Understanding the mechanism of enhanced alcoholysis of biomass carbohydrates to alkyl levulinates over bifunctional catalysts: does it resemble that in water?

Zhang, Yuxuan; Ju, Zhaoyang; Chen, Xueli; Qian, Lei; Mei, Jiaqi; Han, Lujia; Li, Dong; Xiao, Weihua

doi:10.1039/d3gc00913k

Cited by 5 publications

(3 citation statements)

References 72 publications

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“…Thus, in this microreview, we summarized the performance of heterogeneous catalysts in the conversion of the biomass-derived molecules into alkyl levulinates and described the design and development of the heterogeneous catalysts that facilitated excellent yields of the target products. We believe that this microreview will furnish subsequent studies with valuable information on the Alkyl levulinates can be synthesized directly from carbohydrates such as cellulose, glucose, and fructose [16,17]. However, this method has frequently given target products in relatively low yields and selectivities due to the formation of multiple products [18].…”

Section: Introductionmentioning

confidence: 98%

“…The addition of alkyl levulinates to biodiesel can address these drawbacks because of their properties such as low toxicity, high lubricity, flash point stability, and moderate flow properties under low-temperature conditions [3,11,15]. Alkyl levulinates can be synthesized directly from carbohydrates such as cellulose, glucose, and fructose [16,17]. However, this method has frequently given target products in relatively low yields and selectivities due to the formation of multiple products [18].…”

Section: Introductionmentioning

confidence: 99%

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Conversion of Biomass-Derived Molecules into Alkyl Levulinates Using Heterogeneous Catalysts

Yamanaka,

Shimazu

2023

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Alkyl levulinates are promising and versatile biomass-derived chemicals, which are utilized as fuel additives, flavoring agents, fragrances, solvents, and precursors for synthesizing valuable γ-valerolactone. A method for synthesizing alkyl levulinates involves the esterification of levulinic acid with the corresponding alkyl alcohols in the presence of solid acid catalysts that have abundant Brønsted acid sites. Alkyl levulinates can also be synthesized from other biomass-derived molecules such as furfuryl alcohol and furfural via alcoholysis and one-pot conversion, respectively. Thus far, various heterogeneous catalysts have been developed for the conversion of the biomass-derived molecules (levulinic acid, furfuryl alcohol, and furfural) into alkyl levulinates. To obtain the target products in high yields, numerous strategies have been employed including increasing Brønsted acidity, dispersing and incorporating Brønsted acid sites, inducing the formation of mesopores, and inducing a synergistic effect of metal–Brønsted acid sites that are present on a catalyst surface. Here, we summarily reviewed the performances of the heterogeneous catalysts in the conversions, describing the design and development of the heterogeneous catalysts that ensured the excellent yield of alkyl levulinates.

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Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Conversion of Biomass-Derived Molecules into Alkyl Levulinates Using Heterogeneous Catalysts

Yamanaka,

Shimazu

2023

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“…It has been proposed that base-mediated enhanced proton transfer through a water bridge causes stabilization of the transition state in the H 2 heterolysis rate-determining reaction step. Ghorbanpour et al showed that in the reaction of decomposition of formic acid, more hydrogen gas is released when sodium formate is used. , Alkyl levulinates (ALs) are biomass-based chemicals with many applications in various fields and can replace chemicals produced from petrochemical pathways. − Among the uses of ALs, one can mention their role as a solvent, additive, and precursor in producing gamma-valerolactone (GVL). Ethyl levulinate (EL) is an ester with a fruity odor and can be prepared from levulinic acid (LA) or the reaction between furfuryl alcohol and ethanol. − Considering the existence of various sources for EL production, it can be pointed out that this combination is a suitable option for biofuel additives .…”

Section: Introductionmentioning

confidence: 99%

Hydrogenation of Ethyl Levulinate to Gamma-Valerolactone with Formic Acid and a Palladium–Manganese Catalyst Immobilized on Dendritic Fibrous Nanosilica (DFNS)

