Effect of cesium on alcohol synthesis, water-gas shift reaction, and ester hydrogenolysis over copper-zinc oxide catalysts

Thesis/Dissertation · Thu Jan 01 00:00:00 EST 1987

OSTI ID:5659636

Young, C W

This study comprises three subjects: (1) the effects of cesium doping and water concentration in the synthesis gas on methanol synthesis rate and the water-gas shift (WGS) reaction; (2) the hydrogenolysis of alkyl esters; and (3) the effect of cesium on higher alcohol synthesis, as well as the investigation of the chain growth reaction in higher alcohol synthesis over the Cu/ZnO catalysts. A two-parameter kinetic model quantitatively demonstrated that the maximum rate of methanol synthesis is determined by the balance between the promotional effect of cesium and the retarding effect stemming from the blockage of hydrogen activing sites. Another six-parameter kinetic model, in which the methanol and WGS reactions were considered simultaneously, can account for methanol activity in the water dependence study. At higher water concentrations, the cesium-doped catalysts were more active than the undoped catalyst for methanol synthesis, which was quantitatively shown to be due to the promotion of the WGS reaction by the cesium doping. The inhibition effect that occurred at high water concentrations in methyl acetate hydrogenolysis is due to the blockage of hydrogen activating sites. In addition, the kinetics of hydrogenolysis of n-propyl acetate resulted in a -0.49 order with respect to n-propyl acetate and a +1.83 order to hydrogen, which are in fair agreement with those derived in terms of Langmuir-Hinshelwood type kinetics. The aldehydic species involved in the hydrogenolysis of esters was evidence by a isopropylamine trapping experiment.

• Research Organization: Lehigh Univ., Bethlehem, PA (USA)
• OSTI ID: 5659636
• Resource Relation: Other Information: Thesis (Ph. D.)
• Country of Publication: United States
• Language: English

Related Subjects

10 SYNTHETIC FUELS
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALCOHOLS
SYNTHESIS
COPPER
CATALYTIC EFFECTS
ESTERS
HYDROGENATION
WATER GAS
CHEMICAL SHIFT
ZINC OXIDES
CATALYSIS
MATHEMATICAL MODELS
CHALCOGENIDES
CHEMICAL REACTIONS
ELEMENTS
FLUIDS
FUEL GAS
FUELS
GAS FUELS
GASES
HYDROXY COMPOUNDS
INTERMEDIATE BTU GAS
METALS
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
TRANSITION ELEMENTS
ZINC COMPOUNDS
090221* - Alcohol Fuels- Chemical Synthesis- (1976-1989)
090121 - Hydrocarbon Fuels- Chemical Synthesis- (1976-1989)
400201 - Chemical & Physicochemical Properties