In Situ Catalytic Hydrogenation of Biomass‐Derived Methyl Levulinate to γ‐Valerolactone in Methanol

Tang, Xing; Li, Zheng; Zeng, Xianhai; Jiang, Yetao; Liu, Shijie; Lei, Tingzhou; Sun, Yong; Lin, Lu

doi:10.1002/cssc.201403392

Cited by 61 publications

(41 citation statements)

References 66 publications

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“…When the reaction was conducted at 200°C for 1 h, a X ML of only 10.2% with a S GVL of 96.5% was obtained (Table , entry 4). The low X ML is mainly ascribed to insufficient H 2 supply by MeOH reforming and/or inferior ML hydrogenation at a relatively low temperature . Moreover, almost no by‐products from the hydrocarboxylation of GVL were detected in this case.…”

Section: Resultsmentioning

confidence: 78%

“…However, no detectable MHP intermediate could be observed, indicating that the reduction of ML to MHP is the rate‐determing step and the intramolecular transesterification of MHP to GVL is a fast step under the conditions applied in this study . Besides the main product GVL, small amount of by‐products could form through the hydrocarboxylation/alkoxycarbonylation of GVL with CO 2 in MeOH followed by hydrogenation (Scheme ) …”

Section: Resultsmentioning

confidence: 86%

“…According to NH 3 ‐TPD analysis (Fig. S12 in the File S1), the adsorption of humins brought about a lot of acid sites, which should be responsible for the increase in the selectivity of by‐products …”

Section: Resultsmentioning

confidence: 99%

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Hydrogenation of methyl levulinate to γ‐valerolactone over Cu─Mg oxide using MeOH as in situ hydrogen source

Cao

Wei

Liu

et al. 2018

J of Chemical Tech & Biotech

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BACKGROUND γ‐Valerolactone (GVL) is a versatile biomass‐derived platform molecule that could serve as a building block to produce chemicals, materials and fuels, but the production of GVL from biomass via a cost‐competitive method is challenging. In this contribution, a robust Cu─Mg oxide was prepared as an efficient bifunctional catalyst for both H2 production by MeOH reforming and hydrogenation of methyl levulinate (ML) to GVL in MeOH medium. RESULTS Cu0.87Mg0.13Ox prepared by a urea hydrolysis method offered a GVL yield up to 90.6% at 220°C in 4 h without external hydrogen. This catalyst could be reused for at least seven consecutive cycles without loss of its activity. Notably, Cu0.87Mg0.13Ox also provided nearly 70% GVL yield in methanolysis products of cellulose in the presence of humins. Characterization of the catalyst indicates that the incorporation of MgO greatly facilitates the stabilization of Cu+ species that possess a better catalytic performance in ML hydrogenation compared with metallic Cu. CONCLUSION This robust Cu0.87Mg0.13Ox could greatly contribute to develop a highly facile and desirable two‐step strategy for GVL production from cellulose, through the integration of ML production by methanolysis of cellulose, H2 formation by MeOH reforming and ML hydrogenation in MeOH medium. © 2018 Society of Chemical Industry

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Section: Resultsmentioning

confidence: 78%

Section: Resultsmentioning

confidence: 86%

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Hydrogenation of methyl levulinate to γ‐valerolactone over Cu─Mg oxide using MeOH as in situ hydrogen source

Cao

Wei

Liu

et al. 2018

J of Chemical Tech & Biotech

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“…2.5‐15 MPa), followed by acid/base‐mediated lactonization can afford GVL with reduced oxygen content . To increase the economic benefit of the catalytic process, some efforts have been made on the development of non‐noble metal particles (e. g., Ni, Cu and Co) and even transition metal oxides (e. g., ZrO 2 , ZrNi, TiZr, and ZrFeO x ) for the selective conversion of levulinates to GVL in good yields by using formic acid or alcohol as hydrogen‐donor (H‐donor) . The synergistic effect of Lewis acid‐base pair sites is verified to be responsible for achieving the high efficiency in the production of GVL from alkyl levulinates in alcohol via cascade Meerwein‐Ponndorf‐Verley (MPV) reduction and lactonization ,.…”

