Orange peel waste (OPW), a significant biomass byproduct derived from the juice processing industry, can be used as valuable resource to produce various chemicals, including methyl levulinate (ML) and limonene (LIM). This study introduces a tandem catalytic process involving the dehydrogenation of LIM into p-cymene and the (transfer) hydrogenation of ML into γ-valerolactone (GVL), unlocking the full potential of OPW chemo-catalytic valorisation in the spirit of circular economy. This process is promoted by the heterogeneous Pd/ZrO2 and t-ZrO2 catalysts in the presence of ethanol as hydrogen-donor solvent. Under batch conditions, Pd/ZrO2 not only shows superior performance in the transfer hydrogenation of ML compared to t-ZrO2, but also promotes the conversion of LIM into p-cymene primarily through the hydrogenation/dehydrogenation route. Most important, Pd/ZrO2 exhibits good activity in the simultaneous upgrading of both ML and LIM across various ML:LIM ratios. Continuous gas-flow conditions result in improved outcomes in terms of ML and LIM conversion, as well as GVL and CYM selectivity. Notably, a strong correlation between CYM and H2 yields has been established providing compelling evidence for the LIM isomerization-dehydrogenation pathway. However, the simultaneous upgrading of LIM and ML was found to be not efficient in the gas-phase due to side oligomerization reactions.

Tandem reductive catalytic upgrading of orange peel waste derived methyl levulinate and limonene into γ-valerolactone and p-cymene promoted by Pd/ZrO2 and ZrO2 catalysts / Allegri, A.; Paone, E.; Bosticco, C.; Pedullà, A.; Musolino, M. G.; Cavani, F.; Tabanelli, T.; Albonetti, S.. - In: MOLECULAR CATALYSIS. - ISSN 2468-8231. - 555:(2024), p. 113840. [10.1016/j.mcat.2024.113840]

Tandem reductive catalytic upgrading of orange peel waste derived methyl levulinate and limonene into γ-valerolactone and p-cymene promoted by Pd/ZrO2 and ZrO2 catalysts

Paone, E.
;
Musolino, M. G.;
2024-01-01

Abstract

Orange peel waste (OPW), a significant biomass byproduct derived from the juice processing industry, can be used as valuable resource to produce various chemicals, including methyl levulinate (ML) and limonene (LIM). This study introduces a tandem catalytic process involving the dehydrogenation of LIM into p-cymene and the (transfer) hydrogenation of ML into γ-valerolactone (GVL), unlocking the full potential of OPW chemo-catalytic valorisation in the spirit of circular economy. This process is promoted by the heterogeneous Pd/ZrO2 and t-ZrO2 catalysts in the presence of ethanol as hydrogen-donor solvent. Under batch conditions, Pd/ZrO2 not only shows superior performance in the transfer hydrogenation of ML compared to t-ZrO2, but also promotes the conversion of LIM into p-cymene primarily through the hydrogenation/dehydrogenation route. Most important, Pd/ZrO2 exhibits good activity in the simultaneous upgrading of both ML and LIM across various ML:LIM ratios. Continuous gas-flow conditions result in improved outcomes in terms of ML and LIM conversion, as well as GVL and CYM selectivity. Notably, a strong correlation between CYM and H2 yields has been established providing compelling evidence for the LIM isomerization-dehydrogenation pathway. However, the simultaneous upgrading of LIM and ML was found to be not efficient in the gas-phase due to side oligomerization reactions.
2024
Orange peel waste, Dehydrogenation, Catalytic transfer hydrogenation, Methyl levulinate, γ-valerolactone, Limonene
p-cymene, Zirconia, Palladium
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.12318/142666
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