Ni Supported on Natural Clays as a Catalyst for the Transformation of Levulinic Acid into γ-Valerolactone without the Addition of Molecular Hydrogen
γ-Valerolactone (GVL) is a valuable chemical that can be used as a clean additive for automotive fuels. This compound can be produced from biomass-derived compounds. Levulinic acid (LA) is a compound that can be obtained easily from biomass and it can be transformed into GVL by dehydration and hydro...
| Main Authors: | , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2020-07-01
|
| Series: | Energies |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1996-1073/13/13/3448 |
| _version_ | 1797563372016762880 |
|---|---|
| author | Adrián García Rut Sanchis Francisco J. Llopis Isabel Vázquez María Pilar Pico María Luisa López Inmaculada Álvarez-Serrano Benjamín Solsona |
| author_facet | Adrián García Rut Sanchis Francisco J. Llopis Isabel Vázquez María Pilar Pico María Luisa López Inmaculada Álvarez-Serrano Benjamín Solsona |
| author_sort | Adrián García |
| collection | DOAJ |
| description | γ-Valerolactone (GVL) is a valuable chemical that can be used as a clean additive for automotive fuels. This compound can be produced from biomass-derived compounds. Levulinic acid (LA) is a compound that can be obtained easily from biomass and it can be transformed into GVL by dehydration and hydrogenation using metallic catalysts. In this work, catalysts of Ni (a non-noble metal) supported on a series of natural and low-cost clay-materials have been tested in the transformation of LA into GVL. Catalysts were prepared by a modified wet impregnation method using oxalic acid trying to facilitate a suitable metal dispersion. The supports employed are attapulgite and two sepiolites with different surface areas. Reaction tests have been undertaken using an aqueous medium at moderate reaction temperatures of 120 and 180 °C. Three types of experiments were undertaken: (i) without H<sub>2</sub> source, (ii) using formic acid (FA) as hydrogen source and (iii) using Zn in order to transform water in hydrogen through the reaction Zn + H<sub>2</sub>O → ZnO + H<sub>2</sub>. The best results have been obtained combining Zn (which plays a double role as a reactant for hydrogen formation and as a catalyst) and Ni/attapulgite. Yields to GVL higher than 98% have been obtained at 180 °C in the best cases. The best catalytic performance has been related to the presence of tiny Ni particles as nickel crystallites larger than 4 nm were not present in the most efficient catalysts. |
| first_indexed | 2024-03-10T18:41:43Z |
| format | Article |
| id | doaj.art-9d3be6fa4adf4e31a20e53e4b2a03ce9 |
| institution | Directory Open Access Journal |
| issn | 1996-1073 |
| language | English |
| last_indexed | 2024-03-10T18:41:43Z |
| publishDate | 2020-07-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Energies |
| spelling | doaj.art-9d3be6fa4adf4e31a20e53e4b2a03ce92023-11-20T05:47:10ZengMDPI AGEnergies1996-10732020-07-011313344810.3390/en13133448Ni Supported on Natural Clays as a Catalyst for the Transformation of Levulinic Acid into γ-Valerolactone without the Addition of Molecular HydrogenAdrián García0Rut Sanchis1Francisco J. Llopis2Isabel Vázquez3María Pilar Pico4María Luisa López5Inmaculada Álvarez-Serrano6Benjamín Solsona7Departament d’Enginyeria Química, ETSE, Universitat de València, Av. Universitat, Burjassot, 46100 Valencia, SpainDepartament d’Enginyeria Química, ETSE, Universitat de València, Av. Universitat, Burjassot, 46100 Valencia, SpainDepartament d’Enginyeria Química, ETSE, Universitat de València, Av. Universitat, Burjassot, 46100 Valencia, SpainDepartament d’Enginyeria Química, ETSE, Universitat de València, Av. Universitat, Burjassot, 46100 Valencia, SpainSepiolsa, Avda. del Acero, 14-16, Pol. UP-1 (Miralcampo), 19200 Azuqueca de Henares, SpainDepartamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, SpainDepartamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, SpainDepartament d’Enginyeria Química, ETSE, Universitat de València, Av. Universitat, Burjassot, 46100 Valencia, Spainγ-Valerolactone (GVL) is a valuable chemical that can be used as a clean additive for automotive fuels. This compound