Base-free conversion of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid in ionic liquids

Yan, Dongxia; Xin, Jiayu; Shi, Chao; Lü, Xingmei; Ni, Lingli; Wang, Gongying; Zhang, Suojiang

doi:10.1016/j.cej.2017.04.021

Cited by 82 publications

(49 citation statements)

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“…An initial water content of 3.5 %a nd af ructose loading of 14 % were selected. [45] ChemSusChem 2019, 12,4452 -4460 www.chemsuschem.org this purpose, reaching7 4% yield in 10 min at 14 %f ructose loading. The success of PTSA for the dehydration of HMF has already been established in various differents ystems and HCl has been shown to be an effective catalyst in aw ide variety of solvents.…”

Section: Selection Of the Acid Catalystmentioning

confidence: 99%

“…[34] A5 2% yield was obtained in 3husing Amberlyst-15 in [bmim][PF 6 ]a t8 0 8C, with the process showingi mprovement (80 %y ield) on addition of DMSO. Some researchers have focused on the oxidation of the HMF formed in the reaction media directly to 2,5 furandicarboxylic acid (FDCA), which can be separated by water addition, [44,45] but this reactionp rovedt ob en onselective. [36] However,i ng eneral, satisfactory results have not been obtainedi ni onicl iquidsw ith noncoordinatinga nions, such as [BF 4 ] À ,[ PF 6 ] À ,[ OTf] À ,a nd [NTf 2 ] À .S hi and co-workers analyzed the effect of anions on the dehydration of fructosea nd, through am olecular dynamics study,s howedt hat chloride anions, in contrast to triflate,t end to form ac entralized structure around the fructosem olecule through hydrogen bonds.…”

Section: Introductionmentioning

confidence: 99%

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Rapid, High‐Yield Fructose Dehydration to 5‐Hydroxymethylfurfural in Mixtures of Water and the Noncoordinating Ionic Liquid [bmim][OTf]

2019

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The noncoordinating ionic liquid [bmim][OTf] (bmim=1‐butyl‐3‐methylimidazolium) is an effective and versatile solvent for the high‐yield dehydration of fructose to the platform chemical 5‐hydroxymethylfurfural (HMF) over short reaction times. In contrast to prior studies in which low yields were obtained for this transformation in ionic liquids (ILs) with noncoordinating anions, this contribution reveals that the water content is an essential parameter for an efficient reaction in ILs. Achieving the optimum amount of water can increase the yield dramatically by regulating the acidity of the catalyst and partially suppressing the side reaction caused by self‐condensation of HMF. Using acid catalysis in [bmim][OTf] with 3.5 % water content, yields above 80 % can be achieved at 100 °C in only 10 min, even at high (14 %) fructose loading. These results also suggest that [bmim][OTf] represents a superior medium for solvent extraction of HMF compared to halide‐based ILs, allowing the option of isolation or further valorization of the HMF formed.

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Section: Selection Of the Acid Catalystmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Rapid, High‐Yield Fructose Dehydration to 5‐Hydroxymethylfurfural in Mixtures of Water and the Noncoordinating Ionic Liquid [bmim][OTf]

2019

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“…Notably,i midazolium-based ILs show preferable solubility for furan compounds, including HMF and FDCA, compared with conventional aqueous solutionso ro rganic solvents. [20] The oxidation of HMF in imidazole ILs would eliminate the use of additional base, mineral acids, andc omplex downstream processes, whichi se conomically more feasible and more environmentally friendly.R ecently,w ed emonstrated ab ase-free conversion of HMF to FDCA in ILs by using Fe-Zr-O catalysts, and ay ield of 60 % was obtained. [4b, 20b] Particularly,I Ls are also favored for the synthesis of HMF by acid-catalyzed dehydration of sugars or cellulose.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid with Heteropoly Acids and Ionic Liquids

