Efficient microwave-assisted synthesis of 5-hydroxymethylfurfural from concentrated aqueous fructose

Studies on the HCl-catalysed microwave-assisted dehydration of highly concentrated aqueous fructose (27 wt %) to 5-hydroxymethylfurfural (HMF) revealed a significant increase in the fructose conversion rate over the conventional heated systems. Water, being the most benign solvent and therefore ideal for green and sustainable chemistry, normally is a poor solvent for the dehydration process resulting in low HMF selectivities and yields. However, reaction at 200 °C with microwave irradiation with a short reaction time of only 1 s resulted in good HMF selectivity of 63% and fructose conversion of 52%, while prolonged irradiation for 60 s (or more) resulted in nearly full fructose conversion (95%) but lower HMF yield (53%). Decreasing the fructose concentration significantly improved the HMF selectivity, but possibly made the production route less attractive from an industrial point of view due to the resultant low throughput.     

Production of 5-hydroxymethylfurfural in ionic liquids under high fructose concentration conditions

Acid-promoted, selective production of 5-hydroxymethylfurfural (HMF) under high fructose concentration conditions was achieved in ionic liquids (ILs) at 80 °C. A HMF yield up to 97% was obtained in 8 min using 1-butyl-3-methylimidazolium chloride ([C₄mim]Cl) catalyzed with 9 mol % hydrochloric acid. More significantly, an HMF yield of 51% was observed when fructose was loaded at a high concentration of 67 wt % in [C₄mim]Cl. Water content below 15.4% in the system had little effect on HMF yield, whereas a higher water content was detrimental to both reaction rate and HMF yield. In situ NMR analysis suggested that the transformation of fructose to HMF was a highly selective reaction that proceeded through the cyclic fructofuranosyl intermediate pathway. This work increased our capacity to produce HMF, and should be valuable to facilitate cost-efficient conversion of biomass into biofuels and bio-based products.     

Effect of Formic Acid on Conversion of Fructose to 5-Hydroxymethylfurfural in Aqueous/Butanol Media

Acid-catalyzed dehydration of carbohydrates into 5-hydroxymethylfurfural (HMF), a valuable biomass-derived intermediate, has received increasing attention. Efficient methods for HMF production are needed for successful commercialization of HMF in the near future. A new process for the dehydration of sugars into 5-hydroxymethylfurfural in aqueous/butanol media enhanced by using formic acid was developed. The effects of formic acid concentration, reaction temperature, and reaction time on the fructose conversion and HMF yield showed the significant influences of these process variables. The optimum conditions were found to be 2.5?mol/L formic acid concentration, 170°C and 70?min. Under such conditions, a fructose conversion of 98.3% with a HMF yield of 69.2% was achieved. The application of the butanol solvent and formic acid led to the conversion of fructose to HMF with high yield. The catalytic system in this study has prospects for commercial application due to its less corrosion and convenient downstream separation.     

Conversion of biomass into 5-hydroxymethylfurfural using solid acid catalyst

5-Hydroxymethylfurfural (HMF) was produced from monosaccharide (fructose and glucose), polysaccharide (inulin) and the Jerusalem artichoke juice by a simple one-pot reaction including hydrolysis and dehydration using solid acid under mild condition. Hydrated niobium pentoxide (Nb(2)O(5)·nH(2)O(2)) after pretreatment showed high catalytic activities for dehydration of mono- and polysaccharide to HMF at 433 K in water-2-butanol (2:3 v/v) biphasic system, giving high HMF yield of 89% and 54% from fructose and inulin, respectively. The HMF yield was up to 74% and 65% when inulin and Jerusalem artichoke juice were hydrolyzed by exoinulinase. The solid acid made the process environment-friendly and energy-efficient to convert carbohydrates into bio-fuels and platform chemicals.     

