Selective transformation of biomass-derived 5-hydroxymethylfurfural into 2,5-dihydroxymethylfuran via catalytic transfer hydrogenation over magnetic zirconium hydroxides

An economical and effective approach for the selective transformation of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-dihydroxymethylfuran (DHMF) was developed by catalytic transfer hydrogenation over various magnetic zirconium hydroxides (MZHs). As expected, MZH with a moderate Zr/Fe molar ratio of 2 displayed the highest catalytic activity, resulting in 98.4% HMF conversion and 89.6% DHMF yield at 150 °C for 5 h in the presence of 2-butanol that simultaneously acted as the hydrogen donor and reaction solvent, which was ascribed to its appropriate specific surface area, pore size and acid-base content. Moreover, a plausible reaction mechanism for the catalytic transfer hydrogenation of HMF into DHMF over MHZ(Zr/Fe=2) was also proposed, in which the basic hydroxyl groups with the aid of acidic zirconium metal centers were considered to be responsible for the pivotal hydride transfer via a six-membered ring structure.     

An ionic liquid reaction and separation process for production of hydroxymethylfurfural from sugars

Hydroxymethylfurfural (HMF) is viewed as a potential platform material to make a variety of chemicals and products out of renewable resources. In this work, a complete ionic liquid reaction and separation process is presented for nearly stoichiometric conversion of fructose into HMF. The silicalite adsorbent material is demonstrated for separation of 99% pure HMF out of ionic liquid reaction mixtures through a packed column and for recovery of the unconverted sugars and reaction intermediates along with the ionic liquid. Membrane‐coated silicalite particles are prepared and studied for a practical adsorption process with separation performances comparable to or better than the powder material. It is discovered that nearly all the fresh fructose feed could be converted into HMF with the recycled ionic liquid under suitable reaction conditions. These research results lead to a new HMF production process much simpler than the current paraxylene manufacturing process from petroleum oil. © 2013 American Institute of Chemical Engineers AIChE J, 60: 300–314, 2014     

Dehydration of fructose into 5-hydroxymethylfurfural in the presence of ionic liquids

The acid-catalyzed dehydration of fructose was performed in a microbatch reactor at 80 °C using two commercially available ionic liquids, a hydrophilic one, 1-butyl 3-methyl imidazolium tetrafluoroborate (BMIM⁺BF₄⁻), and a hydrophobic one, 1-butyl 3-methyl imidazolium hexafluorophosphate (BMIM⁺PF₆⁻). When the reaction is carried out in 1-butyl 3-methyl imidazolium tetrafluoroborate as solvent and Amberlyst-15 as catalyst, a yield up to 50% in 5-hydroxymethylfurfural (HMF) is obtained within around 3 h. When the reaction is carried out now in 1-butyl 3-methyl imidazolium tetrafluoroborate and in 1-butyl 3-methyl imidazolium hexafluorophosphate as solvents and Amberlyst-15 as catalyst, DMSO is used as a co-solvent, in order, in particular, to solubilize fructose in the hydrophobic ionic liquid. Under these conditions, both ionic liquids allow the reaction to work more rapidly than in DMSO alone and with yields in HMF close to 80% within 24 h.     

The preparation of 5-hydroxymethylfurfuraldehyde from high fructose corn syrup and other carbohydrates

5-Hydroxymethylfurfuraldehyde (HMF) was prepared from high fructose corn syrup (HFCS), or crystalline D -fructose, in high yield and purity. A 95–97% conversion of fructose to HMF was achieved using 25 mol% (based on fructose) boron trifluoride etherate catalyst in dimethyl sulphoxide, under a nitrogen atmosphere, a reaction temperature of 273 K and 30 min reaction time. Inferior yields of HMF were obtained from glucose and starch.     

Ring opening polymerization of 2,5-dihydro-2,5-dimethoxyfuran by electrochemical initiation

Summary 2,5-Dihydro-2,5-dimethoxyfuran (DHMF) was polymerized via constant current electrolysis (CCE), in CH₃CN-NaClO₄ solvent-electrolyte couple. Poly(DHMF) was obtained from the anolyte. The effect of current density, temperature, monomer and electrolyte concentrations on the polymer yield have been examined. The apparent activation energy for CCE of DHMF was found to be 37.2 kj/mol. The FTIR and ¹H-NMR analyses show that DHMF polymerizes by a ring opening. Molecular weight of poly(DHMF) was found by using cryoscopy.     

