Detailed Mechanism of Ethanol Transformation into Syngas on Catalysts Based on Mesoporous MgAl2O4 Support Loaded with Ru + Ni/(PrCeZrO or MnCr2O4) Active Components
Научная публикация
| Общее |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Конференция |
XI International Conference Mechanisms of Catalytic Reactions
07-11 окт. 2019
,
Сочи
|
| Журнал |
Topics in Catalysis
ISSN: 1022-5528
, E-ISSN: 1572-9028
|
| Вых. Данные |
Год: 2020,
Том: 63,
Номер: 1-2,
Страницы: 166-177
Страниц
: 12
DOI:
10.1007/s11244-020-01222-1
|
| Ключевые слова |
Complex oxides; DFT analysis; DRIFT in situ; Ethanol; Mechanism; Microcalorimetry; MnCr2O4; Ni + Ru; PrCeZrO; Selective oxidation; SSITKA; Syngas |
| Авторы |
Sadykov Vladislav A.
1,2
,
Eremeev Nikita F.
1
,
Sadovskaya Ekaterina M.
1,2
,
Chesalov Yurii A.
1
,
Pavlova Svetlana N.
1
,
Rogov Vladimir A.
1,2
,
Simonov Mikhail N.
1,2
,
Bobin Aleksei S.
1,2
,
Glazneva Tatiana S.
1,2
,
Smal Ekaterina A.
1
,
Lukashevich Anton.I.
1
,
Krasnov Aleksei V.
1
,
Avdeev Vasilii I.
1
,
Roger Anne-Cecile
3
|
| Организации |
| 1 |
Boreskov Institute of Catalysis
|
| 2 |
Novosibirsk State University
|
| 3 |
University of Strasbourg
|
|
Информация о финансировании (1)
|
1
|
Российский фонд фундаментальных исследований
|
18-58-16007
|
Mechanism of ethanol partial oxidation into syngas over catalysts based on mesoporous MgAl2O4 spinel loaded with fluorite PrCeZrO or spinel MnCr2O4 oxides and promoted by Ru + Ni was studied by in situ FTIRS and 18O SSITKA. Surface species (ethoxy, adsorbed ethanol, acetaldehyde, acetate, etc.) were identified and their thermal stability and reactivity were estimated. Analysis of kinetics of the 18O transfer into reaction products (CO, CO2, CH3CHO) allowed to estimate the rates of steps and present a scheme of the reaction mechanism including (1) fast CH3CHO 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 CO2 along with H2 and H2O; (3) water gas shift reaction by redox mechanism affecting CO/CO2 ratio and their oxygen isotope fraction. Strong interaction of PrCeZrO or MnCr2O4 oxides with MgAl2O4 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.