Isopropanol Dehydrogenation over Cu/C and Pt/C Catalysts Albert Vannice, Robert Rioux Department of Chemical Engineering, Penn

State University, University Park, PA 16802 Introduction Although studied and utilized to a much lesser extent than hydrogenation reactions, dehydrogenation reactions involving organic compounds can also play an important role in the production of fine chemicals. Dehydrogenation reactions are typically endothermic and conversions can be equilibrium controlled; in addition, low H2 pressures may enhance deactivation due to coking, and a selectivity consideration of dehydrogenation versus dehydration as well as hydrogenolysis can become important when oxygenates are the reactants.The dehydrogenation of alcohols to aldehydes or ketones is a well-known industrial process, and these reactions are primarily carried out on copper catalysts because of their high selectivity to the dehydrogenation product. The principal catalyst that has been used in these reactions is copper chromite; however, new EPA restrictions now prohibit the disposal of chromite in landfills. Thus, there is an incentive to develop new replacement Cu catalysts which contain no chromium. Results and Discussion Isopropyl alcohol dehydrogenation over carbon-supported Cu catalysts was studied and compared to UHP Cu powder and a Cu chromite catalyst. Low dispersions of Cu (ca. 0.02-0.17) were obtained in all these catalysts. Cu dispersed on an activated carbon heat treated at 1223K had the highest turnover frequency (TOF = 0.052 s-1 at 448K) of all the Cu/C catalysts, and it was more than double that on an industrial Cu chromite catalyst. The rate with this 5.0% Cu/C catalyst (6.0 mole s-1 g-1) was close to that of the chromite catalyst containing 40% Cu (10.6 mole s-1 g-1). The steady-state selectivity to acetone was 100% for all catalysts except those containing the nitric acid-treated carbon. In the absence of Cu, the nitric acid-treated carbon produced propylene under steady-state reaction conditions, and reduction at 573K decreased activity compared to reduction at 423K. This dehydration reaction is associated with the presence of oxygen-containing acidic groups on the C surface. The apparent activation energy for acetone formation was typically near 20 kcal/mole for all the Cu/C catalysts and the Cu powder, but it was near 12 kcal/mole for the Cu chromite catalyst. A DRIFT spectrum under reaction conditions indicated the presence of an isopropoxide species and molecularly adsorbed IPA on the surface. A Langmuir-Hinshelwood model, which assumed removal of the first hydrogen atom as the rate determining step and incorporated adsorbed IPA, hydrogen, acetone and a surface isopropoxide species in the site balance, provided a rate expression that fit the kinetic data well and gave physically meaningful values for the enthalpies and entropies of adsorption. Pt dispersed on the same C supports

gave lower activation energies and TOFs that were 10-fold higher; however, the same reaction model fit these data for Pt.