HMF Production Research Articles

Production of high-yield 5-hydroxymethylfurfural from crystalline cellulose via one-pot conversion in molten salt hydrate/acetone and separation

5-hydroxymethylfurfural (5-HMF) is a crucial biomss-derived fuel precursor with versatile conversion pathways to advanced fuels. However, direct production of 5-HMF from crystalline cellulose is critical challenging due to the inefficient deconstruction of recalcitrant cellulose structure. Molten salt hydrates (MSHs) are unique in cellulose deconstruction and dissolution. In this work, a biphasic system of LiBr hydrate/acetone was established. It was found that 93.4% yield of 5-HMF can be efficiently converted from fructose without any catalysts. With the addition of AlCl3 to adjust Lewis acidity, an enhanced 5-HMF yield of 75.1% together with 13.7% of glucose were directly produced from cellulose, showing a promising carbon balance of 88.8%. A proposed mechanism for cellulose conversion was studied by density functional theory (DFT) calculations, demonstrating that the isomerization of glucose to fructose rather than crystalline cellulose hydrolysis was the rate-determining step. After reaction, the formed 5-HMF can be efficiently recycled from solvent via hyper-cross-linked polymer adsorption and the reaction system can be recycled for more than 5 times without reducing 5-HMF selectivity.

Production of furfural and 5-hydroxymethyl furfural from Camellia oleifera fruit shell in [Bmim]HSO4/H2O/1,4-dioxane biphasic medium

The high-value utilization of Camellia oleifera fruit shell (CFS), which is an important waste in edible tea oil processing, is of great significance for the sustainable development of Camellia oleifera industry. In this study, the CFS after being simply pretreated (PCFS) to remove crude fat, pigment, et al., was used as material to produce furfural (FF) and 5-hydroxymethyl furfural (5-HMF) catalyzed by 1-butyl-3-methylimidazole hydrogen sulfate ([Bmim]HSO4). On the basis of comparing the superiority of microwave heating and traditional oil bath heating, on the basis of comparing the in-situ extraction of FF and HMF with four common solvents including 1,4-dioxane, methyl isobutyl ketone (MIBK), benzene, and cyclohexane, the [Bmim]HSO4/H2O/1,4-dioxane biphasic catalytic reaction system assisted by microwave irradiation was established. In this reaction system, FF was the chief product and 5-HMF was the chief by-product. The highest yields of FF and 5-HMF were 67.54 mol% and 20.97 mol%, respectively. The yield of FF was much higher than that of 5-HMF under the same reaction conditions. The kinetic analysis indicated that the hemicellulose hydrolysis to xylose catalyzed by [Bmim]HSO4 was the rate-limiting step in the production of FF. The cellulose hydrolysis to glucose and the subsequent isomerization of glucose to fructose were the rate-limiting steps in the production of 5-HMF. The rapid formation of other by-products was also one of the reasons for low yield of 5-HMF. [Bmim]HSO4 still performed excellent stability and catalytic activity after three times of cycles. FF with a purity of 95.26% could be obtained from the 1,4-dioxane phase under vacuum distillation. The relative contents of hemicellulose and cellulose and the crystallinity index of cellulose in PCFS residues decreased with the enhancement of reaction temperature and retention time. The biphasic medium used in this study was efficient for the production of FF from CFS.

Production of HMF and DMF biofuel from carbohydrates through catalytic pathways as a sustainable strategy for the future energy sector

In recent years, green energy sources have been proposed as alternatives for fossil fuels to meet energy demand while minimizing environmental pollution and global climate change. In this context, agricultural residues can be catalytically converted into furan derivatives. Among furan-based compounds, 5-hydroxymethylfurfural (HMF) and 2,5-dimethylfuran (DMF) are the valuable chemicals that can be converted into desired materials, including fuels. This review article discusses various catalytic HMF and DMF production pathways and the influence of feedstocks, catalysts, solvents, and hydrogen donors on the process yield. Additionally, reaction temperature and H2 pressure effects on the feedstock conversion and HMF and DMF production yields are also presented. The primary attention has been devoted to the literature published in the last five years. However, additional relevant examples have also been discussed to clarify the topic further where necessary. This review aims at providing state-to-the-art information on the current developmental state of DMF and HMF production for researchers in this field.

