Rapid conversion of cellulose to 5-hydroxymethylfurfural using single and combined metal chloride catalysts in ionic liquid

Direct conversion of cellulose into 5-hydroxymethylfurfural(HMF) was performed by using single or combined metal chloride catalysts in 1-ethyl-3-methylimidazolium chloride(Cl) ionic liquid.Our study demonstrated formation of 2-furyl hydroxymethyl ketone(FHMK),and furfural(FF) simultaneously with the formation of HMF.Various reaction parameters were addressed to optimize yields of furan derivatives produced from cellulose by varying reaction temperature,time,and the type of metal chloride catalyst.Catalytic reaction by using FeCl3 resulted in 59.9% total yield of furan derivatives(HMF,FHMK,and FF) from cellulose.CrCl3 was the most effective catalyst for selective conversion of cellulose into HMF(35.6%) with less concentrations of FHMK,and FF.Improving the yields of furans produced from cellulose could be achieved via reactions catalyzed by different combinations of two metal chlorides.Further optimization was carried out to produce total furans yield 75.9% by using FeCl3/CuCl2 combination.CrCl3/CuCl2 was the most selective combination to convert cellulose into HMF(39.9%) with total yield(63.8%) of furans produced from the reaction.The temperature and time of the catalytic reaction played an important role in cellulose conversion,and the yields of products.Increasing the reaction temperature could enhance the cellulose conversion and HMF yield for short reaction time intervals(5~20 min).     

金属卤化物促进糖类催化转化制备5-羟甲基糠醛

研究了碱金属卤化物对AlCl₃催化葡萄糖转化制备5-羟甲基糠醛（HMF）的促进作用. 结果表明,NaF对反应有显著抑制作用,而NaI和NaBr对反应有显著促进作用,而且NaI比NaBr的促进效果更明显. 在N,N-二甲基乙酰胺（DMAC）中,以NaI为添加剂,130 ℃反应15 min,AlCl₃催化葡萄糖转化制备HMF,葡萄糖转化率由71%提高到86%,HMF收率由36%提高到62%. AlCl₃-NaI-DMAC体系也可用于果糖、甘露糖等单糖,蔗糖、麦芽糖、纤维二糖等二糖,以及菊粉等多糖的转化. 以蔗糖为原料,HMF收率可达63%.     

Dehydration of glucose into 5-hydroxymethylfurfural in SO_3H-functionalized ionic liquids

The continuous dehydration of D-glucose into 5-hydroxymethylfurfural（HMF） was carried out under mild conditions,using SO3H-functionalized acidic ionic liquids as catalysts and H2O-4-methyl-2-pentanone（MIBK） biphasic system as solvent.High glucose conversion of 97.4% with HMF yield of 75.1%was obtained at 120 8C for 360 min,also,small amounts of levulinic acid（LA） and formic acid were generated.Generally,the dosage of catalyst and the initial content of glucose influenced the reaction significantly; the HMF selectivity decreased with the excessive elevation of temperature and prolonging of time; and water content in the system had a negative effect on the reaction.The ionic liquid catalyst could be recycled and exhibited constant activity for five successful runs.This paper provided a new strategy for HMF production from glucose.     

Cellulose sulfuric acid as a bio-supported and recyclable solid acid catalyst for the synthesis of 5-hydroxymethylfurfural and 5-ethoxymethylfurfural from fructose

In this study, we have developed a new and green method for the synthesis of 5-hydroxymethylfurfural (HMF) and 5-ethoxymethylfurfural (EMF) from fructose using cellulose sulfuric acid as catalyst. Firstly, HMF was synthesized from fructose, and a high yield of 93.6 % was obtained in DMSO for 45 min in the presence of cellulose sulfuric acid. Cellulose sulfuric acid also showed high catalytic activity for the synthesis of EMF. EMF was obtained in a high yield of 84.4 % by the etherification of HMF under the optimal reaction conditions. More importantly, a high EMF yield of 72.5 % was also obtained from fructose through one-pot reaction strategy, which integrated the dehydration of fructose into HMF and the followed etherification of HMF into EMF. The reaction work-up was very simple and the catalyst could be reused several times without the loss of its catalytic activity.     

离子液体中微波辅助的 Lewis 酸催化纤维素制备 5-羟甲基糠醛

 以离子液体 1-丁基-3-甲基咪唑氯为溶剂, 以 CrCl3•6H2O 为催化剂, 直接转化纤维素生成 5-羟甲基糠醛 (HMF). 考察了微波辐射条件、反应温度、反应时间及催化剂用量对 HMF 产率的影响. 结果表明, 在最佳条件下, HMF 产率可达 55%.     

