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Title: Modifiers in rhodium catalysts for carbon monoxide hydrogenation: Structure-activity relationships

Miscellaneous ·
OSTI ID:5813278

More efficient manufacture of oxygenates from syngas can fulfill a vital need for additives to transportation fuels. To achieve this, a much better understanding of the factors that control catalytic syngas reactions is needed, especially those that produce oxygenates rather than hydrocarbons. Some of the multi-functional systems used here are not only a better catalyst for oxygenates, but also provide an excellent system to investigate the effect of modifiers on the reaction pathways. Catalytic hydrogenation of carbon monoxide on supported rhodium catalysts gives rise to a variety of products such as hydrocarbons, alcohols, aldehydes, acids, esters and ethers. The effect of metal precursor, the support, and the nature and the amount of modifier on the rates and selectivity to these products is studied. Sodium and molybdenum modified Rh/Al{sub 2}O{sub 3} catalysts are investigated in detail. Also a new method of kinetic analysis, the delplot method, was developed and used. The delplot method sorts products according to their rank, finds the number and location of slow steps in a reaction network and separates regimes of conversion where product rank changes. Catalysts were also investigated using a battery of characterization techniques such as chemisorption, FTIR, XRD, XPS, TEM/EDX, TPD, ISS, ESR and solid-state NMR. Results from kinetics, characterization and test reaction studies are consistent with a dual-site mechanism where carbon monoxide is activated by Rh and hydrogen is activated by MoO{sub 3-x}. Increased activity and selectivity is attributed to a more effective hydrogenation capability provided by partially reduced molybdena. Addition of sodium to Rh/Al{sub 2}O{sub 3} decreases the rate of carbon monoxide hydrogenation substantially.

Research Organization:
Delaware Univ., Newark, DE (USA)
OSTI ID:
5813278
Resource Relation:
Other Information: Thesis (Ph. D.)
Country of Publication:
United States
Language:
English