TMP-1 (terminal double bond) was more reactive than TMP-2 (internal double bond), isooctane was the sole product, and double bond isomerization did not play an important role under the conditions used. Kinetic models were formulated on the basis of the two-step Horiuti–Polanyi mechanism, assuming rate limitation by the first hydrogen insertion. The difference in the activities (Ni > Co > Pt) of the three catalysts was concluded to be due to the number of active sites because turnover frequencies (TOFs) were of the same order of magnitude. However, in some features, Pt was found to deviate from Ni and Co in the hydrogenation of TMP-1 and TMP-2. Activation energies were higher (Eapp,TMP-1 = 49 kJ/mol on Pt and 34-35 kJ/mol on Ni and Co; Eapp,TMP-2 = 65 kJ/mol on Pt and 43-49 kJ/mol on Ni and Co) and hydrogen adsorption equilibrium constants were larger by two orders of magnitude (KH = 38 × 10−4 m3/mol on Pt, 0.16 × 10−4 m3/mol on Ni, and 0.30 × 10−4 m3/mol on Co). In addition, catalyst deactivation through the formation of carbonaceous deposits was considerably faster on Pt.

The kinetic equations developed in this work are applicable as such in reactor design because mass transfer, hydrogen solubility, and solvent effect were taken into account in the parameter optimization. In the hydrogenation of aromatics, valuable information was obtained on how to describe hydrogenation reactions in multicomponent mixtures, such as real diesel fractions. The results from the hydrogenation of TMP-1 and TMP-2 provide information that can be applied to the selection of an optimal catalyst material as well as in the design and optimization of industrial-scale reactors.

This thesis consists of an overview and of the following 6 publications:

  1. Rautanen P. A., Lylykangas M. S., Aittamaa J. R. and Krause A. O. I., 2001. Liquid phase hydrogenation of naphthalene on Ni/Al2O3. Studies in Surface Science and Catalysis 133, pages 309-316.
  2. Lylykangas M. S., Rautanen P. A. and Krause A. O. I., 2002. Liquid-phase hydrogenation kinetics of multicomponent aromatic mixtures on Ni/Al2O3. Industrial & Engineering Chemistry Research 41, number 23, pages 5632-5639.
  3. Karinen R. S., Lylykangas M. S. and Krause A. O. I., 2001. Reaction equilibrium in the isomerization of 2,4,4-trimethyl pentenes. Industrial & Engineering Chemistry Research 40, number 4, pages 1011-1015.
  4. Lylykangas M. S., Rautanen P. A. and Krause A. O. I., 2003. Liquid-phase hydrogenation kinetics of isooctenes on Ni/Al2O3. AIChE Journal 49, number 6, pages 1508-1515.
  5. Lylykangas M. S., Rautanen P. A. and Krause A. O. I., 2004. Liquid-phase hydrogenation kinetics of isooctenes on Co/SiO2. Applied Catalysis A: General, in press.
  6. Lylykangas M. S., Rautanen P. A. and Krause A. O. I., 2004. Hydrogenation and deactivation kinetics in the liquid-phase hydrogenation of isooctenes on Pt/Al2O3. Industrial & Engineering Chemistry Research, accepted for publication.

Keywords: hydrogenation, liquid phase, aromatic compounds, alkenes, kinetic modeling, heterogeneous catalysts

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© 2004 Helsinki University of Technology

Last update 2011-05-26