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Title: Kinetics of the higher alcohol synthesis over a K-promoted CuO/ZnO/Al[sub 2]O[sub 3]

Abstract

Detailed kinetic experiments of higher alcohol synthesis over K-promoted CuO/ZnO/Al[sub 2]O[sub 3] catalysts have been performed using an internal recycle reactor operated at 4 MPa and between 548 and 578 K. It was found that a 0.5% K-promoted catalyst, a stoichiometric H[sub 2]/CO ratio (approximately 2), and a low (2%) CO[sub 2] concentration were favorable for isobutanol yield. In contrast, for the synthesis of methanol, a higher K loading, H[sub 2]/CO ratio, and CO[sub 2] concentration were found to be favorable. The results suggest that isobutanol synthesis requires a balanced level of oxidation (Cu/Cu[sup 1+]), as conformed by in situ X-ray photoelectron spectroscopy, while methanol synthesis requires a greater degree of oxidation (more Cu[sup 1+]). Contact time experiments showed the selectivity of aldehydes to pass through a maximum, suggesting the intermediacy of aldehydes in a classic aldol'' condensation mechanism. In extended time-on-stream experiments, initial deactivation was accounted for by a loss in BET surface area and a loss in Cu/Zn ratio. Greater deactivation at higher temperatures resulted in lower final activities; nevertheless steady-state isobutanol yields increased significantly at higher temperatures.

Authors:
; ;  [1]
  1. Imperial Coll. of Science, Technology, and Medicine, London (United Kingdom). Dept. of Chemical Engineering and Chemical Technology
Publication Date:
OSTI Identifier:
6961107
Resource Type:
Journal Article
Journal Name:
Industrial and Engineering Chemistry Research; (United States)
Additional Journal Information:
Journal Volume: 33:9; Journal ID: ISSN 0888-5885
Country of Publication:
United States
Language:
English
Subject:
10 SYNTHETIC FUELS; 2-METHYLPROPANOL; SYNTHESIS; CARBON MONOXIDE; METHANATION; COPPER OXIDES; CATALYTIC EFFECTS; METHANOL; POTASSIUM; ZINC OXIDES; ALUMINIUM OXIDES; CATALYSTS; CHEMICAL REACTION KINETICS; CHEMICAL REACTION YIELD; DEACTIVATION; ALCOHOLS; ALKALI METALS; ALUMINIUM COMPOUNDS; CARBON COMPOUNDS; CARBON OXIDES; CHALCOGENIDES; CHEMICAL REACTIONS; COPPER COMPOUNDS; ELEMENTS; HYDROXY COMPOUNDS; KINETICS; METALS; ORGANIC COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; REACTION KINETICS; TRANSITION ELEMENT COMPOUNDS; YIELDS; ZINC COMPOUNDS; 100200* - Synthetic Fuels- Production- (1990-)

Citation Formats

Boz, I, Sahibzada, M, and Metcalfe, I S. Kinetics of the higher alcohol synthesis over a K-promoted CuO/ZnO/Al[sub 2]O[sub 3]. United States: N. p., 1994. Web. doi:10.1021/ie00033a001.
Boz, I, Sahibzada, M, & Metcalfe, I S. Kinetics of the higher alcohol synthesis over a K-promoted CuO/ZnO/Al[sub 2]O[sub 3]. United States. https://doi.org/10.1021/ie00033a001
Boz, I, Sahibzada, M, and Metcalfe, I S. 1994. "Kinetics of the higher alcohol synthesis over a K-promoted CuO/ZnO/Al[sub 2]O[sub 3]". United States. https://doi.org/10.1021/ie00033a001.
@article{osti_6961107,
title = {Kinetics of the higher alcohol synthesis over a K-promoted CuO/ZnO/Al[sub 2]O[sub 3]},
author = {Boz, I and Sahibzada, M and Metcalfe, I S},
abstractNote = {Detailed kinetic experiments of higher alcohol synthesis over K-promoted CuO/ZnO/Al[sub 2]O[sub 3] catalysts have been performed using an internal recycle reactor operated at 4 MPa and between 548 and 578 K. It was found that a 0.5% K-promoted catalyst, a stoichiometric H[sub 2]/CO ratio (approximately 2), and a low (2%) CO[sub 2] concentration were favorable for isobutanol yield. In contrast, for the synthesis of methanol, a higher K loading, H[sub 2]/CO ratio, and CO[sub 2] concentration were found to be favorable. The results suggest that isobutanol synthesis requires a balanced level of oxidation (Cu/Cu[sup 1+]), as conformed by in situ X-ray photoelectron spectroscopy, while methanol synthesis requires a greater degree of oxidation (more Cu[sup 1+]). Contact time experiments showed the selectivity of aldehydes to pass through a maximum, suggesting the intermediacy of aldehydes in a classic aldol'' condensation mechanism. In extended time-on-stream experiments, initial deactivation was accounted for by a loss in BET surface area and a loss in Cu/Zn ratio. Greater deactivation at higher temperatures resulted in lower final activities; nevertheless steady-state isobutanol yields increased significantly at higher temperatures.},
doi = {10.1021/ie00033a001},
url = {https://www.osti.gov/biblio/6961107}, journal = {Industrial and Engineering Chemistry Research; (United States)},
issn = {0888-5885},
number = ,
volume = 33:9,
place = {United States},
year = {1994},
month = {9}
}