Efficient and selective conversion of sucrose to 5-hydroxymethylfurfural promoted by ammonium halides under mild conditions

The highly efficient and selective production of 5-hydroxymethylfurfural (HMF) from sucrose has been achieved in the presence of metal chlorides and ammonium halides under mild conditions. Notably, an 87% yield of HMF from sucrose was obtained with a catalyst system composed of CrCl(3) and NH(4)Br at 100°C for 1.0 h in N,N-dimethylacetamide (DMAc) solvent. The effect of the reaction temperature and time was investigated in detail, and a possible mechanism for this catalytic process has been proposed. In addition, NH(4)Br is an effective promoter in the conversion of glucose and fructose to HMF.     

Catalytic hydrolysis of lignocellulosic biomass into 5-hydroxymethylfurfural in ionic liquid

Production of 5-hydroxymethylfurfural (HMF) from cellulose catalyzed by solid acids and metal chlorides was studied in the 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) under microwave irradiation. Among the applied catalysts, the use of CrCl₃/LiCl resulted in the highest yield of HMF. The effects of catalyst dosage (mole ratio of catalyst to glucose units in the feedstock) and reaction temperature on HMF yields were investigated to obtain optimal process conditions. With the 1:1 mol ratio of catalyst to glucose unit, the HMF yield reached 62.3% at 160 °C for 10 min. Untreated wheat straw was also investigated as feedstock to produce HMF for the practical use of raw biomass, in which the HMF yield was comparable to that from pure cellulose. After the extraction of HMF, [BMIM]Cl and CrCl₃/LiCl could be reused and exhibited no activity loss after three successive runs.     

Conversion of hexose into 5-hydroxymethylfurfural in imidazolium ionic liquids with and without a catalyst

Conversion of fructose and glucose into 5-hydroxymethylfurfural (HMF) was investigated in various imidazolium ionic liquids, including 1-butyl-3-methylimidazolium chloride (BmimCl), 1-hexyl-3-methylimidazolium chloride (HmimCl), 1-octyl-3-methylimidazolium chloride (OmimCl), 1-benzyl-3-methylimidazolium chloride (BemimCl), 1-Butyl-2,3-dimethylimidazolium chloride (BdmimCl), and 1-butyl-3-methylimidazolium p-toluenesulfonate (BmimPS). The acidic C-2 hydrogen of imidazolium cations was shown to play a major role in the dehydration of fructose in the absence of a catalyst, such as sulfuric acid or CrCl₃. Both the alkyl groups of imidazolium cations and the type of anions affected the reactivity of the carbohydrates. Although, except BmimCl and BemimCl, other four ionic liquids could only achieve not more than 25% HMF yields without an additional catalyst, 60–80% HMF yields were achieved in HmimCl, BdmimCl, and BmimPS in the presence of sulfuric acid or CrCl₃ in sufficient quantities.     

Production of furans from rice straw by single-phase and biphasic systems

5-Hydroxymethylfurfural (HMF) and furfural, both of which can be derived from renewable sources, are key components for the production of different chemicals and fuels. In this study, rice straw, a cheap, abundant, and mainly unused agricultural waste, is converted to furans by a dilute acid hydrolysis process. The highest yield of HMF in a single-phase hydrolysis was 15.3 g/kg straw, attained at 180 °C during 3 h with 0.5% sulfuric acid, while the maximum yield of furfural, 59 g/kg straw, was obtained at 150 °C during 5 h. Different extracting solvents, including 2-PrOH, 1-BuOH, methyl isobutyl ketone (MIBK), and acetone at 180 °C for 3 h as well as tetrahydrofuran (THF) at 150 °C for 5 h were examined in biphasic systems. Use of the solvents generally improved the production of HMF compared to the single aqueous phase process. The best results of HMF production, more than 59 g/kg straw, were obtained in the systems containing either 2-PrOH or 1-BuOH. Using THF as an extracting solvent, a relatively high furfural yield, 118.2 g/kg straw, was obtained, and 96% of furfural produced in this system was extracted into THF during the process.     