High yield production and purification of 5‐hydroxymethylfurfural

Conversion of carbohydrates to 5‐hydroxymethylfurfural (HMF) will provide a new step toward achieving renewable biomass‐based chemicals and fuels platform. Recently, the excellent yield of HMF (91.0%) in dimethyl sulfoxide (DMSO) catalyzed by sulfonated carbon was demonstrated, but the separation of HMF from the reaction mixture remains challenging because of the high boiling point of DMSO. As a solution, herein, low boiling point solvent tetrahydrofuran (THF) mixed with DMSO was used for the fructose dehydration and high yield of HMF (98.0%) was still obtained. Besides, the stability of the sulfonated carbonaceous catalyst was also confirmed. More importantly, HMF from the reaction solution was successfully separated by using simple extraction method, and high purity of HMF (ca. 96.4%) was obtained. Compared with pure DMSO solvent, the combination of low boiling point THF with DMSO not only gives higher yield of HMF, but also improves the separation efficiency and reduces environmental risk. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2558–2566, 2013     

Reactive adsorption for the selective dehydration of sugars to furans: Modeling and experiments

5‐hydroxymethylfurfural (HMF) can be produced from the acid‐catalyzed dehydration of fructose, but its yield is limited due to subsequent HMF degradation to side products. A reactive adsorption process is proposed to improve the yield to HMF. Separate experimental single‐component isotherms of fructose, HMF, formic acid, and levulinic acid on carbon BP2000 and reaction kinetics of the fructose dehydration to HMF in aqueous solution of HCl are presented to develop empirical isotherms and kinetic rate constants, respectively. These submodels are subsequently integrated in an adsorptive reactor at a range of temperatures (100–150^°C) with different loadings of adsorbent. It is shown that the adsorbent improves HMF yield compared to the single‐solution phase (adsorbent‐free case). Low temperatures and high‐adsorbent loadings improve HMF yield. Under certain conditions both reactive adsorption and the commonly used reactive extraction can result in a similar improvement in HMF yield. HMF recovery from the solid adsorbent has been identified as a major challenge that can be ameliorated through adsorbent and solvent selection. The framework outlined here can be applied to any aqueous phase chemistry where the desired product is an intermediate in a reaction cascade. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3378–3390, 2013     

HMF路线合成生物基单体2,5-呋喃二甲酸的研究进展

2,5-呋喃二甲酸（FDCA）是合成聚（呋喃二甲酸乙二醇酯）（PEF）等生物基聚酯的重要单体,具有广阔的应用前景。FDCA能否实现低廉、高效的大规模生产,是生物基聚酯开发的关键。目前,FDCA合成的研究广受关注,工业化开发也正在进行中。本文对合成生物基单体FDCA的5-羟甲基糠醛（HMF）路线进行综述,重点介绍了水、高沸点有机溶剂、低沸点有机溶剂、双相体系和离子液体中的糖类脱水合成HMF,无碱水溶液、碱性水溶液和有机溶剂中的HMF氧化合成FDCA以及糖类一锅法合成FDCA的研究进展。在比较各种合成方法的基础上,认为当前应着重研究开发低沸点溶剂中糖类脱水合成HMF以及无碱水溶液或有机溶剂中低廉高效的HMF氧化新方法,并向着糖类一锅法合成FDCA的方向发展。     

固体酸催化果糖制备5-羟甲基糠醛的研究

研究了以二甲基亚砜为溶剂、TiO_2-SiO_2为催化剂催化果糖脱水生成5-羟甲基糠醛(HMP)的反应,分别考察了不同摩尔比TiO_2-SiO_2催化剂、反应时间、催化剂用量、果糖添加量等工艺参数对果糖脱水制备HMF催化活性的影响.在TiO_2-SiO_2作为催化剂、150℃和反应3 h的条件下,5-羟甲基糠醛的收率可达83.8%.     

Catalytic dehydration of glucose to 5‐hydroxymethylfurfural with a bifunctional metal‐organic framework

Glucose conversion to 5‐hydroxymethylfurfural (HMF) generally undergoes catalytic isomerization reaction by Lewis acids followed by the catalytical dehydration to HMF with Brönsted acid. In this work, a sulfonic acid functionalized metal‐organic framework MIL‐101(Cr)‐SO₃H containing both Lewis acid and Brönsted acid sites, was examined as the catalyst for γ‐valerolactone‐mediated cascade reaction of glucose dehydration into HMF. Under the optimal reaction conditions, the batch heterogeneous reaction gave a HMF yield of 44.9% and selectivity of 45.8%. Reaction kinetics suggested that the glucose isomerization in GVL with 10 wt % water follows the second‐order kinetics with an apparent activation energy of 100.9 kJ mol^?1. Continuous reaction in the fixed‐bed reactor showed that the catalyst is highly stable and able to provide a steady HMF yield. This work presents a sustainable and green process for catalytic dehydration of biomass‐derived carbohydrate to HMF with a bifunctional metal‐organic framework. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4403–4417, 2016     