Highly efficient and N-bromosuccinimide-mediated conversion of carbohydrates to 5-hydroxymethylfurfural under mild conditions

Highly efficient and selective conversion of different carbohydrates to 5-hydroxymethylfurfural (HMF) has been successfully performed with N-bromosuccinimide (NBS) as a promoter. In the presence of single NBS, a 64.2 % yield of HMF from fructose was obtained in N-methylpyrrolidone for 2 h. The effects of time, temperature and reaction media are discussed. It was concluded that the preliminary bromination of substrate could improve the generation of HMF compared to the direct dehydration process. Moreover, the HMF yield could be elevated to 79.6 and 82.3 % when FeCl₃ and SnCl₄ were used as the additives, respectively. Furthermore, the addition of CrCl₃ facilitated the conversion pathway from glucose, sucrose, inulin, or cellulose to HMF. A 57.3, 68.2, 62.4, or 6.1 % yield of HMF was, respectively, obtained in the presence of CrCl₃ and NBS under mild conditions, which will therefore generate a promising application strategy for biomass transformation.     

Highly efficient preparation of 5-hydroxymethylfurfural from sucrose using ionic liquids and heteropolyacid catalysts in dimethyl sulfoxide–water mixed solvent

Several types of ILs and solid acids were used as catalysts in one-pot conversion of sucrose to 5-hydroxymethylfurfural (abbreviated as 5-HMF) in a dimethyl sulfoxide (DMSO)/water mixed solvent under hydrothermal conditions. A remarkable 5-HMF yield of 91.8% was achieved catalyzed by the cesium salt of dodecatungstophosphoric acid (Cs_2.3H_0.7PW₁₂O₄₀) within 3 h at 180 ℃. The ionic liquid N-methylimidazolium hydrogen sulfate ([Hmim][HSO₄]) gave the 5-HMF in 82.0% yield from sucrose. To the best of our knowledge, it was almost the highest yield of HMF from sucrose by now. Various reaction parameters including reaction temperature and time and catalyst dosage were optimized. A possible mechanism for this catalytic process was proposed. Furthermore, fructose and glucose were also investigated, good yields of 5-HMF was obtained respectively. This increases the possibility of large-scale production of 5-HMF from carbohydrates.     

Mechanisms and energetics for acid catalyzed β-D-glucose conversion to 5-hydroxymethylfurfurl

Car-Parrinello based ab initio molecular dynamics (CPMD) coupled with metadynamics (MTD) simulations were carried out to investigate the mechanism and energetics for acid-catalyzed β-d-glucose conversion to 5-hydroxymethylfurfurl (HMF) in water. HMF is a critical intermediate for biomass conversion to biofuels. It was found that protonation of the C2-OH on glucose, the breakage of the C2-O2 bond, and the formation of the C2-O5 bond is the critical rate-limiting step for the direct glucose conversion to HMF without converting to fructose first, contrary to the wide-spread assumption in literature that fructose is the main intermediate for glucose conversion to HMF. The calculated reaction barrier of 30-35 kcal/mol appears to be solvent-induced and is in excellent agreement with experimental observations.     

离子液体催化制备5-羟甲基糠醛的研究进展

本文综述了离子液体催化制备5-羟甲基糠醛的研究进展。运用离子液体作为反应溶剂和催化剂,与常规合成HMF的方法相比,其反应在常压、低温下进行,更易于操作控制;副反应数量明显减少,HMF的产率稳定,可达90%;离子液体催化活性稳定,可重复利用,减少了有机溶剂的使用量;利用离子液体作为媒介,能将反应原料从单一的果糖扩展到葡萄糖和纤维素等廉价原料,降低了生产成本。由此可见,运用离子液体催化制备HMF将是今后研究的重点和发展的必然趋势。     

Soybean Hulls Pretreated Using Thermo-Mechanical Extrusion—Hydrolysis Efficiency,Fermentation Inhibitors,and Ethanol Yield

Soybean hulls were subjected to thermo-mechanical extrusion pretreatment at various in-barrel moisture contents and screw speeds. Extrusion degraded the lignocellulosic structure and enhanced enzymatic hydrolysis of soybean hulls, with up to 155% increase in glucose yield as compared to untreated substrate. Greater glucose yields were observed at higher in-barrel moistures (45% and 50%) and lower screw speed (280 and 350 rpm). Maximum 74% cellulose to glucose conversion resulted from using a two-enzyme cocktail consisting of cellulase and β-glucosidase. Conversion increased to 87% when a three-enzyme cocktail having a cell wall degrading enzyme complex was used for hydrolysis. Fermentation inhibitors, such as furfural, 5-(hydroxymethyl)-2-furaldehyde (HMF), and acetic acid, were found in the extrusion pretreated soybean hulls and hydrolysate. However, their concentrations were below the known thresholds for inhibition. Fermentation of hydrolysate by Saccharomyces cerevisiae led to high yields of ethanol, with concentration ranging from 13.04 to 15.44 g/L.     