Section: Introductionmentioning

confidence: 99%

Porous Zr‐Bibenzyldiphosphonate Nanohybrid with Extra Hydroxy Species for Enhancive Upgrading of Biomass‐Based Levulinates

Yang¹,

Zhao²,

Li³

et al. 2018

ChemistrySelect

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Lewis acidic and/or basic sites are typically clarified to play a positive role in the cascade hydrogen transfer and lactonization process, while the influence of Brønsted acid species on the catalyst activity and stability is rarely studied. In this work, a new acid‐base bifunctional hybrid BPhZr with augmented average pore diameter was prepared from the assembly of ([1, 1’‐biphenyl]‐4,4’‐diylbis(methylene))diphosphonic acid with zirconium via a facile solvothermal method. The effects of reaction parameters, substrate scope, and metal ion type were investigated. Besides the promotional effect of moderate Lewis acid/base sites and improved texture properties, the presence of Brønsted acidic species (e. g., –OH) in BPhZr was demonstrated to positively promote the synthesis of γ‐valerolactone (GVL; ca. 95% yield) from levulinates via cascade transfer hydrogenation and lactonization. In comparison with previously reported catalysts, the BPhZr hybrid exhibited a superior activity in terms of TOF (3.2 h−1) and activation energy (21 kJ/mol) for the reaction. Moreover, BPhZr was found to be highly stable and recyclable in five consecutive cycles, showing no significant decrease in GVL yield and selectivity.

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“…For example, diphenolic acid, synthesized by the condensation of LA with phenols, has been envisaged as a desirable substitute for 4,4′‐(propane‐2,2‐diyl)diphenol in the polycarbonate and epoxy‐resin industries . Similarly, methyl levulinate (ML) has found application in the synthesis of γ‐valerolactone, which is used as a solvent and an alternative fuel additive . Furthermore, ethyl levulinate (EL) is considered as a new biobased diluent for biodiesel owing to its high saturated fatty acid content …”

Section: Introductionmentioning

confidence: 99%

Catalytic Conversion of Carbohydrates to Levulinate Ester over Heteropolyanion‐Based Ionic Liquids

et al. 2016

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An efficient one-pot approach for the production of levulinate ester from renewable carbohydrates is demonstrated over heteropolyanion-based ionic liquid (IL-POM) catalysts with alcohols as the promoters and solvents. The relationships between the structure, acidic strength, and solubility of the IL-POM in methanol and the catalytic performance were studied intensively. A cellulose conversion of 100 % could be achieved with a 71.4 % yield of methyl levulinate over the catalyst [PyPS] PW O [PyPS=1-(3-sulfopropyl)pyridinium] at 150 °C for 5 h. This high efficiency is ascribed to the reasonably high activity of the ionic liquid (IL) catalyst and reaction coupling with rapid in situ esterification of the generated levulinic acid with the alcohol promoter, which allows the insolubility of cellulose encountered in biomass conversion to be overcome. Furthermore, the present process exhibits high feedstock adaptability for typical carbohydrates and handy catalyst recovery by a simple self-separation procedure through temperature control.

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In Situ Catalytic Hydrogenation of Biomass‐Derived Methyl Levulinate to γ‐Valerolactone in Methanol

Cited by 61 publications

References 66 publications

Hydrogenation of methyl levulinate to γ‐valerolactone over Cu─Mg oxide using MeOH as in situ hydrogen source

Hydrogenation of methyl levulinate to γ‐valerolactone over Cu─Mg oxide using MeOH as in situ hydrogen source

Porous Zr‐Bibenzyldiphosphonate Nanohybrid with Extra Hydroxy Species for Enhancive Upgrading of Biomass‐Based Levulinates

Catalytic Conversion of Carbohydrates to Levulinate Ester over Heteropolyanion‐Based Ionic Liquids

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