Heterogenization of Heteropolyacid with Metal-Based Alumina Supports for the Guaiacol Gas-Phase Hydrodeoxygenation
Because of the global necessity to decrease CO<sub>2</sub> emissions, biomass-based fuels have become an interesting option to explore; although, bio-oils need to be upgraded, for example, by catalytic hydrodeoxygenation (HDO), to reduce oxygen content. This reaction generally requires b...
| Main Authors: | , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2023-02-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/28/5/2245 |
| _version_ | 1827752486682755072 |
|---|---|
| author | Rita F. Nunes Daniel Costa Ana M. Ferraria Ana M. Botelho do Rego Filipa Ribeiro Ângela Martins Auguste Fernandes |
| author_facet | Rita F. Nunes Daniel Costa Ana M. Ferraria Ana M. Botelho do Rego Filipa Ribeiro Ângela Martins Auguste Fernandes |
| author_sort | Rita F. Nunes |
| collection | DOAJ |
| description | Because of the global necessity to decrease CO<sub>2</sub> emissions, biomass-based fuels have become an interesting option to explore; although, bio-oils need to be upgraded, for example, by catalytic hydrodeoxygenation (HDO), to reduce oxygen content. This reaction generally requires bifunctional catalysts with both metal and acid sites. For that purpose, Pt-Al<sub>2</sub>O<sub>3</sub> and Ni-Al<sub>2</sub>O<sub>3</sub> catalysts containing heteropolyacids (HPA) were prepared. HPAs were added by two different methods: the impregnation of a H<sub>3</sub>PW<sub>12</sub>O<sub>40</sub> solution onto the support and a physical mixture of the support with Cs<sub>2.5</sub>H<sub>0.5</sub>PW<sub>12</sub>O<sub>40</sub>. The catalysts were characterized by powder X-ray diffraction, Infrared, UV-Vis, Raman, X-ray photoelectron spectroscopy and NH<sub>3</sub>-TPD experiments. The presence of H<sub>3</sub>PW<sub>12</sub>O<sub>40</sub> was confirmed by Raman, UV-Vis and X-ray photoelectron spectroscopy, while the presence of Cs<sub>2.5</sub>H<sub>0.5</sub>PW<sub>12</sub>O<sub>40</sub> was confirmed by all of the techniques. However, HPW was shown to strongly interact with the supports, especially in the case of Pt-Al<sub>2</sub>O<sub>3</sub>. These catalysts were tested in the HDO of guaiacol, at 300 °C, under H<sub>2</sub> and at atmospheric pressure. Ni-based catalysts led to higher conversion and selectivity to deoxygenated compound values, such as benzene. This is attributed to both a higher metal and acidic contents of these catalysts. Among all tested catalysts, HPW/Ni-Al<sub>2</sub>O<sub>3</sub> was shown to be the most promising, although it suffered a more severe deactivation with time-on-stream. |
| first_indexed | 2024-03-11T07:17:06Z |
| format | Article |
| id | doaj.art-e2b2549d4df141d5ab9c3ec29fe1f550 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T07:17:06Z |
| publishDate | 2023-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-e2b2549d4df141d5ab9c3ec29fe1f5502023-11-17T08:13:59ZengMDPI AGMolecules1420-30492023-02-01285224510.3390/molecules28052245Heterogenization of Heteropolyacid with Metal-Based Alumina Supports for the Guaiacol Gas-Phase HydrodeoxygenationRita F. Nunes0Daniel Costa1Ana M. Ferraria2Ana M. Botelho do Rego3Filipa Ribeiro4Ângela Martins5Auguste Fernandes6Centro de Química Estrutural, Institute of Molecular Sciences, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, PortugalCentro de Química Estrutural, Institute of Molecular Sciences, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, PortugalBSIRG-iBB-Institute for Bioengineering and Biosciences, Chemical Engineering Department, Universidade de Lisboa, 1049-001 Lisbon, PortugalBSIRG-iBB-Institute for Bioengineering and Biosciences, Chemical Engineering Department, Universidade de Lisboa, 1049-001 Lisbon, PortugalCentro de Química Estrutural, Institute of Molecular Sciences, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, PortugalDEQ, Instituto Superior de Engenharia de Lisboa, Instituto Politécnico de Lisboa, Rua Conselheiro Emídio Navarro, 1959-007 Lisboa, PortugalCentro de Química Estrutural, Institute of Molecular