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Multiproduct Steady-State Isotopic Transient Kinetic Analysis of the Ethanol Coupling Reaction over Hydroxyapatite and Magnesia
journal contribution
posted on 2015-03-06, 00:00 authored by Sabra Hanspal, Zachary D. Young, Heng Shou, Robert J. DavisThe
Guerbet coupling of ethanol into butanol was investigated using
multiproduct steady-state isotopic transient kinetic analysis (SSITKA)
in a comparative study between stoichiometric hydroxyapatite (HAP)
and magnesia (MgO) catalysts at 613 and 653 K, respectively. The steady-state
catalytic reactions were conducted in a gas-phase, fixed-bed, differential
reactor at 1.3 atm total system pressure. Multiproduct SSITKA results
showed that the mean surface residence time of reactive intermediates
leading to acetaldehyde was significantly shorter than that of intermediates
leading to butanol on both HAP and MgO. This finding may suggest that
the dehydrogenation of ethanol to acetaldehyde is fast on these surfaces
compared with C–C bond formation. If adsorbed acetaldehyde
is a key reaction intermediate in the Guerbet coupling of ethanol
into butanol, then SSITKA revealed that the majority of adsorbed acetaldehyde
produced on the surface of MgO desorbs into the gas-phase, whereas
the majority of adsorbed acetaldehyde on HAP likely undergoes sequential
aldol-type reactions required for butanol formation. Adsorption microcalorimetry
of triethylamine and CO2 showed a significantly higher
number of acid and base sites on the surface of HAP compared with
those on MgO. Diffuse reflectance infrared Fourier transform spectroscopy
of adsorbed ethanol followed by stepwise temperature-programmed desorption
revealed that ethoxide is more weakly bound to the HAP surface compared
with MgO. A high surface density of acid–base site pairs along
with a weak binding affinity for ethanol on HAP may provide a possible
explanation for the increased activity and high butanol selectivity
observed with HAP compared with MgO catalysts in the ethanol coupling
reaction.
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Multiproduct SSITKA resultssystem pressuresurface residence timesurface densityreactive intermediatesstoichiometric hydroxyapatiteethanolCO 2HAP surfaceMgO desorbsAdsorption microcalorimetryMagnesiaThe Guerbetbinding affinity1.3 atmDiffuse reflectanceMgO catalystsbutanol formation653 Kacetaldehydebutanol selectivitybase sites
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