A practical and efficient synthesis of methyl levulinate from cellulosic biomass catalyzed by an aluminum-based mixed acid catalyst system

Tominaga, Ken-ichi; Nemoto, Koji; Kamimura, Yoshihiro; Yamada, Airi; Yamämoto, Yasushi; Sato, Koichi

doi:10.1039/c6ra15638j

Cited by 23 publications

(19 citation statements)

References 48 publications

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“…Isomerization of glucose to fructose could be achieved using biological or chemical catalysts including homogeneous base/acid catalysts or heterogeneous solid catalysts . Many types of research contributed to the acid-catalyzed isomerization of d -glucose to d -fructose promoted by aluminum-based catalysts. , Ekeberg et al reported that the addition of aluminum oxide to a boiling solution of glucose-containing pyridine leads to a significantly higher reaction rate of the aldose–ketose transformation and it showed a substantially higher yield of fructose (50%) compared with the classical Lobry de Bruyn–Alberda–van Ekenstein transformation . In order to increase the yield of fructose, the hydroxide-containing resin was further modified with sodium aluminate to obtain a resin-bound aluminate …”

Section: Introductionmentioning

confidence: 99%

Mechanism of Glucose–Fructose Isomerization over Aluminum-Based Catalysts in Methanol Media

Zhang

Zhao

et al. 2019

ACS Sustainable Chem. Eng.

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The catalytic isomerization of glucose to fructose has been deemed a vital step in biorefinery, while the isomerization mechanism in alcoholic media still remains ambiguous. Hereby, density functional theory (DFT) calculations were carried out to investigate the isomerization mechanism of glucose over aluminum-based catalysts in methanol media. Al3+ was apt to coordinate with methanol and cyclic β-d-glucose (CDG) to form various complexes. It was found that [Al(CH3O)2(CH3OH)2]+ was the most stable one in +1 charge complexes based on the DFT calculations and ESI-MS experiments. Furthermore, the four-coordination complex [(η2 O4,O6-CDG)Al(CH3O)2]+ was predicted to be the most preferable. Ionic species formed between Al3+ and the solvent can further assemble with glucose to catalyze the isomerization. The isomerization proceeds mainly by three steps, including ring-opening, hydride shift, and ring-closing with the migration of H from the C2–H to the O1–H bond (hydride shift) as the rate-determining step. The coordination of Al3+ with methanol showed a significant catalytic effect by shortening the proton transfer distance, which resulted in a markedly reduced overall reaction barrier for isomerization. The calculations provided a better insight into the glucose transformation in the methanol media with Al-based catalysts.

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Section: Introductionmentioning

confidence: 99%

Mechanism of Glucose–Fructose Isomerization over Aluminum-Based Catalysts in Methanol Media

Zhang

Zhao

et al. 2019

ACS Sustainable Chem. Eng.

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“…The direct production of alkyl levulinates from glucose could be achieved using catalysts having both base and acid sites [6] or Lewis and Brønsted acidic functionalities [7]. Methyl levulinate can be efficiently obtained from pure sugars and lignocellulosic biomasses by combining aluminum salts and organic sulfonic acids [8]. EL could also be proficiently produced by combining iron and aluminum salts with sulfuric acids under relatively mild conditions (T > 453 K).…”

Section: Introductionmentioning

confidence: 99%

Intensification of Processes for the Production of Ethyl Levulinate Using AlCl3·6H2O

Pastore

D'Ambrosio

2021

Energies

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A process for obtaining ethyl levulinate through the direct esterification of levulinic acid and ethanol using AlCl3·6H2O as a catalyst was investigated. AlCl3·6H2O was very active in promoting the reaction and, the correspondent kinetic and thermodynamic data were determined. The reaction followed a homogeneous second-order reversible reaction model: in the temperature range of 318–348 K, Ea was 56.3 kJ·K−1·mol−1, whereas Keq was in the field 2.37–3.31. The activity of AlCl3·6H2O was comparable to that of conventional mineral acids. Besides, AlCl3·6H2O also induced a separation of phases in which ethyl levulinate resulted mainly (>98 wt%) dissolved into the organic upper layer, well separated by most of the co-formed water, which decanted in the bottom. The catalyst resulted wholly dissolved into the aqueous phase (>95 wt%), allowing at the end of a reaction cycle, complete recovery, and possible reuse for several runs. With the increase of the AlCl3·6H2O content (from 1 to 5 mol%), the reaction proceeded fast, and the phases’ separation improved. Such a behavior eventually results in an intensification of processes of reaction and separation of products and catalyst in a single step. The use of AlCl3·6H2O leads to a significant reduction of energy consumed for the final achievement of ethyl levulinate, and a simplification of line-processes can be achieved.

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“…Tominaga and Ding also both reported that acid catalysts containing Lewis and Brønsted acid sites exhibit better catalytic activity for cellulose. 13,14 Phem et al 15 showed that a Brønsted acid was able to catalyze the hydrolysis of cellulose to glucose and the dehydration of fructose to 5HMF, while a Lewis acid catalyzed the isomerization of fructose to glucosides. Ding et al 14 synthesized a niobium-based phosphate (NBPPH1) catalyst with double acid sites for the production of methyl levulinate (ML) from cellulose in methanol and obtained 96% cellulose conversion and a 56 mol% yield after 24 h at 180 °C.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of ethyl levulinate from cellulose over a double acid site catalyst

Huang

Hao

2021

J of Chemical Tech & Biotech

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BACKGROUND: A novel double acid site solid catalyst (Al-OCS-0.1) having an ordered mesoporous structure was synthesized by grafting sulfonic acid groups on an oxidized ordered mesoporous carbon (OOMC) support and loading 10% Al 2 (SO 4 ) 3 .RESULT: Assessments using Field emission scanning electron microscopy, Transmission electron microscopy and X-ray diffraction showed that the OMC structure remained unchanged after the chemical modification and Al 2 (SO 4 ) 3 loading. The Brunauer-Emmett-Teller surface area and average pore size of Al-OCS-0.1 decreased to 181 m 2 g −1 and 7.1 nm after loading Al 2 (SO 4 ) 3 , respectively. Ammonia temperature-programmed desorption (NH 3 -TPD) and Pyridine adsorption infrared spectroscopy (Py-IR) demonstrated that Al-OCS-0.1 had abundant Brønsted and Lewis acid sites. The ammonia desorption of Al-OCS-0.1 increased from 2.0 to 7.2 mmol g −1 after loading Al 2 (SO 4 ) 3 .CONCLUSION: The Al-OCS-0.1 was used to catalyze the synthesis of ethyl levulinate from cellulose in ethanol and gave an extremely high yield of 50.8 mol% after 5 h at 200 °C.

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A practical and efficient synthesis of methyl levulinate from cellulosic biomass catalyzed by an aluminum-based mixed acid catalyst system

Abstract: A combination of aluminum compounds and organic sulfonic acids was an efficient catalyst system for direct methyl levulinate synthesis from both microcrystalline cellulose and wood powder.

Cited by 23 publications

References 48 publications

Mechanism of Glucose–Fructose Isomerization over Aluminum-Based Catalysts in Methanol Media

Mechanism of Glucose–Fructose Isomerization over Aluminum-Based Catalysts in Methanol Media

Intensification of Processes for the Production of Ethyl Levulinate Using AlCl3·6H2O

Synthesis of ethyl levulinate from cellulose over a double acid site catalyst

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