Dehydration of fructose to 5-hydroxymethylfurfural by rare earth metal trifluoromethanesulfonates in organic solvents

The catalytic dehydration of fructose to 5-hydroxymethylfurfural (HMF) was investigated by using various rare earth metal trifluoromethanesulfonates, that is, Yb(OTf)₃, Sc(OTf)₃, Ho(OTf)₃, Sm(OTf)₃, Nd(OTf)₃ as catalysts in DMSO. It is found that the catalytic activity increases with decreasing ionic radius of rare earth metal cations. Among the examined catalysts, Sc(OTf)₃ exhibits the highest catalytic activity. Fructose conversion of 100% and a HMF yield of 83.3% are obtained at 120 °C after 2 h by using Sc(OTf)₃ as the catalyst. Moreover, the catalytic dehydration of fructose was also carried out in different solvents, for example, DMA, 1,4-dioxane, and a mixture of PEG-400 and water. The results show that among the solvents DMSO is the most efficient in promoting the dehydration of fructose to HMF, and no rehydration byproducts such as levulinic acid and formic acid are detected.     

Reaction pathways of glucose during esterification: effects of reaction parameters on the formation of humin type polymers

The formation of humin-type polymers and other products during exposure of glucose to methanol/water mixtures with methanol/water mass ratios from 10 to 0.22 in the presence of the acid catalyst Amberlyst 70 was investigated. In water-rich medium (methanol/water mass ratio: 0.22), dehydration of glucose produced 5-(hydroxymethyl)furfural (HMF), furfural, and substantial amounts of polymer. In methanol-rich medium (methanol/water mass ratio: 10), the hydroxyl and carbonyl groups of glucose, HMF or furfural were protected via etherification and acetalisation. These protections stabilized these reactive compounds and significantly lowered the polymer formation (1.43% of the glucose loaded). The polymerization of glucose and HMF was also favored at high temperatures and long residence times. Conversely, high catalyst dosage mainly accelerated the conversion of glucose to methyl levulinate. Thus, the polymerization of glucose and HMF can be suppressed in methanol/water mixtures with high methanol ratios, at low temperatures and short residence times.     

Studies on Guizotia abyssinica L. oil: Biodiesel synthesis and process optimization

Guizotia abyssinica seeds, a common bird feedstock, have been explored for the potential of biodiesel synthesis. The oil was extracted from the seeds by solvent extraction and composition of G. abyssinica oil was examined. The reaction parameters for biodiesel synthesis have been optimized. Temperature, oil: methanol ratio, catalyst type and catalyst concentration were found to have significant role on ester conversion. According to this study, the maximum yield of ester (98.7%) can be obtained with optimized sodium methoxide catalyst dosage (0.6%) at an operational temperature of 65 °C. Methyl ester of G. abyssinica oil was also studied for its oxidation stability and low temperature properties. Further, the synthesized product was blended in diesel at 5–20% ratios and evaluated for physico-chemical properties.     

Catalytic conversion of cellulose to 5-hydroxymethyl furfural using acidic ionic liquids and co-catalyst

Efficient catalytic conversion of microcrystalline cellulose (MCC) to 5-hydroxymethyl furfural (HMF), is achieved using acidic ionic liquids (ILs) as the catalysts and metal salts as co-catalysts in the solvent of 1-ethyl-3-methylimidazo-lium acetate ([emim][Ac]). A series of acidic ILs has been synthesized and tested in conversion of MCC to HMF. The effect of reaction conditions, such as reaction time, temperature, catalyst dosage, metal salts, water dosage, Cu(2+) concentration and various acidic ILs are investigated in detail. The results show that CuCl(2) in 1-(4-sulfonic acid) butyl-3-methylimidazolium methyl sulfate ([C(4)SO(3)Hmim][CH(3)SO(3)]), is found to be an efficient catalyst for catalytic conversion of MCC to HMF, and 69.7% yield of HMF is obtained. A mechanism to explain the high activity of CuCl(2) in [C(4)SO(3)Hmim][CH(3)SO(3)] is proposed. To the best of our knowledge, this report first proposes that the Cu(2+) and [C(4)SO(3)Hmim][CH(3)SO(3)] show better catalytic performance in catalytic conversion of MCC to HMF.     