can be produced from biomass-derived compounds. Levulinic acid (LA) is a compound that can be obtained easily from biomass and it can be transformed into GVL by dehydration and hydrogenation using metallic catalysts. In this work, catalysts of Ni (a non-noble metal) supported on a series of natural and low-cost clay-materials have been tested in the transformation of LA into GVL. Catalysts were prepared by a modified wet impregnation method using oxalic acid trying to facilitate a suitable metal dispersion. The supports employed are attapulgite and two sepiolites with different surface areas. Reaction tests have been undertaken using an aqueous medium at moderate reaction temperatures of 120 and 180 °C. Three types of experiments were undertaken: (i) without H<sub>2</sub> source, (ii) using formic acid (FA) as hydrogen source and (iii) using Zn in order to transform water in hydrogen through the reaction Zn + H<sub>2</sub>O → ZnO + H<sub>2</sub>. The best results have been obtained combining Zn (which plays a double role as a reactant for hydrogen formation and as a catalyst) and Ni/attapulgite. Yields to GVL higher than 98% have been obtained at 180 °C in the best cases. The best catalytic performance has been related to the presence of tiny Ni particles as nickel crystallites larger than 4 nm were not present in the most efficient catalysts.https://www.mdpi.com/1996-1073/13/13/3448levulinic acidγ-valerolactonehydrogen from waterZn: Nisepioliteattapulgite |
| spellingShingle | Adrián García Rut Sanchis Francisco J. Llopis Isabel Vázquez María Pilar Pico María Luisa López Inmaculada Álvarez-Serrano Benjamín Solsona Ni Supported on Natural Clays as a Catalyst for the Transformation of Levulinic Acid into γ-Valerolactone without the Addition of Molecular Hydrogen Energies levulinic acid γ-valerolactone hydrogen from water Zn: Ni sepiolite attapulgite |
| title | Ni Supported on Natural Clays as a Catalyst for the Transformation of Levulinic Acid into γ-Valerolactone without the Addition of Molecular Hydrogen |
| title_full | Ni Supported on Natural Clays as a Catalyst for the Transformation of Levulinic Acid into γ-Valerolactone without the Addition of Molecular Hydrogen |
| title_fullStr | Ni Supported on Natural Clays as a Catalyst for the Transformation of Levulinic Acid into γ-Valerolactone without the Addition of Molecular Hydrogen |
| title_full_unstemmed | Ni Supported on Natural Clays as a Catalyst for the Transformation of Levulinic Acid into γ-Valerolactone without the Addition of Molecular Hydrogen |
| title_short | Ni Supported on Natural Clays as a Catalyst for the Transformation of Levulinic Acid into γ-Valerolactone without the Addition of Molecular Hydrogen |
| title_sort | ni supported on natural clays as a catalyst for the transformation of levulinic acid into γ valerolactone without the addition of molecular hydrogen |
| topic | levulinic acid γ-valerolactone hydrogen from water Zn: Ni sepiolite attapulgite |
| url | https://www.mdpi.com/1996-1073/13/13/3448 |
| work_keys_str_mv | AT adriangarcia nisupportedonnaturalclaysasacatalystforthetransformationoflevulinicacidintogvalerolactonewithouttheadditionofmolecularhydrogen AT rutsanchis nisupportedonnaturalclaysasacatalystforthetransformationoflevulinicacidintogvalerolactonewithouttheadditionofmolecularhydrogen AT franciscojllopis nisupportedonnaturalclaysasacatalystforthetransformationoflevulinicacidintogvalerolactonewithouttheadditionofmolecularhydrogen AT isabelvazquez nisupportedonnaturalclaysasacatalystforthetransformationoflevulinicacidintogvalerolactonewithouttheadditionofmolecularhydrogen AT mariapilarpico nisupportedonnaturalclaysasacatalystforthetransformationoflevulinicacidintogvalerolactonewithouttheadditionofmolecularhydrogen AT marialuisalopez nisupportedonnaturalclaysasacatalystforthetransformationoflevulinicacidintogvalerolactonewithouttheadditionofmolecularhydrogen AT inmaculadaalvarezserrano nisupportedonnaturalclaysasacatalystforthetransformationoflevulinicacidintogvalerolactonewithouttheadditionofmolecularhydrogen AT benjaminsolsona nisupportedonnaturalclaysasacatalystforthetransformationoflevulinicacidintogvalerolactonewithouttheadditionofmolecularhydrogen |