Production Of 5-hydroxymethylfurfural Research Articles

Unveiling kinetics post Rate-Determining step in Brønsted Acid-Catalyzed reactions of Fructose: A strategy for 5-Hydroxymethylfurfural production from concentrated feedstock

The development of high-yielding catalytic systems is pivotal in biomass upgrading. However, the investigation of kinetics in these complex reaction systems is often highly challenging, especially when reactions leading to byproduct formation are obscured by a preceding, slow rate-determining step. In this work, we introduce a unique approach to kinetic analysis that enables the investigation of reactions occurring post rate-determining step. The technique was applied to the conversion of sugars to 5-hydroxymethylfurfural (HMF), an important platform molecule for sustainable chemical production. Screening experiments were carried out to identify a catalytic solvent system that achieves a balance between solvent stability, HMF yield, and cost-effectiveness. Our kinetic analysis on the identified system reveals that the fructose reactant undergoes a rate-determining dehydration step to form an unstable reactive intermediate. The post rate-determining step kinetics show multiple competitive reactions between the slow-forming unstable intermediate and other reactive species, such as the hexose reactants or the HMF product, ultimately lowering the HMF selectivity. The calculated relative activation energies of reactions post rate-determining step provide intuitive insights into the effects of temperature, co-existing reactive species, as well as the previously unexplained effect of feed concentration on HMF selectivity. Additionally, we propose a novel reaction strategy that significantly enhances HMF yield when compared to a traditional batch synthesis. Notably, a high HMF yield of 74 % was achieved with an extreme 55 wt% fructose loading on an aqueous basis (20 wt% loading on a total weight basis) in a low-boiling 80 wt% dioxane/water mixture using an HCl catalyst at 393 K.

Sn-modified SBA-15 with tailored acid properties for efficient 5-hydroxymethylfurfural production from glucose

Interest in production and utilization of 5-hydroxymethylfurfural (5-HMF) has risen greatly as 5-HMF is considered as an extremely important platform compound. It remains a huge challenge to develop efficient and low-cost solid catalysts with suitable acid properties for sustainable production of 5-HMF from glucose. Herein, a bifunctional Sn-modified SBA-15 (Sn–OH/SBA-15) catalyst containing both Lewis and Brønsted acid sites was fabricated. Dimethyldichlorostannane was grafted onto mesoporous SBA-15, and the methyl groups were then converted to hydroxyl groups by calcination. The synergistic effects of Lewis and Brønsted acid significantly boosted the synthesis of 5-HMF from glucose adopting the one-pot method. By optimizing the reaction conditions, the Sn–OH/SBA-15 sample was able to achieve a glucose conversion of 96.9% with a 5-HMF yield of 70.6% (180 °C, 5 h). Moreover, the catalyst demonstrated superior recyclability and reusability. This work would enlighten the exploitation and preparation of highly efficient catalysts for the transformation of carbohydrates into value-added chemicals.

Regioselectivity and confinement effects for catalytic conversion of carbohydrates within zeolite H-BEA

Zeolites have established the importance during biomass conversion, and H-form zeolites, although extensively used, produce hydroxymethylfurfural (HMF) with low yields. Herein, dispersion-corrected density functional calculations are employed with aim to comprehensively understand glucose conversion to HMF within zeolite H-BEA and unravel the role of confinement effects. The low HMF yields originate from regioselectivity: The preferentially activated O3 and O6 sites are significantly driven to humin precursors, while less reactive O1 and O2 sites lead favorably to HMF. Glucose-to-fructose isomerization occurs only at O5 site, while seems unnecessary for HMF production. Owing to the peculiar confinement effects, HMF precursors are prone to emerge within H-BEA, both upon dehydration and during catalysis, while may turn to be acyclic within aqueous solutions. Direct conversion to levulinic acid without HMF as intermediate thus becomes difficult within acidic zeolites. Results facilitate catalyst design for biomass conversion, and further understanding of regioselective catalysis and confinement effects.