Catalytic production of hydroxymethylfurfural from sucrose using 1-methyl-3-octylimidazolium chloride ionic liquid

Hydroxymethylfurfural (HMF) is an important chemical intermediate, but it has not been widely used because of low yields and high production costs. Sucrose is available at lower costs than other sugars and thus could be a biomass-derived abundant source for HMF production. In this study, a catalytic process for efficiently producing HMF from sucrose was scrutinized using 1-methyl-3-octylimidazolium chloride ([MOIM]Cl) as a reaction solvent, and HCl and metal chlorides (CrCl₂ and Zncl₂) as a catalyst. The rate of sucrose hydrolysis was relatively much faster in the reactions with HCl than without it. The hydrolysis of sucrose to fructose and glucose was affected by its reaction time. The mixed solvent of 50% [MOIM]Cl and 50% sucrose solution with HCl was more effective in HMF synthesis than single solvent alone. The addition of ZnCl₂ and CrCl₂ increased HMF yields by approximately 1.2–1.8-fold and its higher yield was found in the latter. The highest yield (82.0±3.9 wt%) in HMF production was achieved in the reaction mixture containing 5 g [MOIM]Cl and 5 mL of 20% sucrose solution with 0.5M HCl plus CrCl₂ at 30 min reaction time. However, 0.3 M HCl was more effective for the HMF productivity than 0.5 M HCl.     

Carbocatalyst in biorefinery: Selective etherification of 5-hydroxymethylfurfural to 5,5′(oxy-bis(methylene)bis-2-furfural over graphene oxide

Hydroxymethylfurfural (HMF) is an important biomass based building block which can be efficiently produced from carbohydrates, while the utility of HMF warrants further exploration. Herein, we explored a green method for the transformation of HMF into a symmetrical ether named 5′-oxy(bis-methylene)-2-furaldehyde (OBMF) promoted by graphene oxide (GO). HMF conversion in no-polar solvents was obviously higher than that in polar solvents. Water existed in the reaction system could significantly decrease the OBMF yield. Moreover, the high catalytic performance of GO was closely related to oxygen containing groups on GO. A maximum OBMF yield of 86% was obtained under optimized conditions.     

葡萄糖催化脱水制取5-羟甲基糠醛研究进展

5-羟甲基糠醛(HMF)是重要的平台化合物,是制取生物液体燃料和其他许多重要精细化工品的前驱体。以木质纤维素为原料,通过水解得到葡萄糖,葡萄糖继续脱水可以得到5-羟甲基糠醛。本文对近年来利用葡萄糖制取5-羟甲基糠醛的研究进行了综述,重点阐述了葡萄糖脱水制取5-羟甲基糠醛过程的反应机理、反应体系和催化剂,并对未来可能取得突破的研究重点进行了评述与展望。     

Commercially attractive process for production of 5-hydroxymethyl-2-furfural from high fructose corn syrup

5-Hydroxymethyl-2-furfural (HMF) was prepared with high fructose corn syrup (HFCS) manufactured directly from industry. Equipped industrial process and cheaper availability considered HFCS-90 as a competitive starter for production of HMF. Readily evaporable solvent, 1,4-dioxane was found as a promising reaction media from the screening of various solvents and readily available cation exchange resin, Amberlyst-15 was used as a solid acid catalyst. Parametric variation studies including amount of catalyst, concentration of HFCS-90, and reaction temperature were performed to achieve a maximum HMF yield of 80% at 100 °C within 3 h. In particular, use of readily evaporable solvent and heterogeneous catalyst allowed highly practical purification of HMF, which still remains as a major obstacle to the commercialization of HMF. With filtration, evaporation, and extraction, HMF was simply isolated in 72% yield and ¹H NMR spectra of the isolated HMF confirmed that its purity was sufficient for use in next step of reactions. In addition, all solvents could be recycled with distillation and catalyst was reused up to 5 cycles without a significant loss of activity.     

Polymer-supported N-heterocyclic carbene-iron(III) catalyst and its application to dehydration of fructose into 5-hydroxymethyl-2-furfural

Polymer-supported NHC–metal catalysts were prepared from chloromethyl polystyrene resin via two-step reaction. Metals were loaded into 1.6 – 16 mol% of total imidazolium and the remaining imidazolium chloride salt provided ionic liquid moiety. The formation of metal complex with the polymer-supported NHC ligand was analyzed by ATR FT-IR, XRD, and XPS. The synthesized polymer-supported NHC–metal catalysts were applied to the dehydration of fructose into HMF. The environmentally benign and inexpensive polymer-supported NHC–Fe^III catalyst showed good catalytic activity and yielded HMF at 73% (with a conversion of 97%). It could also be reused without significant loss of catalytic activity.     