Techno-Economic Analysis of FDCA Production through Electrocatalytic Processes

The conversion of biomass into high-value chemicals and its coupling with electrochemical industry represent a viable sustainable alternative to the use of traditional petrochemical processes. The aim of this paper is to investigate the electrochemical production process of 2,5-furandicarboxylic acid (FDCA) starting from lignocellulosic biomass, which provides 5-hydroxymethylfurfural (HMF) as reaction intermediate. The process investigated is based on the scale-up of a model proposed in literature, characterized by the continuous oxidation of HMF into FDCA, catalysed by Ni/NiOOH foam, and its recovery by two-step pH-shift crystallization and subsequent filtration. The imposed productivity is 10000 tons y−1 with an overall process yield of about 70% and a separation efficiency of 95%. From the techno-economic analysis, the estimated minimum selling price (MSP) of FDCA is about 3.67 € kg−1 which is compared with the market price of terephthalic acid, showing no current feasibility of the process on industrial scale. Several factors contribute to the increase in the FDCA price: the high cost of production of HMF, the use of large quantities of acidic and basic substances, the low process yield. Sensitivity analysis shows the impact of HMF, hydrogen and electricity costs on FDCA price.

Study on application of Cr-Cu/ZSM-5 zeolite catalyst for conversion of corn-cob derived glucose to hydroxymethyl furfural

Cr-Cu/ZSM-5 zeolite catalysts were prepared by ion exchanged method and were characterized by XRD, SEM-EDS. The catalysts were applied to catalyze the transformation of corn-cob derived glucose into 5-hydroxymethyl furfural (HMF) under suitable reaction conditions. The effect of reaction conditions such as: catalyst dosage, temperature and reaction time on the yield of HMF product was investigated. The highest HMF yield of 32.6% was obtained when transformation carried out at suitable reaction conditions.

Catalytic Hydroconversion of 5-HMF to Value-Added Chemicals: Insights into the Role of Catalyst Properties and Feedstock Purity.

5-hydroxymethylfurfural (HMF) is an important bio-derived platform molecule that is generally obtained from hexoses via acid-catalyzed dehydration. It can be effectively transformed into a variety of value-added derivatives, thus being an ideal candidate for fossil replacement. Both HMF oxidation and hydrogenation processes enable the synthesis of numerous chemicals, monomers for polymerization, and biofuel precursors. This Review summarizes the most recent advances in heterogeneous catalytic hydroconversion of HMF into valuable chemicals with strong focus on 2,5-bishydroxymethyl furan (BHMF), 2,5-bishydroxymethyltetrahydrofuran (BHMTHF), and 2,5-dimethyltetrahydrofuran (DMTHF). In addition, multifunctional catalytic systems that enable a tunable production of various HMF derived intermediates are discussed. Within this chemistry, the surprising impact of HMF purity on the catalytic performance, such as selectivity and activity, during its upgrading is highlighted. Lastly, the remaining challenges in the field of HMF hydroconversion to the mentioned chemicals are summarized and discussed, taking into account the knowledge gain of catalyst properties and feedstock purity.

Subcritical water hydrolysis of N-acetyl-D-glucosamine: Hydrolysis mechanism, reaction pathways and optimization for selective production of 5-HMF and levulinic acid

In this study, the subcritical water hydrolysis of N-acetyl-d-glucosamine (NAG), a monomer of abundant renewable marine biopolymer chitin, for production of value-added chemicals is investigated. The enhanced ionization of water at subcritical conditions (200 °C; 50–100 bar), provides enough acidity for deacetylation of NAG resulting in 80% yield of acetic acid along with traces of formic acid, lactic acid, glucose, fructose, 5-hydroxymethylfurfural (5-HMF),etc. The significant humin formation indicates that the self-condensation and polymerisation of 5-HMF is favored in water at subcritical conditions. A catalyst p-toluenesulfonic acid (p-TsOH) was employed to selectively convert NAG to levulinic acid (LA) via ring opening of 5-HMF previously formed during hydrolysis. The maximum yield of 27.13 ± 1% and 53.46 ± 1% of 5-HMF and LA, respectively, was obtained at process conditions optimized using Box-Behnken design coupled with response surface methodology. Subcritical water enables greener conversion of NAG to platform chemicals wherein the selective production can be achieved by tuning the process conditions.

