Detailed Mechanism of Ethanol Transformation into Syngas on Catalysts Based on Mesoporous MgAl2O4 Support Loaded with Ru + Ni/(PrCeZrO or MnCr2O4) Active Components

Detailed Mechanism of Ethanol Transformation into Syngas on Catalysts Based on Mesoporous MgAl2O4 Support Loaded with Ru + Ni/(PrCeZrO or MnCr2O4) Active Components

Mechanism of ethanol partial oxidation into syngas over catalysts based on mesoporous MgAl 2 O 4 spinel loaded with fluorite PrCeZrO or spinel MnCr 2 O 4 oxides and promoted by Ru + Ni was studied by in situ FTIRS and 18 O SSITKA. Surface species (ethoxy, adsorbed ethanol, acetaldehyde, acetate, etc...

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Bibliographic Details
Published in:Topics in catalysis Vol. 63; no. 1-2; pp. 166 - 177
Main Authors: Sadykov, Vladislav A., Eremeev, Nikita F., Sadovskaya, Ekaterina M., Chesalov, Yurii A., Pavlova, Svetlana N., Rogov, Vladimir A., Simonov, Mikhail N., Bobin, Aleksei S., Glazneva, Tatiana S., Smal, Ekaterina A., Lukashevich, Anton.I., Krasnov, Aleksei V., Avdeev, Vasilii I., Roger, Anne-Cecile
Format: Journal Article
Language:English
Published: New York Springer US 2020
Springer Nature B.V
Subjects:
Acetaldehyde
Bonding strength
Carbon dioxide
Carbon monoxide
Catalysis
Catalysts
Characterization and Evaluation of Materials
Chemistry
Chemistry and Materials Science
Covalent bonds
Ethanol
Fluorite
Industrial Chemistry/Chemical Engineering
Metal oxides
Original Paper
Oxidation
Oxygen isotopes
Pharmacy
Physical Chemistry
Reaction kinetics
Reaction mechanisms
Reaction products
Rupture
Selectivity
Shift reaction
Spinel
Stability analysis
Strong interactions (field theory)
Synthesis gas
Thermal stability
Water gas
Ni + Ru
Ethanol
DFT analysis
PrCeZrO
Microcalorimetry
DRIFT in situ
Mechanism
Syngas
O
Selective oxidation
Complex oxides
MnCr
SSITKA
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Summary:Mechanism of ethanol partial oxidation into syngas over catalysts based on mesoporous MgAl 2 O 4 spinel loaded with fluorite PrCeZrO or spinel MnCr 2 O 4 oxides and promoted by Ru + Ni was studied by in situ FTIRS and 18 O SSITKA. Surface species (ethoxy, adsorbed ethanol, acetaldehyde, acetate, etc.) were identified and their thermal stability and reactivity were estimated. Analysis of kinetics of the 18 O transfer into reaction products (CO, CO 2 , CH 3 CHO) allowed to estimate the rates of steps and present a scheme of the reaction mechanism including (1) fast CH 3 CHO formation on mixed metal oxide sites; (2) rate-limiting stage of surface oxygen species incorporation into acetaldehyde or ethoxy species with C–C bond rupture yielding CO and CO 2 along with H 2 and H 2 O; (3) water gas shift reaction by redox mechanism affecting CO/CO 2 ratio and their oxygen isotope fraction. Strong interaction of PrCeZrO or MnCr 2 O 4 oxides with MgAl 2 O 4 support results in decreasing constants of main reaction steps in comparison with those for catalysts based on bulk fluorite and spinel oxides, correlating with a higher surface oxygen bonding strength and its low coverage revealed by pulse microcalorimetry. DFT analysis confirmed a low energy barrier of the step of Ru–O oxygen incorporation into C–C bond of ethoxy species with its rupture explaining a higher syngas selectivity for Ru-doped catalysts.
ISSN:1022-5528
1572-9028
DOI:10.1007/s11244-020-01222-1