A Closed-Loop Biorefinery Approach for the Valorization of Winery Waste: The Production of Iron-Sulfonated Magnetic Biochar Catalysts and 5-Hydroxymethyl Furfural from Grape Pomace and Stalks

In this work, a closed-loop strategy for the management and valorization of winery waste was proposed. The exhausted pomace and grape stalks that are typically obtained from white wine industries were used as a source of simple sugars, namely, glucose and fructose, and of lignocellulosic feedstock for the preparation of selective catalysts for the 5-hydroxymethylfurfural (5-HMF) production from fructose. A novel synthetic procedure was developed for the synthesis of iron-sulfonated magnetic biochar catalysts (Fe-SMBCs). Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), BET surface area, porous structure analysis and determination of total amount of acid sites were performed in order to characterize the physico-chemical properties of the synthesized systems. Then, these heterogeneous catalysts were successfully tested via the dehydration of simple sugars into 5-HMF by using methyl isobutyl ketone (MIBK) and gamma valerolactone (GVL) as co-solvents. The optimum 5-HMF yield of 40.9 ± 1.1%mol with a selectivity of 59.8 ± 2.6%mol was achieved by adopting the following optimized conditions: 0.1 g of catalyst, volume ratio of GVL to H2O = 2 to 1, 403 K, 6 h. In addition, the catalyst was easily recycled using an external magnetic field and used for at least five reaction cycles without significant loss of catalytic activity.

An innovative phosphated Zr[sbnd]Si Laponite as a solid acid catalyst for 5-hydroxymethylfurfural production from fructose

The dehydration of fructose is a crucial chemical process for synthesizing valuable chemicals and biofuels. This work explored an attractive strategy for harnessing lignocellulosic biomass through the catalytic conversion of fructose, yielding valuable 5–hydroxymethylfurfural (HMF) chemicals and biofuels. Sustainable and cost–effective methodologies for crafting catalysts via Laponite (Lap) modification to facilitate fructose transformation into HMF within a biphasic system comprising aqueous NaCl and tetrahydrofuran (THF) were examined. The phosphated Zr–grafted Si–enriched Lap (P/Zr–SiLap), as a solid acid catalyst, was synthesized through multiple straightforward steps involving mesoporous silica formation, Zr atom incorporation, and phosphation of pristine Lap. The P/Zr–SiLap catalyst proved to be a most promising catalyst, achieving an optimized HMF yield of 78.4% at 150 °C with a turnover frequency (TOF) for HMF production of 2.8 × 10−5 h−1. Evaluation of the P/Zr–SiLap demonstrated the catalyst's robust endurance, ensuring its high potential for efficient recyclability. The enhanced HMF yield (%) attributable to the P/Zr–SiLap catalyst was systematically correlated with its structure–activity relationship, which was elucidated through various advanced analytical techniques.

Environmental impact of 5-hydroxymethylfurfural production from cellulosic sugars using biochar-based acid catalyst

In this study, HMF was successfully synthesized from a range of cellulosic sugars, utilizing sustainable acidic biochar derived from cassava rhizome (CR). Various acid precursors such as sulfuric acid (H2SO4),p-toluenesulfonic acid (TsOH), and ferric chloride (FeCl3) were chosen. Acids grafted biochar were carried out through a facile hydrothermal method. HMF production was performed at 175 °C for 0.5 h using 10 % of the acidic biochar catalyst in water to isopropanol (i-PrOH) mixture ratio of 1:4. The maximum HMF yields of fructose (53.29 wt%), glucose (2.94 wt%), and cellulose (0.38 wt%) could be achieved over 600-H2SO4, 700-FeCl3, and 400-H2SO4catalysts, respectively. Moreover, the recyclability of the acidic biochar catalysts could distinguish more than five times without significant loss of activity. Remarkably, the life cycle assessment (LCA) and cost analysis of the HMF production process indicated that the future sustainable industrial production of HMF could be realizedinvolving the 600-TsOH catalyst.

Optimizing 5-hydroxymethylfurfural production from biomass carbohydrates: ionic liquid-catalyzed pathways in deep eutectic solvents under sonication and thermal conditions

The synthesis of ionic liquid (IL)-based mesopore SBA-16 catalyst for the conversion of biomass-derived carbohydrates into 5-hydroxymethylfurfural (5-HMF) in the presence of 15 deep eutectic solvents (DESs) under sonication and thermal conditions.

Polystyrene-based catalysts with simultaneous Brønsted and Lewis acidity for hydroxymethylfurfural production from starch: molecular weight and solvent effects

Soluble and reusable polystyrene-based catalysts with Brønsted and Lewis acidity allowed the one-pot synthesis of hydroxymethylfurfural (HMF) from potato starch.