Catalytic Conversion of Glucose into 5-hydroxymethyl furfural over Spent Dry Batteries as Catalysts

Biomass is a popular renewable carbon source because it has a lot of potential as a substitute for scarce fossil fuels and has been used to make essential compounds like 5-hydroxymethylfurfural (HMF). One of the main components of biomass, glucose, has been extensively studied as a precursor for the production of HMF. Several efforts have been made to find efficient and repeatable procedures for the synthesis of HMF, a chemical platform used in the manufacturing of fuels and other high-value compounds. Sulfonated graphite (SG) was produced from spent dry batteries and utilized as a catalyst to convert glucose to 5-hydroxymethylfurfural (HMF). Temperature, reaction time, and catalyst loading were the variables studied. When dimethyl sulfoxide was utilized as the solvent at 180°C after 3 hours of reaction time, the greatest HMF yield, glucose conversion, and selectivity were attained, with 56.53 %, 97.5 %, and 57.979 %, respectively. This study demonstrates how to manufacture sulfonated graphite with increased catalytic activity for converting glucose to key biobased platform chemicals in a long-term sustainable manner.

Process intensification for 5-hydroxymethylfurfural production from sucrose in a continuous fixed-bed reactor

This work proposed the novel continuous production of 5-HMF from sucrose. The production was performed in a biphasic system using a mini fixed-bed reactor packed with dual ion-exchange resins (Amberlyst-21 (A21) and Amberlyst-15 (A15)) as catalyst. The primary role of each catalyst was examined to specify the suitable position in the catalyst bed, followed by the investigation of the major factors affecting the 5-HMF yield. The effects of feed concentration of sucrose, organic-to-aqueous volumetric ratio, residence time, and catalyst-bed configuration on the reaction performance were examined and optimized. The 5-HMF yield of 64.8% was achieved under the optimal conditions as follows: temperature of 120 °C, residence time of 30 min, sucrose concentration of 5 g/L, organic-to-aqueous volumetric ratio of 0.125:1, and catalyst-bed configuration of A15-A15-A21-A15. To demonstrate the stability of catalysts, the system was operated for more than 60 h of time-on-stream without any loss of 5-HMF yield. When compared to the literature, this system offered several advantages in terms of the shorter residence time, lower O:A ratio, and higher yield, demonstrating the promising capability of our proposed process.

Technoeconomic and Life-Cycle Assessment for Electrocatalytic Production of Furandicarboxylic Acid

2,5-Furandicarboxylic acid (FDCA) is a platform chemical for polyethylene furanoate (PEF) manufacturing, a promising biobased and green alternative to polyethylene terephthalate (PET) with a market size of 1.8 million tonne/annum. There are several routes to produce FDCA, all through 5-hydroxymethylfurfural (HMF) conversion. The traditional thermochemical process is highly energy intensive with a low yield. The electrocatalytic pathway, on the other hand, is gaining increased interest for it makes the process control more efficient, achieves a higher yield, and more importantly can be driven by renewable electricity to lower the environmental impact compared to the thermochemical process. This study assesses the economic aspects and environmental impacts of the electrochemical production of FDCA. It is found that the net present value (NPV) of the integrated electrochemical conversion and product separation plant is highly profitable, $72 million for 100 tonne/day production of FDCA, under optimistic conditions. It also reveals that the HMF price has significant impact on process economics, and the current density has the largest scope of improvement. The life-cycle assessment (LCA) results indicate that processes related to HMF production contribute the most to the overall environmental impacts─calling for low impact HMF production processes, with cost reductions─however, the impacts of the electrochemical route are much lower in comparison with the thermochemical route.

