Laboratory of Chemical Technnology

prof.dr.ir. G.B.M.M. Marin
prof.dr.ir. K. van der Wiele

Department of Chemical Process Engineering
Eindhoven University of Technology

Research program

The research activities are situated at the interface between catalysis and reactor engineering with the investigation of reaction kinetics as core competence. The performed kinetic studies are not limited to a quantitative description of the effects of the reaction conditions on rates and selectivities. On a fundamental level they are aimed at a better understanding of the reaction mechanisms, in particular of the catalytic cycles, involved. This is obtained by applying both ex- and in-situ catalyst characterization techniques. The results of the kinetic studies are also used for the scaling up of laboratory results to industrial operation by incorporating the rate equations in the appropriate mathematical models for chemical reactors. The latter are integrated into complete production units i.e. taking into account downstream separation, recirculation and energy management. Economic evaluations of the investigated processes are performed.

Transient kinetics, i.e. the study of the rate of reactions when the conditions are changing on the same time scale as that of the reaction itself, form one of the research topics. Such studies allow to obtain more detailed and more quantitative information on the elementary steps involved. Also, time averaged conversions and selectivities can be favourably influenced by purposely imposing such perturbations. The reactions important for automobile exhaust gas conversion are currently investigated along these lines.

Several reactions occurring at temperatures where radical chemistry in the gas phase becomes important such as the oxidative coupling of methane to ethene, the partial oxidation of methane to synthesis gas and the deposition of silicon from silane are investigated.

The latter reaction as well as the deposition of thin layers of molybdenumdisilicide are studied as examples of chemical vapour deposition, a production technique in fine ceramics and integrated circuits.

Finally, selective oxidations and reductions of polyfunctional molecules such as dialcohols and carbohydrates are investigated. These reactions are catalysed by noble metals and occur in water at mild temperatures. Optimization of the selectivity and life time of the catalysts is performed by the addition of promotors and is guided by in-situ characterization and comprehensive kinetic investiga-tions. Noble metal catalysts are currently also investigated for waste water purification.

The yearly budget of the group amounts to 1,5 MECU, one third of which is financed on contract basis.

Some recent publications

• The kinetics of the molybdate-catalysed epimerization of D-glucose and D-mannose in aqueous solutions,
  A. Cybulski, B.F.M. Kuster and G.B. Marin, Journal of Molecular Catalysis, 68, 87-103, 1991.

• Kinetics of the oxidative coupling of methane at atmospheric pressure in the absence of catalyst,
  Q. Chen, J.H.B.J. Hoebink and G.B. Marin, I&EC; Research, 30, 2088-2097, 1991.

• Characterization of Graphite-supported Platinum Catalysts by Electrochemical Methods and XPS.
  F.A. de Bruijn, G.B. Marin, J.W. Niemantsverdriet, W.H.M. Visscher, J.A.R. van Veen. Surface and Interface Analysis, 19, 537-542, 1992.

• Selective oxidation of methyl a-D-glucoside on carbon supported platinum.
  II. Assessment of the Arrhenius and Langmuir parameters.
  Applied Catalysis A: General 89 (1992) 31-46. Y. Schuurman, B.F.M. Kuster, K. van der Wiele and G.B. Marin.

• Selective oxidation of methyl a-D-glucoside on carbon supported platinum.
  III. Catalyst deactivation.
  Applied Catalysis A: General 89 (1992) 47-68. Y. Schuurman, B.F.M. Kuster, K. van der Wiele and G.B. Marin.

• Ethylene from natural gas: proven and new technologies.
  J.W.M.H. Geerts, J.H.B.J. Hoebink, K. van der Wiele. in: "Novel production methods for ethylene, light hydrocarbons and aromatics" (L.F. Albright, B.L. Crynes, S. Nowak, eds.), Marcel Dekker Inc., New York, 1992, 207-237.

• Pressure and temperature dependence of silicon doping of GaAs using Si2H6 in metalorganic chemical vapour deposition.
  P.R. Hageman, M.H.J.M. de Croon, J.N.H. Reek, L.J. Giling. Journal of Crystal Growth, 116, 169-177, 1992.

• The effects of oscillatory feeding of CO and O2 on the performance of a monolith catalytic converter of automobile exhaust gas.
  The Chemical Engineering Journal, 53 (1993) 47-54. A.B.K. Lie, J. Hoebink and G.B. Marin.

• Catalytic Reaction Engineering,
  Marin, G.B., Moulijn, J.A. and Kapteijn, F. in "Catalysis: an integrated approach to homogeneous, heterogeneous and industrial Catalysis", J.A. Moulijn, P.W.N.M. van Leeuwen, R. van Santen (Eds.), 1993, Elsevier Science Publishers, Amsterdam.

• Pressure and temperature dependence of Zn incorporation in metalorganic chemical vapour deposition grown GaAs and AlGaAs using diethylzinc as precursor.
  P.R. Hageman, M.H.J.M. de Croon, X. Tang, L.J. Giling. Journal of Crystal Growth, 129, 281-288, 1993.

• The effect of pressure on the oxidative coupling of methane in the absence of catalyst.
  Q. Chen, P.M. Couwenberg and G.B. Marin, in press AIChE Journal, 1994.