Ni-Mg/Al Mixed Oxides Prepared from Layered Double Hydroxides as Catalysts for the Conversion of Furfural to Tetrahydrofurfuryl Alcohol
Ni-Mg/Al mixed oxide catalysts (Ni<sub>2</sub>A<sub>l</sub>, Ni<sub>2</sub>Mg<sub>1</sub>Al, and Ni<sub>1</sub>Mg<sub>1</sub>Al) obtained from layered double hydroxides (LDHs) were tested on the one-pot production of tetrahydrof...
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MDPI AG
2023-03-01
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| author | Abdulaziz Aldureid Daniel Montané Jordi Llorca Francesc Medina |
| author_facet | Abdulaziz Aldureid Daniel Montané Jordi Llorca Francesc Medina |
| author_sort | Abdulaziz Aldureid |
| collection | DOAJ |
| description | Ni-Mg/Al mixed oxide catalysts (Ni<sub>2</sub>A<sub>l</sub>, Ni<sub>2</sub>Mg<sub>1</sub>Al, and Ni<sub>1</sub>Mg<sub>1</sub>Al) obtained from layered double hydroxides (LDHs) were tested on the one-pot production of tetrahydrofurfuryl alcohol (TFA) from furfural (FF). Upon calcination at 400 °C and reduction at 500 °C, the LDHs gave catalysts containing small nickel crystallites (<4 nm) dispersed on mixtures of metal oxides and spinel structures. Complete conversion of FF (>99.5%) was achieved on all the catalysts after 4 h at 190 °C and 5.0 MPa of H<sub>2</sub> using 5 wt.% FF in ethanol and a furfural-to-catalyst mass ratio of 7.44 g/g. TFA evolved from the sequential hydrogenation of FF to furfuryl alcohol (FA) to TFA. Competing reaction routes involved decarbonylation of FF to furan (FUR) followed by hydrogenation to tetrahydrofuran (THF) or hydrogenolysis to n-butane (BU) and the hydrogenation of the carbonyl group in FF to form 2-methyl furan (mFUR) and its hydrogenation to 2-methyltetrahydrofuran (mTHF). A third competing route consisted of the nucleophilic addition of FF with ethanol and with FA to form acetals (such as 2-(diethoxymethyl)furan, FDA), which were later converted to difurfuryl ether (DFE) and tetrahydrofurfuryl ethyl ether (TFEE) as final products. Hydrogen pressure favored the production of TFA and diminished the formation of acetals, while temperature reduced the capacity of the catalyst to hydrogenate the furan ring, thus reducing TFA and increasing FA and FUR. An 80% yield to TFA was achieved with the Ni<sub>2</sub>Mg<sub>1</sub>Al catalysts after 6 h at 190 °C and 50 bar H<sub>2</sub>, but a variety of coproducts were present at low concentration. Testing of the catalysts in gas-phase hydrogenation conditions at atmospheric pressure revealed a poorer performance, with FA as the main product. |
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| issn | 2624-8549 |
| language | English |
| last_indexed | 2024-03-11T06:47:04Z |
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| spelling | doaj.art-cb15d668e48c4f55834b0cd7c8a9e1c22023-11-17T10:15:54ZengMDPI AGChemistry2624-85492023-03-015157158810.3390/chemistry5010041Ni-Mg/Al Mixed Oxides Prepared from Layered Double Hydroxides as Catalysts for the Conversion of Furfural to Tetrahydrofurfuryl AlcoholAbdulaziz Aldureid0Daniel Montané1Jordi Llorca2Francesc Medina3Departament d’Enginyeria Química, Universitat Rovira i Virgili, Av. Països Catalans 26, E-43007 Tarragona, SpainDepartament d’Enginyeria Química, Universitat Rovira i Virgili, Av. Països Catalans 26, E-43007 Tarragona, SpainInstitute of Energy Technologies, Department of Chemical Engineering, Barcelona Research Center in Multiscale Science and Engineering, Barcelona East School of Engineering (EEBE), Universitat Politècnica de Catalunya, Eduard Maristany 16, E-08019 Barcelona, SpainDepartament d’Enginyeria