Tin–chromium bimetallic metal–organic framework MIL-101 (Cr, Sn) as a catalyst for glucose conversion into HMF

5-hydroxymethylfurfural (HMF) is considered a promising platform chemical, from which numerous chemicals can be produced. Hence, developing an efficient catalytic system to convert glucose into HMF has drawn considerable attention. In this study, a series of Lewis acidic Sn–Cr bimetallic metal–organic frameworks, MIL-101(Cr, Sn), with different Sn ion loading were synthesized hydrothermally using acetic acid as the mineralizer and water as the solvent. The resulting MIL-101(Cr, Sn) was systematically analyzed as a catalyst for the conversion of sugar to HMF. Moreover, the effects exerted by various reaction parameters on HMF yield and selectivity were investigated. With glucose as the substrate and 0.5-wt% H2SO4 as a catalyst, an 85.75% glucose conversion with 22.64% HMF yield and 26.41% selectivity was achieved. Meanwhile, these parameters were improved via addition of MIL-101(Cr, Sn)-0.1. That is, glucose conversion, HMF yield, and selectivity were increased to 86.36%, 60.75%, and 70.35%, respectively, when using MIL-101(Cr, Sn)-0.1 and H2SO4 as the catalyst under the same reaction conditions. The MIL-101(Cr, Sn) structure enabled high stability of the catalyst in aqueous solutions with different pH values, while improving its thermal stability. Moreover, the catalyst could be reused several times despite a slight reduction in its catalytic activity. The current results illustrate that MIL-101(Cr, Sn) is an excellent acid and sustainable catalyst for the production of HMF from fructose, glucose, and starch.

Dehydration of glucose over sulfate impregnated ZnO (hexagonal-monoclinic) catalyst in dimethyl sulfoxide (DMSO) medium: Production, separation, and purification of 5-hydroxymethylfurfural (5-HMF) with high purity

Dehydration of glucose for the production and separation of 5-hydroxymethylfurfural (5-HMF) with high purity has been performed. For selective production of 5-HMF from glucose, a new sulfated-ZnO catalyst with a combined hexagonal-monoclinic phase was developed and characterized by several techniques. The catalyst characterization results demonstrated a significant variation of physicochemical properties of hexagonal ZnO after sulfate impregnation. The glucose dehydration was performed in a glass reactor in a dimethyl sulfoxide (DMSO) medium. The effect of several important reaction parameters including temperature (120–160 °C), time (1–8 h), catalyst loading (25–100 wt%), and sulfate loading on ZnO with respect to glucose (1.5–4.5M) was evaluated. Results demonstrated that the sulfated-ZnO catalyst containing both the Brønsted (B) and Lewis (L) acid sites was very active and selective to 5-HMF compared to pure hexagonal ZnO containing only Lewis acidic sites (LAS). It was also observed that the higher (B + L) acidity of catalysts propagated the rehydration process, which led to the formation of various unwanted side products. The maximum glucose conversion of 96.2% with ~35% yield of 5-HMF was obtained at 160 °C after 6 h of reaction, with 2.5M-SO42−/ZnO catalyst. Among all others, the 2.5M-SO42−/ZnO catalyst was the best due to the presence of an optimum acidity with an appropriate B/L ratio. Further, the catalyst separation and recycling studies were performed. The results revealed that the 2.5M-SO42−/ZnO catalyst could be recycled multiple times without substantial loss of catalytic activity and 5-HMF yield. Furthermore, a liquid-liquid extraction process was developed, demonstrating that almost 100% of 5-HMF could be extracted from the product solution with ~97% purity.

Advances of Ionic Liquids and Deep Eutectic Solvents in Green Processes of Biomass-Derived 5-Hydroxymethylfurfural.

5-Hydroxymethylfurfural (HMF) is identified as an important bio-based platform chemical to bridge petroleum-based and biomass-based resources. It can be obtained through dehydration of various carbohydrates as well as converted to value-added fuels and chemicals. As designer solvents, ionic liquids (ILs) and deep eutectic solvents (DESs) have been widely used in catalytic transformation of biomass derivatives to various chemicals. This Review summarizes recent progress in experimental and theoretical studies on dehydration of carbohydrates such as fructose, glucose, sucrose, cellobiose, chitosan, cellulose, inulin, and even raw biomass to generate HMF using ILs and DESs as catalysts/cocatalysts and/or solvents/cosolvents. It also gives an overview of IL and DES-involved catalytic transformation of HMF to downstream products via oxidation, reduction, esterification, decarboxylation, and so forth. Challenges and prospects of ILs and DESs are also proposed for further production of HMF and HMF derivatives from biomass in green and sustainable processes.