Diastase Enzyme activity and Hydroxymethylfurfural production during thermal processing of honey

The thermal treatment of honey is used to prevent honey crystallization which is one of the main problems that face beekeepers. In this study three samples of honey were heated at 40, 60, 80 and 100 °C, as a function of time in hours (h). Heating the samples at 40 °C did not show any significant effect on hydroxymethylfurfural (HMF) production or diastase enzyme activity up to 95 hours. Heating to higher temperatures 60, 80 and 100 °C resulted in a regular increase in HMF content and drop-off in diastase activity as a function of time. The HMF content reached 40 mg/kg after 80, 12.5 and 6 hours. For the three samples at 60, 80 and 100 °C respectively. Conversely, diastase enzyme activity reached close to 8 IU after 96, 12.5 and 5 hours. For the following temperatures 60, 80 and 100 °C respectively. The results showed that heating temperatures up to 40 °C is safe for long-term storage, while heating at 60 °C could be used but for a shorter treatment time. Results showed that the must temperature does not exceed 60 °C for 5 hours or 80 °C for one hour to preserve the honey's quality. The reaction rate constants and activation energy Ea of HMF formation in three samples were found 83.07, 91.79 and 89.57 kJ.mol-1 respectively. Therefore, honey can be preserved in this way, while at the same time the HMF remains below the permissible values, and the enzymatic activity remains at its highest level.

Designed synthesis N-doped sulfonated bifunctional catalyst for efficient 5-hydroxymethylfurfural production: A pyridinic N-triggered proton-shift mechanism at basic sites

Considering the essential role of acidic/basic sites in efficient 5-hydroxymentylfurfural (5-HMF) production from cellulose, the superiority of acid-base bifunctional catalysts was unfolded. However, the lack of in-depth research on catalytic mechanism of active sites, especially the basic sites, greatly hinders its chemical utilization. Herein, N-doped sulfonated bifunctional catalysts were rationally designed. The synthesized NCS-1H catalyst exhibited outstanding activity and recyclability. Favorable 5-HMF yield of 50.0 % with 62.9 % of selectivity was obtained. Spin polarized density function theory (DFT) analysis revealed a pyridinic N-triggered proton-shift mechanism of glucose isomerization. Catalyzed by pyridinic N, the proton of glucose on C2 was shifted to O5, leading to the cleavage of C1-O1 bond. As a result, an enol intermediate was formed and converted to fructose. Compared to pyrrolic N and graphitic N, pyridinic N significantly reduced the reaction energy barrier of rate-determining step to 0.79 eV, i.e., C1-O1 bond cleavage.

Valorization of beverage waste as a sugar source for 5-hydroxymethylfurfural production

This study highlights the valorization of beverage waste as a promising sugar-based raw material for 5-hydroxymethylfurfural (5-HMF) production. In this work, both beverage waste purification and 5-HMF production were experimentally demonstrated through the practicality and effectiveness of continuous-flow processes. In the purification process, solid and liquid impurities were wholly eliminated through membrane filtration and a two-stage adsorption process using activated carbon. The purified beverage waste primarily consisted of fructose, glucose, and sucrose, offering a plentiful source of sugar. A mini fixed-bed reactor was employed to thoroughly investigate the impact of various operating variables on continuous 5-HMF production from synthetic beverage waste. The variables considered included residence time, reaction temperature, catalyst type, solvent type, water content, and sugar concentration. The optimization analysis was conducted to achieve both high 5-HMF yield and productivity. The optimal condition, which resulted in the 5-HMF yield of 42.6% and productivity of 3.3e−3 kg5-HMF/kgcat-h, was obtained with a residence time of 15 min, sugar feed concentration of 10 g/L, reaction temperature of 120 °C, and water content of 10 g/L. Dimethyl sulfoxide (DMSO) and Amberlyst 15 were the selected solvent and catalyst, respectively. The feasibility of producing 5-HMF from actual beverage waste was validated under optimal conditions. Furthermore, the stability of the catalyst was demonstrated over 24 h of time-on-stream. The proposed processes offer the potential for continuous purification of beverage waste and the efficient production of 5-HMF.

