- New generation biofuels: γ-Valerolactone into valeric esters in one pot
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Ethyl valerate and pentyl valerate, suitable as a gasoline additive and diesel component respectively, can be obtained in a one pot one step reaction from γ-valerolactone, readily available from lignocellulosic biomass. The reaction takes place in ethanol under H2 through nucleophilic addition of the alcohol to the carboxylic group giving hydroxypentanoate, dehydration to pentenoate and hydrogenation to the saturated ester. The bifunctional catalyst used consists of a non noble metal, namely copper, supported on an amorphous weakly acidic material, therefore representing an interesting alternative to Pt-zeolite catalysts. Pentyl valerate can be obtained in one pot with conversions >90% and selectivity up to 83%.
- Chan-Thaw, Carine E.,Marelli, Marcello,Psaro, Rinaldo,Ravasio, Nicoletta,Zaccheria, Federica
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- Hydrogenation of γ-valerolactone in ethanol over Pd nanoparticles supported on sulfonic acid functionalized MIL-101
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A ligand-based solid solution approach is employed to incorporate sulphonic acid functional groups into the porous coordination polymer Cr-MIL-101. Loaded with Pd nanoparticles these Pd/MIL-101-SO3H materials act as bifunctional catalysts for the one-pot conversion of γ-valerolactone into ethyl valerate (up to 83% yield). The catalysts were extensively characterized before and after reaction. The influence of the sulfonic acid group density and the reaction conditions on the catalytic activity was systematically investigated and the reaction network for γ-valerolactone upgrading was discussed.
- Zhang, Damin,Ye, Feiyang,Guan, Yejun,Wang, Yimeng,Hensen, Emiel J. M.
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- Stabilization of cobalt catalysts by embedment for efficient production of valeric biofuel
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We herein report, for the first time, a bifunctional base-metal catalyst (Co@HZSM-5) that acts as an efficient alternative to noble-metal catalysts (e.g., Pt, Ru) for the conversion of levulinic acid into valeric biofuel under batch and fixed-bed reactor conditions. The cobalt nanoparticles were embedded in HZSM-5 crystals and catalyzed the sequential hydrogenations of the ketone and alkene functional groups; meanwhile, the acidic zeolite catalyzed the ring opening of the γ-valerolactone intermediate. Although base metals (e.g., Co) are abundant and inexpensive, their sintering and/or leaching under liquid-phase conditions always lead to the irreversible deactivation of the catalyst. In this system, the embedment structure stabilizes the nanoparticles, and Co@HZSM-5 could be used up to eight times. This work provides a practical clue toward the stabilization of base-metal catalysts and will inspire the development of large-scale biorefinery.
- Sun, Peng,Gao, Guang,Zhao, Zelun,Xia, Chungu,Li, Fuwei
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p. 4136 - 4142
(2015/02/19)
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