et al. 2019

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2,5‐Furandicarboxylic acid (FDCA) is regarded as an important bioderived substitute for petrochemically derived terephthalic acid (PTA), which is widely applied in the polymer industry. This work delineates the base‐free oxidation of 5‐hydroxymethylfurfural (HMF) to FDCA in an ionic liquid/heteropoly acid (IL–HPA) catalytic system. HPAs displayed high activity for selective oxidation; their active center (Mo/V) was activated by O2 and transformed from oxygen single and double bonds to epoxy groups, resulting in an FDCA yield of 89 % for HPMV6 (HPM=H3PMo12O40) in the presence of [Bmim]Cl (1‐butyl‐3‐methylimidazolium chloride) under optimized reaction conditions. The high solubility of imidazole ILs for FDCA improved the affinity of HMF and the active centers of the catalyst and protected the furan ring from oxidative cleavage. Furthermore, multiple hydrogen bonds simultaneously formed between the electronegative anions and hydroxy protons of HMF, as well as the hydrogen atoms of the imidazole rings and hydroxy groups, promoting the transformation to aldehyde groups. Various starting materials were studied, and a moderate FDCA yield was obtained from glucose. This work provides an interesting IL–HPA catalytic system for the base‐free synthesis of FDCA from accessible monosaccharides and illustrates the great potential of FDCA production from renewable carbohydrates.

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“…ILs can be used not only in the biomass pretreatment process but also in the conversion of biomass derivant to fine chemicals and biofuel. ILs were regarded as commendable solvents or catalyst for the conversion of biomass derivant …”

Section: Introductionmentioning

confidence: 99%

“…30 ILs can be used not only in the biomass pretreatment process but also in the conversion of biomass derivant to fine chemicals and biofuel. ILs were regarded as commendable solvents 24,31 or catalyst 32 for the conversion of biomass derivant. 33 However, most pieces of literature have focused on the application of ILs in the hydrolysis of cellulose to glucose.…”

Section: Introductionmentioning

confidence: 99%

Direct conversion of cellulose to sorbitol via an enhanced pretreatment with ionic liquids

Gao

Xin

Yan

et al. 2018

J of Chemical Tech & Biotech

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BACKGROUND Direct conversion of cellulose into platform chemicals, is regarded as one of the most promising aspects of biomass resource utilization. However, the development of direct conversion of cellulose to high value‐added chemicals such as sorbitol still remains a tremendous problem owing to the robust structure of cellulose to resist degradation. RESULTS In this study, ball‐milled microcrystalline cellulose was dissolved in ionic liquids, and finally converted to sorbitol smoothly through hydrolytic hydrogenation processes. Both ball‐milling and ionic liquids dissolution can effectively destroy the strong inter‐ and intramolecular hydrogen bond network formed between hydroxyl groups within cellulose. Furthermore, water‐soluble ionic cellulose came into being due to the dissolution of cellulose in ionic liquids, which increased the contact of cellulose to catalyst remarkably. The crystalline index of cellulose can be reduced from 79.9% to 3.2% under an optimum ball‐milling time of 4 h, and the preferred cellulose dissolution solvent was selected to be [Amim]Cl. Finally, the final product, sorbitol was successfully synthesized over the catalysis of Nafion NR50 and Ru/AC (active carbon) with the sorbitol yield to be 34.3% at 150 °C for 1 h. CONCLUSION This study proposed a novel approach about direct conversion of cellulose to sorbitol with ionic liquids as well as extended the application of ionic liquids in the field of conversion of renewable biomass to platform chemicals. © 2018 Society of Chemical Industry

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Base-free conversion of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid in ionic liquids

Cited by 82 publications

References 55 publications

Rapid, High‐Yield Fructose Dehydration to 5‐Hydroxymethylfurfural in Mixtures of Water and the Noncoordinating Ionic Liquid [bmim][OTf]

Rapid, High‐Yield Fructose Dehydration to 5‐Hydroxymethylfurfural in Mixtures of Water and the Noncoordinating Ionic Liquid [bmim][OTf]

Highly Efficient Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid with Heteropoly Acids and Ionic Liquids

Direct conversion of cellulose to sorbitol via an enhanced pretreatment with ionic liquids

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