Enhanced 5-hydroxymethylfurfural production from cellulose in monophasic molten salt hydrate: Insights into the effect of catalyst acidity on conversion

Production of 5-HMF from cellulose is a promising approach for advanced bio-fuels preparation, but the degradation of active 5-hydroxymethylfurfural (5-HMF) is a critical challenge affecting 5-HMF selectivity. To address this issue, biphasic reaction system consisting of water and organic solvent is generally used to in-situ extract 5-HMF into organic phase to inhibit product degradation. Despite the high 5-HMF selectivity achieved in biphasic system, low product concentration and difficulty in separation restrict its industrial applications. Molten salt hydrate (MSH) is unique in cellulose conversion and 5-HMF preservation. In this work, MSH of LiBr was used as monophasic solvent for cellulose conversion and an acidity tunable solid acid AlSiO-x was used as the catalyst. It was found that a relatively high 5-HMF yield of 44.5% together with carbon balance of 75.0% were obtained at 170 °C for 20 min, which is higher than the results ever reported. Importantly, this work proved that the ratio of total Brønsted to Lewis acid sites on solid acid is the key issue affected 5-HMF yield. After reaction, solid acid can be recycled for more than 5 times without catalytic performance decline, and the dissolved 5-HMF can be sufficiently separated from MSH via hyper cross-linked polymer (HCP) adsorption.

One-pot Conversion of Sago Pith Waste (SPW) into 5-Hydroxymethyl Furfural (HMF)

Hydroxymethyl furfural (HMF) is widely understood to be a robust substitute feedstock for a wide array of petroleum-derived products such as plastic and fuel. Previous research delved into the use of waste (i.e., biomass) to produce HMF. These waste products stemmed from sugarcane bagasse, algae, bread, and banana. Our study is the first to report the use of sago pith waste (SPW), a by-product of the sago starch industry, for HMF production via simultaneous conversion in one pot. The production of HMF in such a manner not only yields an industrially important product (i.e., HMF) but also confers a sustainable waste management solution to the sago starch industry. SPW primarily consists of starch and fiber, and since the density of SPW affects the feed rate of the reactor, it is necessary to optimize the reaction temperature, sample volume, and amount of activated carbon to elucidate reaction conditions with a high HMF yield. By adding activated carbon and sodium chloride into the reaction mixture with a Bronsted-Lewis acid, we obtained 50-60% mole of HMF from SPW in a simultaneous reactor system at 160°C for 8 minutes.

Impact of Porous Silica Nanosphere Architectures on the Catalytic Performance of Supported Sulphonic Acid Sites for Fructose Dehydration to 5-Hydroxymethylfurfural.

5-hydroxymethylfurfural represents a key chemical in the drive towards a sustainable circular economy within the chemical industry. The final step in 5-hydroxymethylfurfural production is the acid catalysed dehydration of fructose, for which supported organoacids are excellent potential catalyst candidates. Here we report a range of solid acid catalysis based on sulphonic acid grafted onto different porous silica nanosphere architectures, as confirmed by TEM, N2 porosimetry, XPS and ATR-IR. All four catalysts display enhanced active site normalised activity and productivity, relative to alternative silica supported equivalent systems in the literature, with in-pore diffusion of both substrate and product key to both performance and humin formation pathway. An increase in-pore diffusion coefficient of 5-hydroxymethylfurfural within wormlike and stellate structures results in optimal productivity. In contrast, poor diffusion within a raspberry-like morphology decreases rates of 5-hydroxymethylfurfural production and increases its consumption within humin formation.

Kinetic Modeling of Cornstalk Cellulose Hydrolysis in Supercritical Water: A Comparative Study of the Effects of Temperature and Residence Time on Derivative Production

Kinetic modeling is essential in understanding and controlling the process of cellulose hydrolysis for producing value-added cellulose derivatives. This study aims to adopt a set of dominate kinetic ordinary differential equations of cornstalk cellulose hydrolysis in supercritical water for mechanism-based prediction of the production of cellulose, glucose, fructose, glyceraldehyde, erythrose, 5-hydroxymethyl furfural, glycolaldehyde, threose, aldose, and other cellulose derivatives from cornstalks under processing conditions with a pressure of 89 MPa and a temperature of 378 °C, as considered in a recent experimental study in the literature. The yield rates of several cellulose derivatives, e.g., glucose, fructose, 5-HMF, and erythrose as predicted by the present model, are close to those of experimental measurements. The model is further used to predict the yield rates of a few new cellulose derivatives, e.g., glycolaldehyde, threose, and aldose, that are potentially generated in cornstalk cellulose hydrolysis in supercritical water. The present model and computational simulations can be utilized as a rational tool to predict, control, and optimize the derivative yields in cellulose hydrolysis in supercritical water via tuning the process parameters, and, therefore, are useful for the optimal production of targeted bio-based fuels and chemicals from cornstalks and other agricultural and municipal wastes.

