Production Of 5-hydroxymethylfurfural Research Articles

Kinetics of 5-hydroxymethylfurfural production from monosaccharides in media containing an ionic liquid and a solid acid catalyst

Glucose and mannose, the major structural units found in softwood hemicelluloses, were used to produce 5-hydroxymethylfurfural (HMF) in the ionic liquid 1-butyl-3-methylimidazolium chloride, in the presence of a commercial zeolite (which acted as an acidic catalyst), and in the presence or absence of co-catalysts. Experiments were performed under diverse operational conditions, and the reaction kinetics were interpreted by a mechanism involving three major reactions (non-productive substrate conversion, HMF generation, and HMF decomposition). Activation energies were determined for the best reaction medium.

Continuous 5-Hydroxymethylfurfural Production from Monosaccharides in a Microreactor

5-Hydroxymethylfurfural (HMF) was effectively produced from monosaccharides in a microreactor. A biphasic reaction system was employed to achieve the immediate extraction of produced HMF and suppress the overreaction. A microreactor was utilized to ensure that the reaction occurred under segmented flow to enhance the extraction efficiency. Through many attempts using phosphate buffer saline (PBS) as the reaction phase and 2-sec-butyl phenol (2BP) as the extraction phase, the favorable conditions were determined. By using PBS with pH of 2.0 and 2BP at a volume ratio of 3 to PBS, 80.9 mol % of fructose and 75.7 mol % of glucose were converted into HMF, respectively, at 180 °C. By comparing the results obtained through monophasic reactions, it was confirmed that the biphasic system successfully suppressed both the overreaction and the byproducts. The system employed only a simple experimental apparatus and the acid solution and organic solvent reagents without any complex expensive catalyst.

Polar aprotic solvent-water mixture as the medium for catalytic production of hydroxymethylfurfural (HMF) from bread waste

Valorisation of bread waste for hydroxymethylfurfural (HMF) synthesis was examined in dimethyl sulfoxide (DMSO)-, tetrahydrofuran (THF)-, acetonitrile (ACN)-, and acetone-water (1:1v/v), under heating at 140°C with SnCl4 as the catalyst. The overall rate of the process was the fastest in ACN/H2O and acetone/H2O, followed by DMSO/H2O and THF/H2O due to the rate-limiting glucose isomerisation. However, the formation of levulinic acid (via rehydration) and humins (via polymerisation) was more significant in ACN/H2O and acetone/H2O. The constant HMF maxima (26–27mol%) in ACN/H2O, acetone/H2O, and DMSO/H2O indicated that the rates of desirable reactions (starch hydrolysis, glucose isomerisation, and fructose dehydration) relative to undesirable pathways (HMF rehydration and polymerisation) were comparable among these mediums. They also demonstrated higher selectivity towards HMF production over the side reactions than THF/H2O. This study differentiated the effects of polar aprotic solvent-water mediums on simultaneous pathways during biomass conversion.

Production of 5-(hydroxymethyl)-furfural from water-soluble carbohydrates and sugarcane molasses

In this work, two catalytic systems were applied for the production of 5-(hydroxymethyl)-furfural (HMF) from different water-soluble carbohydrates. These systems combined Lewis (ZnCl2 and AlCl3) and Brønsted (HCl) acids in a biphasic system composed of an extraction solvent (ES) and a reaction solvent (RS). Tetrahydrofuran (THF) was used to control yield losses that are due to undesirable side reactions by promoting the continuous extraction of HMF from the aqueous phase, which was nearly saturated with sodium chloride (NaClaq). HMF production was enhanced when high temperatures (180°C) and high ES/RS ratios (10) were employed in short reaction times (60min). The combination of Lewis and Brønsted acids and the use of the THF/NaClaq biphasic system proved to be the right choice for HMF production. AlCl3/HCl was best for glucose dehydration while ZnCl2/HCl gave higher HMF yields from sucrose and sugarcane molasses (65.6 and 49.6%, respectively). Compared to synthetic mixture containing the same amount of sugars, no matrix interference was observed during dehydration of sugarcane molasses. ZnCl2/HCl humins were primarily composed of furan derivatives, whereas AlCl3/HCl humins had higher molecular mass and benzofurans content, which were a result of the higher acidity of this reaction system.