Lipase-catalyzed methanolysis of palm oil in presence and absence of organic solvent for production of biodiesel

Enzymatic production of methyl esters (biodiesel) by methanolysis of palm oil in presence and absence of organic solvent was investigated using Candida antarctica lipase immobilized on acrylic resin as a biocatalyst. Although, at least molar equivalent of methanol (methanol-palm oil ratio 3:1) is required for the complete conversion of palm oil to methyl esters, lipase catalyzed methanolysis of palm oil in absence of organic solvent was poisoned by adding more than 1/3 molar equivalent of methanol. The use of polar organic solvents prevented the lipase to be poisoned in methanolysis with a molar equivalent of methanol, and tetrahydrofuran (THF) was found to be the most effective. The presence of water in methanolysis of palm oil both in presence and absence of THF inhibited the reaction rate but this inhibition was considerably low in THF containing system. The palm oil-lipase (w/w) ratio significantly influenced the activity of lipase and the optimal ratio in presence and absence of THF was 100 and 50, respectively.     

The influence of the initial and catalyst concentrations on the dehydration of d-fructose

The dehydration at 95° of d-fructose (0.25m-1.0m) to 5-hydroxymethyl-2-furaldehyde (HMF) and the rehydration of HMF (0.25-1.0m) to levulinic and formic acids in 0.5-2m HCl has been studied. The conversion rate of d-fructose was proportional to the Hammett activity. The acidity had a smaller influence on the conversion rate of HMF, although it was not proportional to the catalyst concentration. The rehydration of HMF was faster in the presence of d-fructose. The yield of levulinic acid was independent of the catalyst concentration, but was lower at higher initial concentrations of d-fructose and HMF, and a kinetic model has been derived. The formation of humin was of an overall order 1.3 in an intermediate between d-fructose and HMF, and of an order 1.7 in an intermediate between HMF and levulinic acid.     

Glucose reactions with acid and base catalysts in hot compressed water at 473 K

The effects of the homogeneous catalysts (H(2)SO(4) and NaOH) and heterogeneous catalysts (TiO(2) and ZrO(2)) on glucose reactions were examined in hot compressed water (473 K) by a batch-type reactor. From the homogeneous catalyst studies, we confirmed that the acid catalyst promoted dehydration, while isomerization of glucose to fructose was catalyzed by alkali. Anatase TiO(2) was found to act as an acid catalyst to promote formation of 5-hydroxymethylfuraldehyde (HMF). Zirconia (ZrO(2)) was a base catalyst to promote the isomerization of glucose. The effects of the additives were also confirmed through fructose reactions.     

A new method for extraction of iron-molybdenum cofactor (FeMoco) from nitrogenase adsorbed to DEAE-cellulose. 2. Solubilization of FeMoco in a wide range of organic solvents

While the iron-molybdenum cofactor (FeMoco) of nitrogenase, a constituent of the active site for nitrogen reduction, can be extracted into N-methylformamide (NMF) and pyrrollidinone, the inability to solubilize it in any other organic solvents has hampered further understanding of its structure and chemical properties. A method to solubilize FeMoco, prepared in N,N-dimethylformamide (DMF) with Bu4N+ as counterion [McLean, P. A., Wink, D. A., Chapman, S. K., Hickman, A. B., McKillop, D. M., & Orme-Johnson, W. H. (1989) Biochemistry (preceding paper in this issue)], in acetonitrile, acetone, methylene chloride, tetrahydrofuran, and benzene is reported. FeMoco evaporated to dryness in vacuo dissolves readily in good yield (55-100%) and with no significant loss in specific activity. In addition, FeMoco can be extracted directly into these solvents from MoFe protein bound to a DEAE-Sepharose column if the protein is pretreated with DMF. Methods have also been developed to extract fully active FeMoco into acetone and acetonitrile in the absence of any amide solvents (NMF or DMF). Extraction of FeMoco into acetone (30% yield) involves only pretreatment of column-bound protein with methanol, while extraction into acetonitrile (22% yield) requires pretreatment with methanol followed by THF. We conclude that the presence of a suitable soluble cation confers solubility to the cofactor in many common organic solvents and that the solubility of FeMoco in a given solvent may be independent of the ability of that solvent to extract the cofactor from column-bound protein.     

