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Interaction of water-gas shift species with chromia-promoted magnetite

Thesis/Dissertation ·
OSTI ID:7180586

The interactions of H/sub 2/, H/sub 2/O, CO, and CO/sub 2/ were studied with respect to the mechanism of water-gas shift over chromia-promoted magnetite. Areas of study were pair-sites as adsorption sites. H/sub 2//H>O coadsorption and oxygen transfer between CO and CO/sub 2/. Adsorption on pair-sites consisting of adjacent, dissimilar atoms does not follow the Langmuir isotherm. Monte Carlo simulations and simple statistical arguments were used to study the number of available sites as a function of coverage. The deviations from the Langmuir isotherm cannot be observed unless surface coverages are measured with an uncertainty less than about 8% of the saturation coverage. The adsorption of H/sub 2//H/sub 2/O mixtures on chromia-promoted magnetite at 637 K was investigated. Data were collected volumetrically at constant H/sub 2/:H/sub 2/O ratios and fit to Langmuir-type adsorption isotherms. For a given H/sub 2/ partial pressure, a lower extent of H/sub 2/ adsorption was observed at a higher H/sub 2/O partial pressure, indicating that competition for adsorption sites occurred. At a constant H/sub 2/:H/sub 2/O ratio, the H/sub 2/ coverage as a function of H/sub 2/ partial pressure passed through a maximum, indicating that H/sub 2/ is dissociatively adsorbed. Equilibrium rates of adsorption/desorption and interconversion of CO and CO/sub 2/ were studied using isotopically labelled species. The interconversion of CO and CO/sub 2/ over chromia-promoted magnetite at 627 K occurs through an adsorbed intermediate. A kinetic model using rate constants calculated from the isotopic exchange data was found to be in good agreement with the water-gas shift rate.

Research Organization:
Wisconsin Univ., Madison (USA)
OSTI ID:
7180586
Country of Publication:
United States
Language:
English