Valorization of starchy, cellulosic, and sugary food waste into hydroxymethylfurfural by one-pot catalysis

This study aimed to produce a high-value platform chemical, hydroxymethylfurfural (HMF), from food waste and evaluate the catalytic performance of trivalent and tetravalent metals such as AlCl3, CrCl3, FeCl3, Zr(O)Cl2, and SnCl4 for one-pot conversion. Starchy food waste, e.g., cooked rice and penne produced 4.0–8.1 wt% HMF and 46.0–64.8 wt% glucose over SnCl4 after microwave heating at 140 °C for 20 min. This indicated that starch hydrolysis was effectively catalyzed but subsequent glucose isomerization was rate-limited during food waste valorization, which could be enhanced by 40-min reaction to achieve 22.7 wt% HMF from cooked rice. Sugary food waste, e.g., kiwifruit and watermelon, yielded up to 13 wt% HMF over Sn catalyst, which mainly resulted from naturally present fructose. Yet, organic acids in fruits may hinder Fe-catalyzed dehydration by competing for the Lewis sites. In contrast, conversion of raw mixed vegetables as cellulosic food waste was limited by marginal hydrolysis at the studied conditions (120–160 °C and 20–40 min). It is interesting to note that tetravalent metals enabled HMF production at a lower temperature and shorter time, while trivalent metals could achieve a higher HMF selectivity at an elevated temperature. Further studies on kinetics, thermodynamics, and reaction pathways of food waste valorization are recommended.

Valorization of cellulosic food waste into levulinic acid catalyzed by heterogeneous Brønsted acids: Temperature and solvent effects

This study presents the catalytic valorization of vegetable waste into levulinic acid (LA) over a solid Brønsted acid, Amberlyst 36, in aqueous solution with/without polar aprotic solvent (dimethyl sulfoxide, DMSO). With the aid of microwave heating, the cellulosic structure in the vegetable started hydrolysis at 120°C. Increasing temperature to 135–150°C accelerated the yield of LA to 13–17Cmol% in 5min in aqueous solution due to the reduction of mass transfer limitations. At the same time, the generation of insoluble humins became more rapid and significant, leading to lesser amount of total soluble products. In comparison, in the DMSO-water mixture, the early-stage reaction produced up to 17Cmol% of hydroxymethylfurfural (HMF), which was gradually rehydrated to LA with increasing reaction time. This probably illustrated the effects of DMSO, i.e., increased accessibility of glucose to protons for rapid HMF formation and preferential solvation of HMF to dampen further rehydration. The maximum yield of soluble products in DMSO-water mixture at 120–150°C was higher than that in aqueous solution, which was attributed to the enhanced dissolution of cellulose in DMSO as supported by the SEM images. The XRD patterns of the reacted solids demonstrated more intensive peaks at the early stage of the reaction followed by broadening peaks at the later stage, indicating the hydrolysis of amorphous cellulose and formation of insoluble solids on the surface. Therefore, water serves as a green solvent for LA production while DMSO-water mixture is needed for HMF production from vegetable waste.

Pretreatment technologies of lignocellulosic biomass in water in view of furfural and 5-hydroxymethylfurfural production- A review

Lignocellulosic biomasses are strongly connected composites of cellulose, hemicelluloses, and lignin. A pretreatment is required in order to make these components available for their later conversion into chemicals. At this point, two strategies have to be considered: to either produce chemicals via microorganism or enzymes (1), or by chemical conversion (2). The focus of this article is the second strategy, which is chemical conversion, performed in water to produce the final products furfural and 5-hydroxymethylfurfural (HMF). Reviewed first is the composition of cellulose and hemicelluloses as well as their degradation chemistry in water. Then, fundamental modes of action and process parameters of pretreatment methods in aqueous solution are summarized. The pretreatment methods discussed here are steam explosion, treatment with hot liquid water, diluted and concentrated acids, as well as alkaline solutions. Finally, the advantages and disadvantages of these pretreatments are discussed for lignocellulosic biomass.

Exploratory catalyst screening studies on the liquefaction of model humins from C6 sugars

A catalyst screening study is reported on the liquefaction of humins, the solid byproducts from C6 sugar biorefineries for levulinic acid and 5-hydroxymethylfurfural production.

Photoassist-phosphorylated TiO2 as a catalyst for direct formation of 5-(hydroxymethyl)furfural from glucose.

Photo-assisted phosphorylation of an anatase TiO2 catalyst was examined to improve its catalytic performance for the direct production of 5-(hydroxymethyl)furfural (HMF), a versatile chemical platform, from glucose. In phosphorylation based on simple esterification between phosphoric acid and surface OH groups on anatase TiO2 with water-tolerant Lewis acid sites, the density of phosphates immobilized on TiO2 is limited to 2 phosphates nm-2, which limits selective HMF production. Phosphorylation of the TiO2 surface under fluorescent light irradiation increases the surface phosphate density to 50%, which is higher than the conventional limit, thus preventing the adsorption of hydrophilic glucose molecules on TiO2 and resulting in a more selective HMF production over photoassist-phosphorylated TiO2.