贮存时间对不同蜜源蜂蜜中羟甲基糠醛含量增速的影响

为了更好控制蜂蜜在贮藏和流通过程中的羟甲基糠醛含量,研究了其在贮存过程中羟甲基糠醛的增长规律。本文对192个不同蜜源的蜂蜜在常温贮存期间的羟甲基糠醛含量进行了检测,统计了贮存时间和蜜源对羟甲基糠醛增长速率的影响,并分析了组分对羟甲基糠醛增率的相关性。结果表明,贮存450d内,蜂蜜的羟甲基糠醛增率与贮存时间呈正相关;椴树蜜、洋槐蜜、紫云英蜜和百花蜜的羟甲基糠醛增率无显著差异,且极显著高于枣花蜜;羟甲基糠醛增率与葡萄糖含量呈显著相关;果葡比极显著相关于酸度。     

Comparative LCA studies of simulated HMF biorefineries from maize and miscanthus as an example of first- and second-generation biomass as a tool for process development

5-Hydroxymethylfurfural (HMF) is a versatile platform chemical for a fossil free, bio-based chemical industry. HMF can be produced by using fructose as a feedstock. Using edible, first-generation biomass to produce chemicals has been questioned in terms of potential competition with food supply. Second-generation biomass like miscanthus could be an alternative. However, there is a lack of information if second-generation lignocellulosic biomass is a more sustainable feedstock to produce HMF. Therefore, a life cycle assessment was performed in this study to determine the environmental impacts of HMF production from miscanthus and to compare it with HMF from high-fructose corn syrup (HFCS). HFCS from either Hungary or Baden-Württemberg (Germany) was considered. Compared to the HFCS biorefineries the miscanthus concept is producing less emissions in all impact categories studied, except land occupation. Overall, the production and usage of second-generation biomass could be especially beneficial in areas where the use of N fertilizers is restricted. Besides, conclusions for the further development of the on-farm biorefinery concept were elaborated. For this purpose, process simulations from a previous study were used. Results of the previous study in terms of TEA and the current LCA study in terms of environmental sustainability indicate that the lignin depolymerization unit in the miscanthus biorefinery has to be improved. The scenario without lignin depolymerization performs better in all impact categories. The authors recommend to not further convert the lignin to products like phenol and other aromatic compounds. The results of the contribution analyses show that the major impact in the HMF production is caused by the auxiliary materials in the separation units and the required heat. Further technical development should focus on efficient heat as well as solvent use and solvent recovery. At this point further optimizations will lead to reduced emissions and costs at the same time.     

Alcohol fermentation of sweet potato. I. Acid hydrolysis and factors involved

Factors affecting acid hydrolysis of sweet potato powder (SSP) to fermentable sugars were examined. These include HCl concentration, temperature, time, and levels of SPP. Maximum reducing sugar, reported as dextrose equivalent (DE), was detected after 24 min hydrolysis (1% SPP) in 0.034N HCl heated at 154°C. These samples also had 3.43% droxymethylfurfural (HMF) based on dry weight. A high level of HMF (9.2%) was detected in 1% SPP heated at 154° in 0.10N HCl for 18 min. The lowest concentration of HMF formed (1.8%), at maximal DE of 61%, was established in samples containing 5% SPP and heated at 154° in 0.034N HCl for 48 min. Aqueous extracts of uncured SPP, examined by HPLC, contained glucose, fructose and sucrose, but degraded SPP had only glucose and fructose. Products of degraded SPP, under appropriate conditions, could be used for alcohol fermentation.