Autohydrolysis pretreatment of corn stalk for improved 5-hydroxymethylfurfural production in molten salt hydrate/acetone

Molten salt hydrate (MSH) is unique in cellulose dissolution and in one-pot conversion of crystalline cellulose into 5-hydroxymethylfurfural (5-HMF). However, low yield of 5-HMF was obtained using raw biomass substrate in MSHs. Herein, we investigated conversion of raw biomass towards HMF using MSHs. We showed that the release of acetic acid from hemicellulose degradation in MSH is a key to influence the yield of 5-HMF. Thus, an autohydrolysis pretreatment method was proposed to remove hemicellulose before conversion of cellulose into 5-HMF. After being pretreated at 180 °C for 40 min, hemicellulose was removed from biomass with 91.8% yield of cellulose remained in solid part. By eliminating the negative effect of acetic acid, 5-HMF yield was significantly improved from 40.9% to 64.6%, together with 9.3% yield of glucose for cellulose conversion in MSH/acetone at 180 °C for 20 min.

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

Abstract5‐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.

Hydrothermal processing of agar waste to levulinic acid and fermentation of hydrolysate to bioethanol

Increasing global energy consumption and depleting fossil-fuel reserves prompted the search for green alternatives. This study focuses on conversion of waste agar using different acids/alkalis (0.5% and 1%) as catalysts under varied temperature and time towards galactose (Gal), 5-hydroxymethylfurfural (HMF) and levulinic acid (LA) production in sequential reactions. The optimized process for agar depolymerisation was achieved using 1% acid (H2SO4/HCl) catalysed conditions with a maximum of 11 g/L Gal yield (121 °C; 15 min). Increase in temperature (150 °C) and time (180 min) with 1% HCl/H2SO4 catalyst resulted in improved LA production along with Gal and HMF. The hydrolysis process was optimised for the selective production of LA (10 g/L at 175 °C; 180 min). Further, galactose-rich hydrolysates were assessed for bioethanol production using Saccharomyces cerevisiae that resulted in 3 g/L ethanol. Thus, the study comprehensively demonstrates waste agar utilization to yield biochemicals/fuels in a circular bio-based economy approach.

Acrylamide and 5-Hydroxymethylfurfural in Synthetic Sugar Cane Syrup: Mitigation by Additives.

The ability of additives to reduce the formation of acrylamide in simulated sugar cane syrups was investigated. Organic acids, B vitamins, and inorganic salts were added individually and in combination to simulated thickened cane juice, and the mixtures were heated at 120 °C for 30 min. Calcium chloride (1%), citric acid (0.1%), and vitamin B3 (0.1%) were the most effective individual additives from each chemical family. The effects of CaCl2 (0-1%), citric acid (0-0.125%), and vitamin B3 (0-0.1125%), when added in combination, on the concentrations of acrylamide and hydroxymethylfurfural (HMF) were studied using a Box-Behnken design. Combinations of all three additives lowered the acrylamide production, but only the combination of citric acid and vitamin B3 had a significant synergistic effect. However, all these additives stimulated the production of HMF, and no significant interactive effect between pairs of additives on HMF production was observed. Calcium chloride stimulated the formation of HMF most strongly. These results indicate that certain combinations of these additives effectively reduce acrylamide formation, but they also lead to an increase in the formation of HMF in sugar syrup.

Microwave-assisted alkali pre-treatment medium for fractionation of rice straw and catalytic conversion to value-added 5-hydroxymethyl furfural and lignin production

In the current study, the use of microwave-assisted sodium hydroxide medium (MWSH) for pre-treatment and saccharification of rice straw to obtain sugar syrup for the production of 5-hydroxymethyl furfural (5-HMF) was investigated. The optimization of the MWSH pre-treatment was carried out using central composite methodology, resulting in a maximum reducing sugar yield of 350 mg/g of treated rice straw (TRS) and a glucose yield of 255 mg/g of TRS under the conditions of a microwave power of 681 W, a NaOH concentration of 0.54 M, and a pre-treatment time of 3 min. Additionally, the microwave assisted transformation of sugar syrup with titanium magnetic silica nanoparticle as catalyst, producing 41.1 % yield of 5-HMF from the sugar syrup after 30 min microwave irradiation at 120 °C with catalyst loading of 2.0:200 (w/v)). The structural characterization of the lignin was analysed using 1H NMR techniques, and the surface carbon (C1s spectra) and oxygen (O1s spectra) composition changes of the rice straw during pre-treatment were analysed using X-ray photoelectron spectroscopy. The rice straw based bio-refinery process which contains MWSH pretreatment followed by dehydration of sugars achieved high efficiency of 5-HMF production.