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Calcium Phosphate Catalysts for Ethanol Coupling to Butanol and Butadiene

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Abstract

The catalytic conversion of ethanol to butanol and butadiene at 633 K and atmospheric pressure (7 vol% ethanol) was studied over calcium phosphate materials pretreated over a wide temperature range. For calcium phosphate pretreated at or below 923 K, the resulting solid had an apatite structure identified by X-ray diffraction and strong acid sites probed by triethylamine (TEA) adsorption microcalorimetry. The low temperature pretreated materials were not effective at ethanol coupling reactions but instead were highly selective to acid-catalyzed products ethene and diethyl ether. Pretreatment of calcium phosphate at 973 K transformed the apatite structure to β-tricalcium phosphate, which exposed both acid and base sites evaluated by TEA and CO2 adsorption microcalorimetry. High temperature pretreated calcium phosphate catalysts formed the coupling products butanol and butadiene during ethanol reaction. The butadiene selectivity was improved by supporting calcium phosphate on zirconia.

Graphic abstract

The influence of catalyst structure on the activity and selectivity of calcium phosphates was elucidated for the conversion of ethanol.

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Acknowledgements

This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Catalysis Science Program, under Award # DE-FG02-95ER14549.

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  1. Department of Chemical Engineering, University of Virginia, 102 Engineer’s Way, Charlottesville, VA, 22904-4741, USA

    J. Tyler Prillaman, Naomi Miyake & Robert J. Davis

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  1. J. Tyler Prillaman
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  2. Naomi Miyake
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  3. Robert J. Davis
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Correspondence to Robert J. Davis.

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Prillaman, J.T., Miyake, N. & Davis, R.J. Calcium Phosphate Catalysts for Ethanol Coupling to Butanol and Butadiene. Catal Lett 151, 648–657 (2021). https://doi.org/10.1007/s10562-020-03342-5

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  • DOI: https://doi.org/10.1007/s10562-020-03342-5

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