Improved Production of 5-Hydroxymethylfurfural in Acidic Deep Eutectic Solvents Using Microwave-Assisted Reactions.

Hydroxymethylfurfural (5-HMF) is a key platform chemical, essential for the production of other chemicals, as well as fuels. Despite its importance, the production methods applied so far still lack in sustainability. In this work, acidic deep eutectic solvents (DES), acting both as solvent and catalyst, were studied for the conversion of fructose into 5-HMF using microwave-assisted reactions. These solvents were screened and optimized by varying the hydrogen bond donor (HBD) and hydrogen bond acceptor (HBA). The bio-based solvent γ-valerolactone (GVL) was also applied as additive, leading to a boost in 5-HMF yield. Then, a response surface methodology was applied to further optimize operating conditions, such as reaction time, temperature and wt.% of added GVL. The highest 5-HMF yield attained, after optimization, was 82.4% at 130 °C, in 4 min of reaction time and with the addition of 10 wt.% of GVL. Moreover, a process for 5-HMF recovery and DES reuse was developed through the use of the bio-based solvent 2-methyltetrahydrofuran (2-Me-THF), allowing at least three cycles of 5-HMF production with minimal yield losses, while maintaining the purity of the isolated 5-HMF and the efficacy of the reaction media.

Evaluation of the inhibitory effect of 5-hydroxymethylfurfural (HMF) on ethanol fermentation by using immobilized Saccharomyces cerevisiae in stirred-tank bioreactor and mathematical modeling

During the pretreatment step of ethanol production from renewable resources, formation of the inhibitors can adversly affect the production yields and the environment. The aim of this study was to determine 5-hydroxymethylfurfural (HMF) concentration tolerance of immobilized Saccharomyces cerevisiae during ethanol production in glucose based media and to model ethanol formation, biomass growth, and substrate consumption. Results showed that the highest ethanol yield was calculated as 43.867% (32.07 g/L) in 6 g/L of HMF production. Additionally, the lowest yield and production values were obtained as 32.14% and 3.993 g/L when the system was run with 10 g/L of HMF. Compared to biomass growth, sugar consumption and ethanol production were less affected by HMF. Furthermore, according to modeling parameters (BF, AF, RMSE MAE, and R2 values), Baranyi successfully represented ethanol production, whereas Weibull was chosen as the best model for the representation of sugar consumption and biomass production.

Kinetics for glucose conversion to levulinic acid over solid acid catalyst in γ-valerolactone solution

A CH3-SBA-15-SO3H catalyst was synthesized for the conversion of glucose to levulinic acid. The performance of the catalyst was demonstrated by comparative experiments using γ-valerolactone solution system versus pure water system. Significantly, the conversion efficiency was almost five times higher for γ-valerolactone solution than that of the pure water. The side reactions of the γ-valerolactone solution system were probably less than that of water system. In order to provide a better understanding of the catalytic reaction and guide the engineering design, the kinetics of levulinic acid production from glucose over CH3-SBA-15-SO3H catalyst in γ-valerolactone solution were investigated. The kinetic model was established based on four differential equations, and the model results were fitted well to the experimental results. Notably, the activation energies of the production of 5-HMF and levulinic acid were 76.55 kJ/mol and 62.66 kJ/mol, respectively, which were obviously smaller than those previously reported, this may be attributed to the synergistic effect of the solid acid and the high concentration of γ-valerolactone solution.