Sciences, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, PortugalBecause of the global necessity to decrease CO<sub>2</sub> emissions, biomass-based fuels have become an interesting option to explore; although, bio-oils need to be upgraded, for example, by catalytic hydrodeoxygenation (HDO), to reduce oxygen content. This reaction generally requires bifunctional catalysts with both metal and acid sites. For that purpose, Pt-Al<sub>2</sub>O<sub>3</sub> and Ni-Al<sub>2</sub>O<sub>3</sub> catalysts containing heteropolyacids (HPA) were prepared. HPAs were added by two different methods: the impregnation of a H<sub>3</sub>PW<sub>12</sub>O<sub>40</sub> solution onto the support and a physical mixture of the support with Cs<sub>2.5</sub>H<sub>0.5</sub>PW<sub>12</sub>O<sub>40</sub>. The catalysts were characterized by powder X-ray diffraction, Infrared, UV-Vis, Raman, X-ray photoelectron spectroscopy and NH<sub>3</sub>-TPD experiments. The presence of H<sub>3</sub>PW<sub>12</sub>O<sub>40</sub> was confirmed by Raman, UV-Vis and X-ray photoelectron spectroscopy, while the presence of Cs<sub>2.5</sub>H<sub>0.5</sub>PW<sub>12</sub>O<sub>40</sub> was confirmed by all of the techniques. However, HPW was shown to strongly interact with the supports, especially in the case of Pt-Al<sub>2</sub>O<sub>3</sub>. These catalysts were tested in the HDO of guaiacol, at 300 °C, under H<sub>2</sub> and at atmospheric pressure. Ni-based catalysts led to higher conversion and selectivity to deoxygenated compound values, such as benzene. This is attributed to both a higher metal and acidic contents of these catalysts. Among all tested catalysts, HPW/Ni-Al<sub>2</sub>O<sub>3</sub> was shown to be the most promising, although it suffered a more severe deactivation with time-on-stream.https://www.mdpi.com/1420-3049/28/5/2245biomass valorizationhydrodeoxygenationheteropolyacidheteropolyacid saltbifunctional catalystsguaiacol |
| spellingShingle | Rita F. Nunes Daniel Costa Ana M. Ferraria Ana M. Botelho do Rego Filipa Ribeiro Ângela Martins Auguste Fernandes Heterogenization of Heteropolyacid with Metal-Based Alumina Supports for the Guaiacol Gas-Phase Hydrodeoxygenation Molecules biomass valorization hydrodeoxygenation heteropolyacid heteropolyacid salt bifunctional catalysts guaiacol |
| title | Heterogenization of Heteropolyacid with Metal-Based Alumina Supports for the Guaiacol Gas-Phase Hydrodeoxygenation |
| title_full | Heterogenization of Heteropolyacid with Metal-Based Alumina Supports for the Guaiacol Gas-Phase Hydrodeoxygenation |
| title_fullStr | Heterogenization of Heteropolyacid with Metal-Based Alumina Supports for the Guaiacol Gas-Phase Hydrodeoxygenation |
| title_full_unstemmed | Heterogenization of Heteropolyacid with Metal-Based Alumina Supports for the Guaiacol Gas-Phase Hydrodeoxygenation |
| title_short | Heterogenization of Heteropolyacid with Metal-Based Alumina Supports for the Guaiacol Gas-Phase Hydrodeoxygenation |
| title_sort | heterogenization of heteropolyacid with metal based alumina supports for the guaiacol gas phase hydrodeoxygenation |
| topic | biomass valorization hydrodeoxygenation heteropolyacid heteropolyacid salt bifunctional catalysts guaiacol |
| url | https://www.mdpi.com/1420-3049/28/5/2245 |
| work_keys_str_mv | AT ritafnunes heterogenizationofheteropolyacidwithmetalbasedaluminasupportsfortheguaiacolgasphasehydrodeoxygenation AT danielcosta heterogenizationofheteropolyacidwithmetalbasedaluminasupportsfortheguaiacolgasphasehydrodeoxygenation AT anamferraria heterogenizationofheteropolyacidwithmetalbasedaluminasupportsfortheguaiacolgasphasehydrodeoxygenation AT anambotelhodorego heterogenizationofheteropolyacidwithmetalbasedaluminasupportsfortheguaiacolgasphasehydrodeoxygenation AT filiparibeiro heterogenizationofheteropolyacidwithmetalbasedaluminasupportsfortheguaiacolgasphasehydrodeoxygenation AT angelamartins heterogenizationofheteropolyacidwithmetalbasedaluminasupportsfortheguaiacolgasphasehydrodeoxygenation AT augustefernandes heterogenizationofheteropolyacidwithmetalbasedaluminasupportsfortheguaiacolgasphasehydrodeoxygenation |