Absence of expected side-reactions in the dehydration reaction of fructose to HMF in water over niobic acid catalyst

The catalytic dehydration of fructose (FRU) to 5-hydroxymethylfurfural (HMF) usually runs with the formation of several side products. Among these, levulinic acid (LA) is often reported as the product of a consecutive reaction of HMF re-hydration. In this work, side reactions of the dehydration of FRU performed in very green conditions (water as solvent and niobic acid as solid catalyst) are taken into account. Experimental evidences are given that, in the used conditions: i) HMF is a final stable product, ii) no formation of LA, either deriving from a consecutive reaction of HMF or directly from FRU transformation, was observed, and iii) LA does not react to give condensation products with any other chemical species present in the reaction mixture.     

木质纤维素制备5-羟甲基糠醛的催化过程强化

5-羟甲基糠醛(HMF)是一种链接可再生生物质资源与燃料化合物及化学中间体的重要新型平台化合物。文中对高温(180—200℃)条件下,金属氯化物为催化剂,离子液体[BMIM]Cl为溶剂,木质纤维素(相思木木屑)为原料快速制备HMF和糠醛的反应过程进行了研究。通过对反应温度、原料用量、盐酸(HCl)添加量、催化剂种类及用量等因素进行考察,优化了反应条件。研究结果表明:与文献报道的低温下纤维素降解反应相比,高温条件可使木质纤维素为原料制备HMF的反应过程得到强化。在所考察的金属氯化物催化剂中,CrCl3.6H2O的催化效果最优,其中以CrCl3.6H2O为催化剂,200℃下反应4 min时产物HMF及糠醛的收率分别可达55.0%和22.9%。该高温反应过程反应快速、产物收率高,无需木质纤维素原料的预处理操作,为工业上简单快速制备HMF提供了一种可行方法。     

Conversion of carbohydrates into 5‐hydroxymethylfurfural in a green reaction system of CO2‐water‐isopropanol

In this work, a green reaction system of CO₂‐water‐isopropanol was developed for 5‐hydroxymethylfurfural (HMF) production. The conversion of fructose in a CO₂‐water system was first investigated, and the results showed this system could promote the formation of HMF compared to a pure water system. Then, isopropanol was introduced into the CO₂‐water system and the HMF formation became better because the solvent effect of isopropanol increased the tautomeric composition of fructofuranose, which was easy to form HMF. The existence of isopropanol was found to greatly suppress secondary reactions where HMF was converted to levulinic acid and insoluble humin. Meanwhile, the effects of reaction parameters on the conversion of fructose to HMF in the CO₂‐water‐isopropanol system were analyzed, and a high HMF yield of 67.14% was obtained. Finally, to further illustrate the merits of CO₂‐water‐isopropanol system, productions of HMF from other carbohydrates were tested and satisfactory yields were achieved. © 2016 American Institute of Chemical Engineers AIChE J, 63: 257–265, 2017     

半纤维素六碳糖转化为5-羟甲基糠醛的动力学

选取甘露糖和半乳糖两种典型半纤维素六碳糖作为模化物,考察其在水相中较宽温度（100～200℃）和时间（10～240min）范围内的降解行为。实验结果表明,较高的反应温度能提高六碳糖的转化率和5-羟甲基糠醛（HMF）的产率;在200℃时甘露糖和半乳糖生成的HMF最高产率分别为26.82%和22.86%,乙酰丙酸（LA）的产率低于3%;半乳糖因容易异构化生成塔格糖而非果糖,导致其HMF产率较低。采用六碳糖平行生成HMF和Humin,随后HMF平行生成的LA和Humin的反应模型对六碳糖降解动力学进行分析,揭示了六碳糖的类型对HMF和Humin生成机制的影响。此外,针对六碳糖生成的Humin的Van Krevelen图和FTIR谱图进行分析进一步发现,Humin是通过脱水聚合生成的呋喃环基聚合物,同时其结构特征与单糖类型紧密相关。     

Water-Compatible Lewis Acid-Catalyzed Conversion of Carbohydrates to 5-Hydroxymethylfurfural in a Biphasic Solvent System

Water-compatible lanthanide-based Lewis acids for the efficient conversion of glucose and other carbohydrates to produce 5-hydroxymethylfurfural (HMF) were demonstrated in a biphasic reactor using sec-butyl phenol as the extracting solvent. The reaction of glucose dehydration to HMF was found to proceed under near-neutral conditions (pH?=?5.5) and a moderately high yield of 42?mol?% could be obtained. The combined catalytic system also showed effectiveness to convert other polysaccharides to HMF. Furthermore, the aqueous phase was recycled and used for multiple times without significant loss of catalytic performance.