Production of crude 5-hydroxymethylfurfural from glucose by dual catalysts with functional promoters in low-boiling hybrid solvent

5-Hydroxymethylfurfural (5-HMF) is a value-added versatile platform chemical from renewable biomass resources. In addition to improving the efficiency of catalysts for glucose conversion in reaction media, the product separation and purification represent another significant barrier in large scale production of 5-HMF. In this work, 5-HMF production from carbohydrates using a combination of Lewis and Brønsted acid catalysts was investigated in a low boiling point solvent consisting of ethylene glycol dimethyl ether (GDE) and water, allowing for feasible recycling of catalysts and product separation. High yield (70%) of 5-HMF from glucose is achieved in the presence of reaction additives, isopropanol (IPA) and NaCl, that help to stabilize 5-HMF and promote fructose dehydration, respectively. The results are validated in larger scale (glucose 140 g, reaction volume 2.2 L). To recover product free of the catalysts, the low-boiling polar solvents are evaporated and the crude product containing 80% 5-HMF is recovered by dissolution in a small amount of ethyl acetate (EA) followed by evaporation of EA. This 5-HMF production system offers the advantage of high 5-HMF yield from glucose and the feasibility of product separation.

SOME RECENT DEVELOPMENTS IN VALORIZATION OF CHITOSAN TO A VALUABLE PLATFORM CHEMICAL 5-HYDROXYMETHYLFURFURAL (5-HMF): A SHORT REVIEW

Production of 5-hydroxymethylfurfural (5-HMF) using chitosan will have great relevance in the net-carbon neutral econonmy. Chitosan is a common natural biopolymer with a wide range of uses in pharmacology, controlled drug delivery, healing materials, biosorbents, wastewater treatment, and other fields. Chitosan may be converted into a variety of derivatives and composites, as well as modified and grafted for particular applications. 5-HMF is a very useful platform chemical, and many laboratories and industries throughout the globe are working to produce it in a more sustainable manner utilizing greener biomass. The focus of this brief review is on recent research into 5-HMF synthesis from chitin and chitosan under diverse circumstances, with a particular emphasis on the previous five years. The review gives future scope for sustainable research and innovation in 5-HMF production from chitin biomass.

Conversion of Fructose to 5‐Hydroxymethyl Furfural: Mathematical Solution with Experimental Validation

Conversion of fructose to furan aldehydes is a rapidly developing concept considering the emergent scenario of the replacement of fossil‐derived components to biomass‐derived green precursors. 5‐hydroxymethyl furfural (HMF) and levulinic acid (LA) are the two most important bio‐precursors with expanded downstream utilization in modern industries. Their production from biomass‐derived sugars is a complex reaction due to competitive side reactions with a variety of byproducts. Therefore, their simulated optimization is an important tool that can help for process optimization in an economical way. In this article, we have developed a mathematical solution for fructose conversion, HMF production, and levulinic acid (LA) formation in a reactive environment. The accuracy of the developed model is further verified through experiments and found satisfactory with high accuracy. Therefore, the developed model can be used to simulate the reaction environment and product optimization under a given set of conditions.

Conversion of glucose into 5-hydroxymethylfurfural on granular zeolite catalysts

Biomass-derived 5-hydroxymethylfurfural (5-HMF) is a potential raw material for the production of a wide range of valuable chemicals and biofuels. Industrial production of 5-HMF from hexoses on solid catalysts is promising nowadays. Acid zeolites have great potential in application as catalysts for the dehydration of sugars. The purpose of this work was to obtain granular zeolite catalysts with optimal acidity and evaluate their effectiveness depending on the nature of the binder used. A zeolite catalyst without binder and samples with 10 wt % of kaolin/alumina were prepared. Their porous characteristics and acidity were studied by means of nitrogen low temperature adsorption/desorption, ammonia thermo-programmed desorption, and pyridine adsorption with IR control. The activity and selectivity of the catalysts for 5-HMF synthesis from glucose in the dimethyl sulfoxide medium at 160 ◦C were studied. The high efficiency of granular samples in glucose transformation into 5-HMF is confirmed. They are not only not inferior to, but even superior to, powdered samples. The component sources of Brønsted and Lewis acidity of the ammonium form of zeolite, which demonstrates acceptable activity (selectivity for 5-HMF is 34 %) despite the small number of Lewis centers, are considered in detail. The highest efficiency is demonstrated by the sample with aluminum oxide, which not only does not significantly deteriorate the microporous characteristics but also improves the mesoporosity of the catalyst. The selectivity towards 5-HMF on it reaches 44%. However, the developed mesoporosity of the sample with aluminum oxide is not critical to its activity. The main influence on the effectiveness of the catalyst in the synthesis of 5-HMF is played by the presence of acid centers of medium strength.