Química, Universitat Rovira i Virgili, Av. Països Catalans 26, E-43007 Tarragona, SpainNi-Mg/Al mixed oxide catalysts (Ni<sub>2</sub>A<sub>l</sub>, Ni<sub>2</sub>Mg<sub>1</sub>Al, and Ni<sub>1</sub>Mg<sub>1</sub>Al) obtained from layered double hydroxides (LDHs) were tested on the one-pot production of tetrahydrofurfuryl alcohol (TFA) from furfural (FF). Upon calcination at 400 °C and reduction at 500 °C, the LDHs gave catalysts containing small nickel crystallites (<4 nm) dispersed on mixtures of metal oxides and spinel structures. Complete conversion of FF (>99.5%) was achieved on all the catalysts after 4 h at 190 °C and 5.0 MPa of H<sub>2</sub> using 5 wt.% FF in ethanol and a furfural-to-catalyst mass ratio of 7.44 g/g. TFA evolved from the sequential hydrogenation of FF to furfuryl alcohol (FA) to TFA. Competing reaction routes involved decarbonylation of FF to furan (FUR) followed by hydrogenation to tetrahydrofuran (THF) or hydrogenolysis to n-butane (BU) and the hydrogenation of the carbonyl group in FF to form 2-methyl furan (mFUR) and its hydrogenation to 2-methyltetrahydrofuran (mTHF). A third competing route consisted of the nucleophilic addition of FF with ethanol and with FA to form acetals (such as 2-(diethoxymethyl)furan, FDA), which were later converted to difurfuryl ether (DFE) and tetrahydrofurfuryl ethyl ether (TFEE) as final products. Hydrogen pressure favored the production of TFA and diminished the formation of acetals, while temperature reduced the capacity of the catalyst to hydrogenate the furan ring, thus reducing TFA and increasing FA and FUR. An 80% yield to TFA was achieved with the Ni<sub>2</sub>Mg<sub>1</sub>Al catalysts after 6 h at 190 °C and 50 bar H<sub>2</sub>, but a variety of coproducts were present at low concentration. Testing of the catalysts in gas-phase hydrogenation conditions at atmospheric pressure revealed a poorer performance, with FA as the main product.https://www.mdpi.com/2624-8549/5/1/41heterogeneous catalysismesoporous materials as solid catalystsbiomass valorizationlayered double hydroxidehydrogenation |
| spellingShingle | Abdulaziz Aldureid Daniel Montané Jordi Llorca Francesc Medina Ni-Mg/Al Mixed Oxides Prepared from Layered Double Hydroxides as Catalysts for the Conversion of Furfural to Tetrahydrofurfuryl Alcohol Chemistry heterogeneous catalysis mesoporous materials as solid catalysts biomass valorization layered double hydroxide hydrogenation |
| title | Ni-Mg/Al Mixed Oxides Prepared from Layered Double Hydroxides as Catalysts for the Conversion of Furfural to Tetrahydrofurfuryl Alcohol |
| title_full | Ni-Mg/Al Mixed Oxides Prepared from Layered Double Hydroxides as Catalysts for the Conversion of Furfural to Tetrahydrofurfuryl Alcohol |
| title_fullStr | Ni-Mg/Al Mixed Oxides Prepared from Layered Double Hydroxides as Catalysts for the Conversion of Furfural to Tetrahydrofurfuryl Alcohol |
| title_full_unstemmed | Ni-Mg/Al Mixed Oxides Prepared from Layered Double Hydroxides as Catalysts for the Conversion of Furfural to Tetrahydrofurfuryl Alcohol |
| title_short | Ni-Mg/Al Mixed Oxides Prepared from Layered Double Hydroxides as Catalysts for the Conversion of Furfural to Tetrahydrofurfuryl Alcohol |
| title_sort | ni mg al mixed oxides prepared from layered double hydroxides as catalysts for the conversion of furfural to tetrahydrofurfuryl alcohol |
| topic | heterogeneous catalysis mesoporous materials as solid catalysts biomass valorization layered double hydroxide hydrogenation |
| url | https://www.mdpi.com/2624-8549/5/1/41 |
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