Valorization of (Bio)Ethanol over MoO<sub>3</sub>/(WO<sub>3</sub>-ZrO<sub>2</sub>) Sol-Gel-like Catalysts
Bioethanol, which is currently produced commercially from a growing variety of renewable biomass and waste sources, is an appealing feedstock for the production of fuels and chemicals. The literature clearly shows that bioethanol is a versatile building block to be used in biorefineries. The ethanol...
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2024-03-01
|
| Series: | Reactions |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2624-781X/5/1/12 |
| _version_ | 1797239503837986816 |
|---|---|
| author | Ana Paula Soares Dias Bruna Rijo Manuel Francisco Costa Pereira Rodica Zăvoianu Octavian Dumitru Pavel |
| author_facet | Ana Paula Soares Dias Bruna Rijo Manuel Francisco Costa Pereira Rodica Zăvoianu Octavian Dumitru Pavel |
| author_sort | Ana Paula Soares Dias |
| collection | DOAJ |
| description | Bioethanol, which is currently produced commercially from a growing variety of renewable biomass and waste sources, is an appealing feedstock for the production of fuels and chemicals. The literature clearly shows that bioethanol is a versatile building block to be used in biorefineries. The ethanol conversion using several catalysts with acidic, basic, and redox characteristics results in a diverse assortment of high-value bioproducts. High-acidity tungsten zirconia-based catalysts are stated to compete with traditional zeolitic catalysts and can be employed in the dehydration of ethanol to ethylene, but for a low reaction temperature acetic acid is formed, which causes corrosion issues. WO<sub>3</sub>-ZrO<sub>2</sub> (W/Zr = 1, atomic) catalysts modified with MoO<sub>3</sub> were prepared by a sol-gel-like procedure and tested in a gas phase ethanol conversion in the presence of air. The citrate derived xerogels were annealed at 853 K for 12 h, allowing low surface area (<10 m<sup>2</sup>/g) materials with a Mo-W mixed-oxide-rich surface over tetragonal nanostructured zirconia. Catalysts with MoO3-loading produced mainly acetaldehyde, instead of ethylene, as a result of the high reducibility of Mo<sup>6+</sup> when compared to W<sup>6+</sup>. During the reaction, the Mo<sup>6+</sup> becomes partially reduced, but Mo<sup>6+</sup>/Mo<sup>5+</sup> species are still active for methanol conversion with increased ethylene selectivity due to the high acidity of tetrahedral MO<sub>X</sub> species formed during the reaction. Adding water to ethanol, to simulate bioethanol, only leads to a slight inhibition in ethanol conversion over the MoO<sub>3</sub>/(WO<sub>3</sub>-ZrO<sub>2</sub>) catalysts. The results show that molybdenum oxide deposited on tungstated zirconia catalyst is active, with low sensitivity to water, for the valorization of bioethanol into high-value chemicals, such as ethylene and acetaldehyde, and whose selectivity can be tuned by changing the amount of MoO<sub>3</sub> that is loaded. The MoO<sub>3</sub>/(WO<sub>3</sub>-ZrO<sub>2</sub>) catalysts prepared show catalytic behavior similar to that of noble metal-based catalysts reported in the literature for the dehydrogenation of bioethanol in high-value chemicals. |
| first_indexed | 2024-04-24T17:52:35Z |
| format | Article |
| id | doaj.art-36d50580ceff4b30a08d12b9e8ab06a9 |
| institution | Directory Open Access Journal |
| issn | 2624-781X |
| language | English |
| last_indexed | 2024-04-24T17:52:35Z |
| publishDate | 2024-03-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Reactions |
| spelling | doaj.art-36d50580ceff4b30a08d12b9e8ab06a92024-03-27T14:02:02ZengMDPI AGReactions2624-781X2024-03-015126027310.3390/reactions5010012Valorization of (Bio)Ethanol over MoO<sub>3</sub>/(WO<sub>3</sub>-ZrO<sub>2</sub>) Sol-Gel-like CatalystsAna Paula Soares Dias0Bruna Rijo1Manuel Francisco Costa Pereira2Rodica Zăvoianu3Octavian Dumitru Pavel4Centro de Recursos Naturais e Ambiente (CERENA), Institutto Superior Técnico, University of Lisbon, Av. Rovisco Pais, 1, 1049-001 Lisboa, PortugalCentro de Investigação para a Valorização de Recursos Endógenos (VALORIZA), Polytechnic Institute of Portalegre, Campus Politécnico, 10, 7300-555 Portalegre, PortugalCentro de Recursos Naturais e Ambiente (CERENA), Institutto Superior Técnico, University of Lisbon, Av. Rovisco Pais, 1, 1049-001 Lisboa, PortugalDepartment of Inorganic Chemistry, Organic Chemistry, Biochemistry and Catalysis, Faculty of