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

One‐Pot Conversion of Carbohydrates into 5‐(Hydroxymethyl)furfural using Heterogeneous Lewis‐Acid and Brønsted‐Acid Catalysts

AbstractSn‐β zeolite and PTSA–POM, made from the copolymerization of p‐toluenesulfonic acid (PTSA) and paraformaldehyde (POM), were used for the production of 5‐(hydroxymethyl)furfural (HMF) from glucose in an environmentally friendly solvent system including γ‐valerolactone (GVL) and H2O. The effects of reaction temperature, reaction time, solvent, and catalyst‐to‐reactant ratio on the production of HMF were investigated. The combination of the Brønsted acid and Lewis acid catalysts largely improved the catalytic system and resulted in the production of HMF in 60.1 % yield at 140 °C in 30 min. The presence of water in the solvent had a positive influence on the production of HMF from glucose. The combination of the two catalysts also improved the catalytic performance for the production of HMF from cellulose and corn stalk.

Effect of severity on dilute acid pretreatment of lignocellulosic biomass and the following hydrogen fermentation

This study aimed to investigate the relationship of the severity of dilute acid pretreatment and the following dark hydrogen fermentation performance. Empty palm fruit bunch, rice husk, and pine tree wood were hydrolyzed in 5% (v/v) H2SO4 at 10% (w/v) solid/liquid ratio and 121 °C for 30, 60, and 90 min, and then used as the substrate of batch hydrogen fermentation. The maximum sugar yield was achieved at pretreatment with 60 min reaction time; however, it did not guarantee the maximum H2 production. Hydrolyzate obtained from pretreatment where the combined severity factor was at or over 2.01 showed severe 5-hydroxymethylfurfural production and consequent decrease of H2 production rate. Peak H2 production rates of 2640, 3340, and 2565 mL H2 L−1 day−1 were achieved at the following severity factors: 1.95, 1.86, and 1.83, for empty palm fruit bunch, rice husk, and pine tree wood, respectively.

Salt-Promoted Glucose Aqueous Isomerization Catalyzed by Heterogeneous Organic Base

Effective isomerization of glucose to fructose is a crucial step for 5-hydroxymethylfurfural production from lignocellulose. The present study investigated polystyrene-supported organic bases with varied structural properties for aqueous isomerization of glucose. The results indicate that the heterogeneous organic bases can achieve approximately 30% fructose yields at 120–140 °C. As heterogeneous catalysts, they are generally less efficient than homogeneous organic bases and can lose catalytic activity during recycling likely from thermal-induced byproducts. However, the addition of neutral salt made the heterogeneous organic bases as efficient as homogeneous organic bases, achieving approximately 41% maximum fructose yields at 80–100 °C; and improved the reusability allowing the heterogeneous organic bases to be reused for at least four times without significant loss of catalytic activity.

Integrating Electrocatalytic 5-Hydroxymethylfurfural Oxidation and Hydrogen Production via Co–P-Derived Electrocatalysts

Electrocatalytic biomass valorization with renewable energy input represents a promising way to produce sustainable and nonfossil-based carbon products. Even more desirable is that the oxidative biomass upgrading can be integrated with H2 production in a single electrolyzer. Herein, we report that electrodeposited Co–P can act as competent electrocatalysts for 5-hydroxymethylfurfural (HMF) oxidation to 2,5-furandicarboxylic acid (FDCA) at the anode and H2 production at the cathode simultaneously in alkaline media. When serving as a catalyst precursor on the anode, Co–P was able to achieve a current density of 20 mA/cm2 for HMF oxidation in 1.0 M KOH with 50 mM HMF at 1.38 V vs RHE, prior to the takeoff of the competing reaction, O2 evolution. Long-term chronoamperometry demonstrated a nearly 100% conversation of HMF and a ∼90% yield of FDCA. When HMF oxidation and H2 evolution were integrated in one electrolyzer with a Co–P/Co–P catalyst couple, the potential required to achieve a current density of 20 mA...

Glucose and 5-hydroxymethylfurfural production from cellulosic waste by sequential alkaline and acid hydrolysis

Glucose and 5-hydroxymethylfurfural production from waste paper towel was evaluated by sequential alkaline and acid hydrolysis. Effects of alkali/acid doses, treatment time and temperature on hydrolysis performance were investigated by using Box-Behnken and Box-Wilson statistical experiment design methods. Operation parameters for alkaline hydrolysis were percent NaOH, treatment time and temperature and for acid hydrolysis percent acid and treatment time. Total paper conversion of the sequential process was 72% indicating significant waste reduction beside glucose and 5-hydroxymethylfurfural formation. The maximum yields for glucose and 5-hydroxymethylfurfural were 61.23% and 19.70% in acid and alkaline hydrolysis, respectively. Main products in the effluent of alkaline hydrolysis were glucose and 5-hydroxymethylfurfural. Highest glucose concentration (25.2 gL−1) in alkaline hydrolysis was obtained at 16% NaOH, 119 °C, and 74 min. The 5-hydroxymethylfurfural concentration and paper conversion at this condition was 7.22 gL−1 and 28.47%, respectively. When the solid residue of alkaline hydrolysis was treated with 5% H2SO4 at 135 °C for 120 min then 30.7 gL−1 glucose and 0.87 gL−1 5-hydroxymethylfurfural was obtained with 44.35% paper conversion.

