Hydrogenation Kinetics of 2,2-Dimethylol-1-butanal to Trimethylolpropane over a Supported Nickel Catalyst

The hydrogenation kinetics of 2,2-dimethylol-1-butanal (TMP-aldol) over a supported nickel catalyst was determined with experiments carried out in a batchwise operating autoclave at 50−90 °C and 40−80 bar hydrogen. The reaction mixture was analyzed with gas and liquid chromatography. It was found that TMP-aldol can be hydrogenated with a 100% selectivity to the corresponding triol, trimethylolpropane. The effects of the catalyst activation procedure and the formaldehyde concentration on the hydrogenation kinetics were studied. The hydrogenation experiments revealed that catalyst reduction at a high temperature (400 °C) under hydrogen flow was favorable for the catalyst performance. The reason was a more effective reduction of nickel oxides which was confirmed with thermogravimetry and X-ray photoelectron spectroscopy. The presence of formaldehyde had a considerable retarding effect on the aldol hydrogenation kinetics: the hydrogenation rate was low until all of the formaldehyde was hydrogenated to methanol. The retarding effect was more prominent at higher temperatures than at lower temperatures, which indicates that formaldehyde forms oligomers on the catalyst surface as the temperature increases. A kinetic model was proposed for the aldol hydrogenation. The model includes adsorption, desorption, and surface reaction steps as well as the inhibitory effect of formaldehyde on the aldol hydrogenation kinetics. The model was able to describe the experimentally recorded hydrogenation kinetics of TMP-aldol in the presence and in the absence of formaldehyde.