Chemistry, University of Bucharest, 4-12 Regina Elisabeta Bd., 030018 Bucharest, RomaniaDepartment of Inorganic Chemistry, Organic Chemistry, Biochemistry and Catalysis, Faculty of Chemistry, University of Bucharest, 4-12 Regina Elisabeta Bd., 030018 Bucharest, RomaniaBioethanol, which is currently produced commercially from a growing variety of renewable biomass and waste sources, is an appealing feedstock for the production of fuels and chemicals. The literature clearly shows that bioethanol is a versatile building block to be used in biorefineries. The ethanol conversion using several catalysts with acidic, basic, and redox characteristics results in a diverse assortment of high-value bioproducts. High-acidity tungsten zirconia-based catalysts are stated to compete with traditional zeolitic catalysts and can be employed in the dehydration of ethanol to ethylene, but for a low reaction temperature acetic acid is formed, which causes corrosion issues. WO<sub>3</sub>-ZrO<sub>2</sub> (W/Zr = 1, atomic) catalysts modified with MoO<sub>3</sub> were prepared by a sol-gel-like procedure and tested in a gas phase ethanol conversion in the presence of air. The citrate derived xerogels were annealed at 853 K for 12 h, allowing low surface area (<10 m<sup>2</sup>/g) materials with a Mo-W mixed-oxide-rich surface over tetragonal nanostructured zirconia. Catalysts with MoO3-loading produced mainly acetaldehyde, instead of ethylene, as a result of the high reducibility of Mo<sup>6+</sup> when compared to W<sup>6+</sup>. During the reaction, the Mo<sup>6+</sup> becomes partially reduced, but Mo<sup>6+</sup>/Mo<sup>5+</sup> species are still active for methanol conversion with increased ethylene selectivity due to the high acidity of tetrahedral MO<sub>X</sub> species formed during the reaction. Adding water to ethanol, to simulate bioethanol, only leads to a slight inhibition in ethanol conversion over the MoO<sub>3</sub>/(WO<sub>3</sub>-ZrO<sub>2</sub>) catalysts. The results show that molybdenum oxide deposited on tungstated zirconia catalyst is active, with low sensitivity to water, for the valorization of bioethanol into high-value chemicals, such as ethylene and acetaldehyde, and whose selectivity can be tuned by changing the amount of MoO<sub>3</sub> that is loaded. The MoO<sub>3</sub>/(WO<sub>3</sub>-ZrO<sub>2</sub>) catalysts prepared show catalytic behavior similar to that of noble metal-based catalysts reported in the literature for the dehydrogenation of bioethanol in high-value chemicals.https://www.mdpi.com/2624-781X/5/1/12bioethanol valorizationethyleneacetaldehydesol-gel catalystsWO<sub>3</sub>-ZrO<sub>2</sub>dehydrogenation |
| spellingShingle | Ana Paula Soares Dias Bruna Rijo Manuel Francisco Costa Pereira Rodica Zăvoianu Octavian Dumitru Pavel Valorization of (Bio)Ethanol over MoO<sub>3</sub>/(WO<sub>3</sub>-ZrO<sub>2</sub>) Sol-Gel-like Catalysts Reactions bioethanol valorization ethylene acetaldehyde sol-gel catalysts WO<sub>3</sub>-ZrO<sub>2</sub> dehydrogenation |
| title | Valorization of (Bio)Ethanol over MoO<sub>3</sub>/(WO<sub>3</sub>-ZrO<sub>2</sub>) Sol-Gel-like Catalysts |
| title_full | Valorization of (Bio)Ethanol over MoO<sub>3</sub>/(WO<sub>3</sub>-ZrO<sub>2</sub>) Sol-Gel-like Catalysts |
| title_fullStr | Valorization of (Bio)Ethanol over MoO<sub>3</sub>/(WO<sub>3</sub>-ZrO<sub>2</sub>) Sol-Gel-like Catalysts |
| title_full_unstemmed | Valorization of (Bio)Ethanol over MoO<sub>3</sub>/(WO<sub>3</sub>-ZrO<sub>2</sub>) Sol-Gel-like Catalysts |
| title_short | Valorization of (Bio)Ethanol over MoO<sub>3</sub>/(WO<sub>3</sub>-ZrO<sub>2</sub>) Sol-Gel-like Catalysts |
| title_sort | valorization of bio ethanol over moo sub 3 sub wo sub 3 sub zro sub 2 sub sol gel like catalysts |
| topic | bioethanol valorization ethylene acetaldehyde sol-gel catalysts WO<sub>3</sub>-ZrO<sub>2</sub> dehydrogenation |
| url | https://www.mdpi.com/2624-781X/5/1/12 |
| work_keys_str_mv | AT anapaulasoaresdias valorizationofbioethanolovermoosub3subwosub3subzrosub2subsolgellikecatalysts AT brunarijo valorizationofbioethanolovermoosub3subwosub3subzrosub2subsolgellikecatalysts AT manuelfranciscocostapereira valorizationofbioethanolovermoosub3subwosub3subzrosub2subsolgellikecatalysts AT rodicazavoianu valorizationofbioethanolovermoosub3subwosub3subzrosub2subsolgellikecatalysts AT octaviandumitrupavel valorizationofbioethanolovermoosub3subwosub3subzrosub2subsolgellikecatalysts |