Critical Influence of 5‐Hydroxymethylfurfural Aging and Decomposition on the Utility of Biomass Conversion in Organic Synthesis

Spectral studies revealed the presence of a specific arrangement of 5‐hydroxymethylfurfural (5‐HMF) molecules in solution as a result of a hydrogen–bonding network, and this arrangement readily facilitates the aging of 5‐HMF. Deterioration of the quality of this platform chemical limits its practical applications, especially in synthesis/pharma areas. The model drug Ranitidine (Zantac®) was synthesized with only 15 % yield starting from 5‐HMF which was isolated and stored as an oil after a biomass conversion process. In contrast, a much higher yield of 65 % was obtained by using 5‐HMF isolated in crystalline state from an optimized biomass conversion process. The molecular mechanisms responsible for 5‐HMF decomposition in solution were established by NMR and ESI‐MS studies. A highly selective synthesis of a 5‐HMF derivative from glucose was achieved using a protecting group at O(6) position.     

Metal-free dehydration of glucose to 5-(hydroxymethyl)furfural in ionic liquids with boric acid as a promoter

The dehydration of glucose and other hexose carbohydrates to 5-(hydroxymethyl)furfural (HMF) was investigated in imidazolium-based ionic liquids with boric acid as a promoter. A yield of up to 42% from glucose and as much as 66% from sucrose was obtained. The yield of HMF decreased as the concentration of boric acid exceeded one equivalent, most likely as a consequence of stronger fructose-borate chelate complexes being formed. Computational modeling with DFT calculations confirmed that the formation of 1:1 glucose-borate complexes facilitated the conversion pathway from glucose to fructose. Deuterium-labeling studies elucidated that the isomerization proceeded via an ene-diol mechanism, which is different to that of the enzyme-catalyzed isomerization of glucose to fructose. The introduced non-metal system containing boric acid provides a new direction in the search for catalyst systems allowing efficient HMF formation from biorenewable sources.     

The “one-pot” synthesis of 2,5-diformylfuran,a promising synthon for organic materials in the conversion of biomass

The organic ionic oxidant 4-acetamido-2,2,6,6-tetramethyl-1-oxopiperidinium tetrafluoroborate, [Pip*(O)][BF₄], was found to be compatible with both classical organic solvents and the ionic liquids [BMIm][Cl]/[BMIm][BF₄] (BMIm is 1-butyl-3-methylimidazolium), which are essential in the conversion of cellulose biomass. A unique NMR monitoring procedure developed in our group was used to study the conversion of fructose to 2,5-diformylfuran in ionic liquids. This process can successfully be carried out in a “one-pot” fashion; [Pip*(O)][BF₄] efficiently oxidizes intermediate 5-hydroxymethylfurfural. The reaction is highly selective, giving 2,5-diformylfuran in 95% yield.     

Conversion of Glucose to Valuable Platform Chemicals over Graphene Solid Acid Catalyst

Biomass-derived hexose sugars, the most abundant renewable resources in the world, have potential to be the sustainable resources for production of platform chemicals. Here, conversion of glucose is investigated by using sulfonated graphene (rGO-SO₃H) as solid acid catalyst in water without any organic solvent. At first, graphene functionalized with sulfonic acid groups is prepared by using NaH and propane sultone, and then it is characterized by means of XPS, FT-IR, and TEM to confirm the existence of the sulfonic acid groups. The catalytic activity of rGO-SO₃H in the conversion of glucose to valuable chemicals is studied under different reaction conditions. The maximum yield of 5-hydroxymethylfurfural (HMF) is 28.8%, and the total yield of formic acid, lactic acid and HMF is 51.94% when the reaction is conducted at the optimized reaction condition. In addition, the rGO-SO₃H gives a relatively high total yield of the three kinds of products after five run experiments, indicating that the catalyst shows good thermal stability.     

催化选择转化多羟基化合物制备高附加值化学品研究进展

对近年来催化转化多羟基化合物制备5-羟甲基糠醛、乙二醇、1,2-丙二醇、1,3-丙二醇等高附加值化学品进行了综述. 分析了果糖、葡萄糖、纤维素等不同结构的碳水化合物制5-羟甲基糠醛存在的挑战, 并对相应的解决方法进行了总结. 对于5-羟甲基糠醛的转化, 我们重点讨论了5-羟甲基糠醛选择性氧化制备2,5-二甲酰基呋喃和2,5-呋喃二甲酸以及它们作为聚合单体的潜在应用. 概述了催化氢解纤维素、糖醇、甘油等多羟基化合物制备乙二醇、1,2-丙二醇、1,3-丙二醇等二元醇的方法, 并对可能的机理进行了讨论. 依据近年来多羟基化合物催化选择性转化制备高附加值化学品的研究现状, 对今后的研究热点进行了展望.     

