Journal of Chemical Technology and Biotechnology, Vol.77, No.5, 533-538, 2002
Parallel hydrogenation of 2,2-dimethylol-1-butanal and formaldehyde over supported NiCr and CuCr catalysts
The hydrogenation kinetics of 2,2-dimethylol-l-butanal (TMP-aldol) and formaldehyde were studied over two commercial supported catalysts; NiCr on silica and CuCr on alumina. Both catalysts hydrogenated the aldol selectively to triol, but the kinetic trends differed widely. With the nickel catalyst, the aldol hydrogenation was not started before almost all of the formaldehyde was consumed from the bulk phase, whereas the copper-containing catalyst hydrogenated aldol and formaldehyde in parallel. Rate equations for the hydrogenation of aldol and formaldehyde were derived from a competitive surface mechanism. Since formaldehyde retarded significantly the hydrogenation rate of aldol over NiCr, the kinetic model was modified in order to take into account the inhibitory effect of formaldehyde. With the modified model, the experimental data produced over the NiCr catalyst were rather well described. The data from the experiments over the CuCr catalyst followed pseudo-first order kinetics remarkably well. Furthermore, the kinetic model without the inhibitory effect of formaldehyde was able to describe the governing trends of the data obtained over the CuCr catalyst.