Khabazi,

Najafi Chermahini,

Luque

et al. 2024

Energy Fuels

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Gamma-valerolactone (GVL) is a useful chemical with various applications obtained from the hydrolysis of lignocellulosic biomass. The present study aims to explore the synthesis of GVL through the hydrogenation of ethyl levulinate (EL) using a palladium−manganese bimetallic catalyst immobilized on a dendritic fibrous nanosilica (Pd x% −Mn y% /DFNS). The key strategy in this reaction involves utilizing the formic acid (FA) decomposition reaction to generate indirect hydrogen and catalytic transfer hydrogenation (CTH) process to convert EL to GVL, a safe and environmentally friendly method. As an economical and available source, EL has less acidity than LA and is more easily separated from the reaction medium. Also, FA (as a byproduct in various processes) can be used as a liquid medium to store hydrogen gas (without the risk of explosion). It can be a potential solution for long-term energy storage by considering the necessary infrastructure. This research showed that the catalytic activity of Pd has developed in the presence of Mn and DFNS and can be affordable. In this reaction, various parameters were investigated. Under the best conditions (1 mL of ethyl levulinate, 3 mL of formic acid, 3 mL of deionized water, 2 g of sodium formate, 50 mg of Pd 6% −Mn 3% /DFNS catalyst, and 8 h), the yields obtained for GVL are 70 and 99.5% at 180 and 230 °C, respectively. Meanwhile, the yield of GVL under the same conditions (without formic acid and sodium formate) using direct molecular hydrogen (2 MPa) at 180 °C was 76%. Also, various methods were used to characterize the catalysts, including Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction, Brunauer−Emmett−Teller, inductively coupled plasma mass spectroscopy, X-ray photoelectron spectroscopy, transmission electron spectroscopy, field emission scanning electron microscopy, and elemental mapping.

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In‐Depth Investigation of the Reaction Parameters Tuning the Ethyl Levulinate Synthesis from Fructose and Inulin

Fulignati,

Antonetti,

Raspolli Galletti

et al. 2024

ChemCatChem

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Alkyl levulinates (ALs) are strategic compounds for the development of sustainable energy transition. In this regard, the direct alcoholysis of fructose and inulin for the selective ethyl levulinate (EL) production was investigated with a One‐Factor‐At‐a‐Time (OFAT) approach employing diluted H2SO4 as catalyst to clarify the role of the main reaction parameters (substrate and acid loadings, temperature, reaction time). The OFAT investigation on fructose ethanolysis allowed to reach the EL yield of 91.5 mol%. The inulin ethanolysis was then optimized adopting the multivariate approach based on the Response Surface Methodology (RSM), which highlighted the interplay of the reaction parameters on the selective EL production. This allowed to identify the optimal conditions to reach the highest EL yield (up to 89.3 mol%) and also those which ensured the highest EL concentration, adopting a substrate loading (14 wt%) higher than the majority ones reported in the literature according to the high gravity approach, and the lowest diethyl ether (DEE) by‐product yield. The DEE formation is scarcely investigated in the literature, but it can negatively influence the alcoholysis process, thus it was considered in this work. Moreover, the humin solid residue was deeply characterized to envisage its possible applications, under a circular economy perspective.

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Understanding the mechanism of enhanced alcoholysis of biomass carbohydrates to alkyl levulinates over bifunctional catalysts: does it resemble that in water?

Abstract: The catalytic hydrolysis/alcoholysis of biomass carbohydrates into levulinic acid/levulinate esters (alkyl levulinates) as green biofuels and value-added chemicals holds great promise for achieving the goals of sustainable chemistry. Bifunctional catalysts...

Cited by 5 publications

References 72 publications

Conversion of Biomass-Derived Molecules into Alkyl Levulinates Using Heterogeneous Catalysts

Conversion of Biomass-Derived Molecules into Alkyl Levulinates Using Heterogeneous Catalysts

Hydrogenation of Ethyl Levulinate to Gamma-Valerolactone with Formic Acid and a Palladium–Manganese Catalyst Immobilized on Dendritic Fibrous Nanosilica (DFNS)

In‐Depth Investigation of the Reaction Parameters Tuning the Ethyl Levulinate Synthesis from Fructose and Inulin

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