CrCl3 · 6H2O and Boric Acid as a New Catalytic System: Enhanced 5-Hydroxymethylfurfural Production from Cellulose Under Milder Conditions

CrCl₃ · 6H₂O and Boric Acid as a New Catalytic System: Enhanced 5-Hydroxymethylfurfural Production from Cellulose Under Milder Conditions

Brønsted Acidic Polymer Nanotubes with Tunable Wettability toward Efficient Conversion of One-Pot Cellulose to 5-Hydroxymethylfurfural

Employing renewable and widely available feedstock of cellulose as a raw material for 5-hydroxymethylfurfural (HMF) production opens up the possibility of sustainable biorefinery schemes that do not compete with the food supply. In this work, novel and efficient Brønsted acidic polymer nanotubes were successfully prepared by chemical conjugating grafting −SO3H groups onto the surface of polydivinylbenzene (PDVB) nanotubes, which were derived from cationic polymerization of divinylbenzene. By simply adjusting the grafting amounts of hydrophilic −SO3H groups, catalysts with varied hydrophobic and hydrophilic surface wettability (i.e., catalyst-110° and catalyst-10°) could be obtained. It was demonstrated that as-prepared catalyst-10° possessed the higher strong (143 μmol g–1), very strong (614 μmol g–1), and total acidity (786 μmol g–1) than those of catalyst-110°. Besides, the catalytic performance of the synthesized catalyst-110° and catalyst-10° were investigated and compared for the conversion of cellulose to HMF in an ionic liquid (i.e., 1-ethyl-3-methyl-imidazolium chloride, [EMIM]-Cl) system. Particularly, catalyst-110° exhibited the highest HMF yield of 34.6% on a molar basis, which was comparable with that of catalyst-10° (i.e., 37.1%), indicating that its hydrophobic nature was beneficial for decreasing side-reaction of HMF which tend to convert to some other byproducts during the very one-pot reaction. Furthermore, both catalysts can be easily recovered and reused for at least four times without significant loss of their catalytic activities. This work was the continue efforts for fabrication and application solid catalyst for excellent conversion of one-pot cellulose to HMF.

Fenton-mediated production of hydroxymethylfurfural (HMF) from banana waste

A potentially economical and ecofriendly way of hydroxymethylfurfural (HMF) production was developed on the basis of a waste of banana peel and Fenton reaction. An optimal process condition was obtained by examining the effects of three key parameters including amount of hydrogen peroxide (H2O2), amount of ferrous (Fe2+) ion, and reaction time on HMF yield. This study may offer an alternative route for HMF production, indeed a sustainable one in that it makes the best use of a problematic bio-waste and also takes advantage of the simple nature of the Fenton process.

Sustainable Approach to Catalytic Conversion of Starch-based Biomaterials into Hydroxymethylfurfural Using Ionic Liquids

The concept of sustainable chemistry includes three main parameters; the use of renewable biofeedstock for syntheses of chemical compounds, nontoxic solvents, and eco-friendly processing systems. Until now, many attempts have been made to meet these parameters in chemical synthesis. In hydroxymethylfurfural (HMF) synthesis, most studies have focused on the conversion of cellulosic/ lignocellulosic biomass to HMF. In addition to these biomasses, starch has also been intensively studied for the sustainable synthesis of HMF in ionic liquids. These studies demonstrated that starch-based biomaterials have high potential as renewable feedstocks for HMF synthesis by affording substantial yields of HMF. Starch is a more favorable biofeedstock than other carbohydrate materials because it is available at a relatively low cost and is likely applicable to the cost-effective mass production of HMF. Our studies confirmed the high yields of HMF from starch-based biomaterials in ionic liquid. Based on our results and related data, this review describes the current knowledge on the concept of chemical sustainability, importance of starch-based biomaterials as a biomass source for sustainable production of HMF, nature and application of HMF and ionic liquids, and bioengineering technologies for improving starch quantity and quality. Keywords: Bioengineering, hydroxymethylfurfural, ionic liquid, starch-based biomaterials, sustainable chemistry.

ChemInform Abstract: Catalytic Dehydration of C6 Carbohydrates for the Production of Hydroxymethylfurfural (HMF) as a Versatile Platform Chemical

AbstractReview: 197 refs.