有机相中利用脂肪酶催化的醇解反应拆分炔丙醇酮乙酸酯

 研究了有机相中脂肪酶催化的炔丙醇酮乙酸酯的立体选择性醇解反应, 考察了碱的种类、酰基受体和溶剂等对反应的影响. 结果表明, 以四氢呋喃为溶剂, CH3OH 为酰基受体, Lipase PLG 脂肪酶为催化剂, Na2CO3 为碱性添加剂, 高底物浓度下 40 oC 反应 96 h 后, 底物转化率和产物 ee 值分别达到 49.5% 和 99.5%. 碱的添加极大地提高了反应速度.     

碱催化促进Ni-W/β分子筛催化剂氢解纤维素产1,2-丙二醇的研究

为提高纤维素催化氢解产醇类产物中1,2-丙二醇(1,2-PG)的收率,采用等体积浸渍法制备了以β分子筛为载体负载Ni和W的催化剂。结果表明,当7Ni-20W/β分子筛作为催化剂时,在240℃反应温度和6.0 MPa H_2的条件下反应30 min后,纤维素实现完全转化,1,2-PG和乙二醇(EG)产率分别达到19.3%和45.3%;不同于其他载体催化剂,β分子筛可以明显提高1,2-PG选择性。当不同碱催化剂加入到Ni-W/β分子筛催化剂反应体系后,可以进一步提高1,2-PG的选择性。尤其是当加入Ba(OH)_2后,1,2-丙二醇产率从19.3%提高了32.5%。为了探究碱催化剂在反应中的作用,以葡萄糖为底物进行了一系列的碱催化反应。结果表明,碱催化剂主要作用是有助于将葡萄糖异构化为果糖,从而促进纤维素转化为1,2-PG。催化剂在两次回收重复利用之后1,2-PG的收率只下降3.9%,乙二醇产率收率下降4.1%。     

Selective oxidation of biomass derived 5-hydroxymethylfurfural to 2,5-diformylfuran using sodium nitrite

A mild and simple process for the effective oxidation of 5-hydroxymethylfurfural(HMF) into 2,5-diformylfuran(DFF) has been developed using Na NO_2 as the oxidant. Some important reaction parameters were investigated to optimize the oxidation of HMF into DFF. It was found that the reaction solvent was very crucial for this reaction. Trifluoroacetic acid was the best solvent for the oxidation of HMF into DFF by Na NO_2.Under the optimal reaction condition, almost quantitative HMF conversion and high DFF yield of 90.4% were obtained after 1 h at room temperature.     

在水-四氢呋喃中纤维素转化为5-羟甲基糠醛及副产物鉴定

在酸性条件下,水-四氢呋喃混合溶剂中转化纤维素制备了平台化合物5-羟甲基糠醛（HMF）．在纤维素浓度仅为2.4wt%时,可以得到38.6%的HMF,但是随着纤维素浓度的增加,胡敏素和乙酰丙酸成为主要产物．利用液相色谱-多级串联质谱联用技术检测到了分子式为C9H16O4、 C10H14O4、 C11H12O4、C12H10O5 和C12H16O8的一系列副产物．C9H16O4是通过四氢呋喃开环为1,4-丁二醇再与乙酰丙酸酯化反应得到,而C10H14O4是通过四氢呋喃开环后与HMF醚化得到．C11H12O4是由5-羟甲基糠醛与乙酰丙酸发生酯化反应得到,C12H10O5是由HMF自身醚化得到,而C12H16O8是HMF与葡萄糖经过缩醛反应得到．HMF的自身醚化反应及HMF与1,4-丁二醇的醚化反应是主要的副反应．     

An unexpected reaction between 5-hydroxymethylfurfural and imidazolium-based ionic liquids at high temperatures

A new compound was detected during the production of 5-hydroxymethylfurfural (HMF) from glucose and cellulose in the ionic liquid 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) at high temperatures. Further experiments found that it was derived from the reaction of HMF with [Bmim]Cl. The structure of new compound was established as 1-butyl-2-(5'-methyl-2'-furoyl)imidazole (BMI) based on nuclear magnetic resonance and mass spectrometry analysis, and a possible mechanism for its formation was proposed. Reactions of HMF with other imidazolium-based ionic liquids were performed to check the formation of BMI. Our results provided new insights in terms of side reactions between HMF and imidazolium-based ionic liquids, which should be valuable for designing better processes for the production of furans using biomass and related materials.