The structure and function of supported molybdenum nitride and molybdenum carbide hydrotreating catalysts.

A series of $\gamma$-Al$\rm\sb2O\sb3$ supported molybdenum nitrides and carbides were prepared by the temperature programmed reaction of supported molybdates with ammonia and methane/hydrogen mixtures, respectively. In the first part of this research, the effects of synthesis heating rates and molybdenum loading on the catalytic properties of the materials were examined. A significant amount of excess carbon was deposited on the surface of the carbides during synthesis. The materials consisted of small particles which were very highly dispersed. Oxygen chemisorption indicated that the nitride particles may have been two-dimensional. The dispersion of the carbides, however, appeared to decrease as the loading increased. The catalysts were evaluated for hydrodenitrogenation (HDN), hydrodesulfurization (HDS), and hydrodeoxygenation (HDO). The molybdenum loading had the largest effect on the activity of the materials. For the nitrides, the HDN and HDS activities were inverse functions of the loading. This suggested that the most active HDN and HDS sites were located at the perimeter of the two-dimensional particles. The HDN and HDS activities of the carbides followed the same trend as the oxygen uptake. This result suggested that oxygen titrated the active sites on the supported carbides. Selected catalysts were evaluated for methylcarbazole HDN, dibenzothiophene HDS, and dibenzofuran HDO. The activity and selectivity of the nitrides and carbides were competitive with a presulfided commercial catalyst. In the second part of this work, a series of supported nitrides and carbides were prepared using a wider range of loadings (5-30 wt% Mo). Thermogravimetric analysis was used to determine the temperature at which excess carbon was deposited on the carbides. By modifying the synthesis parameters, the deposition of excess carbon was effectively inhibited. The dispersions of the supported nitrides and carbides were constant and suggested that the materials consisted of two-dimensional raft-like particles. The HDN activity of the nitrides decreased as the loading increased, while that of the carbides was relatively constant. Carbon monoxide and methylamine adsorbed on the same types of sites on the nitrides and carbides. Infrared spectroscopy and temperature programmed desorption revealed that some methylamine underwent HDN on the nitrides and carbides. Carbon monoxide appeared to adsorb on two types of sites. One type of site adsorbed CO which desorbed upon heating while the other type of site adsorbed CO which dissociated when the material was heated. The relative amounts of desorbed CO and methylamine scaled with the activity of the nitrides suggesting that CO and methylamine titrated the active sites. It appeared that the active sites of the supported carbides were different from those on the supported nitrides. It was proposed that the active sites on the supported nitrides were at the perimeter of the two-dimensional particles while the active sites of the carbides were on top of the particles.Ph.D.Applied SciencesChemical engineeringMaterials scienceUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/130225/2/9721968.pd