HMF Production Research Articles

Photocatalytic conversion of sugars to 5-hydroxymethylfurfural using aluminium(III) and fulvic acid

5-hydroxymethylfurfural (HMF) is a valuable and essential platform chemical for establishing a sustainable, eco-friendly fine-chemical and pharmaceutical industry based on biomass. The cost-effective production of HMF from abundant C6 sugars requires mild reaction temperatures and efficient catalysts from naturally abundant materials. Herein, we report how fulvic acid forms complexes with Al3+ ions that exhibit solar absorption and photocatalytic activity for glucose conversion to HMF in one-pot reaction, in good yield (~60%) and at moderate temperatures (80 °C). When using representative components of fulvic acid, catechol and pyrogallol as ligands, 70 and 67% HMF yields are achieved, respectively, at 70 °C. Al3+ ions are not recognised as effective photocatalysts; however, complexing them with fulvic acid components as light antennas can create new functionality. This mechanism offers prospects for new green photocatalytic systems to synthesise a range of substances that have not previously been considered.

Boosting hydrogen evolution via anodic oxidation of 5-hydroxymethylfurfural in anion exchange membrane electrolyzer over a metallic heterostructure

Coupling electrocatalytic 5-hydroxymethylfurfural (HMF) oxidation reaction (HMFOR) with hydrogen evolution reaction (HER) is capable of potentially enhancing energy efficiency for hydrogen production and converting biomass into high-valued products. Herein, a novel metallic heterostructure based on Ni3S2 and Co9S8 (Co9S8@Ni3S2/NF) was designed for H2 production and selective oxidation of HMF into 2, 5-furandicarboxylic acid (FDCA). Benefiting from the merit of metal heterojunction, Co9S8@Ni3S2/NF not only possesses appropriate H∗ adsorption energy, but also promotes the adsorption and desorption process of organic, thus making reaction dynamics for both HER and HMFOR more exceptional. Furthermore, the anion exchange membrane (AEM) electrolyzer with Co9S8@Ni3S2/NF as anode and cathode electrodes toward HMFOR and HER only required a low potential of 1.61 V for continuous hydrogen and FDCA production at the initial current density of 50 mA/cm2. The generation rate of H2 and FDCA are as high as 45.6 L/h/m2 and 7.25 mg/h/cm2, corresponding to the Faraday efficiency of ∼100% and 93.0%, respectively. The in-situ Raman and theoretical calculations demonstrated that the electron transfer from Ni3S2 to Co9S8 at heterogeneous interface contributes to the formation of Ni/Co–OOH, which is the active species of HMFOR.

Sulfonic acid functionalized β zeolite as efficient bifunctional solid acid catalysts for the synthesis of 5-hydroxymethylfurfural from cellulose

Introduction of the sulfonic acid group into H-β zeolite to prepare β-SO3H bifunctional catalysts for the efficient synthesis of 5-hydroxymethylfurfural (HMF) from cellulose. Catalysts characterization, such as XRD, ICP-OES, SEM (Mapping), FTIR, XPS, N2 adsorption-desorption isotherm, NH3-TPD, Py-FTIR demonstrate the sulfonic acid group was successfully grafted onto the β zeolite. A superior HMF yield (59.4 %) and cellulose conversion (89.4 %) was obtained in the H2O(NaCl)/THF biphasic system under 200 °C for 3 h with β-SO3H(3) zeolite as catalyst. More valuable, β-SO3H(3) zeolite converts other sugars and obtains ideal HMF yield, including fructose (95.5 %), glucose (86.5 %), sucrose (76.8 %), maltose (71.5 %), cellobiose (67.0 %), starch (68.1 %), glucan (64.4 %) and also converts plant material (25.1 % for moso bamboo and 18.7 % for wheat straw) with great HMF yield. β-SO3H(3) zeolite catalyst keeps an appreciable recyclability after 5 cycles. Moreover, in the presence of β-SO3H(3) zeolite catalyst, the by-products during the production of HMF from cellulose were detected, and the possible conversion pathway of cellulose to HMF was proposed. The β-SO3H bifunctional catalyst has excellent potential for the biorefinery of high value platform compound from carbohydrates.

A facile and practical conversion of carbohydrates into HMF using metal chlorides in [DMSO][CholineCl] deep eutectic solvent

Biofuels are a type of renewable energy that can become more vital in our lives. There are several advantages to switching to alternative biofuels and green techniques for producing these biofuels from biomass feedstock. 5-Hydroxymethylfurfural (HMF) is a potential precursor for biofuel and is synthesized from biomass sources. DMSO is specifically known as the most effective solvent for the conversion of biomass into HMF, leading to high yields. Due to the high miscibility of DMSO with various organic solvents, isolating HMF from the reaction mixture continues to be complicated. The use of a deep eutectic solvent (DES) in the biomass conversion process is attracting much attention. We have developed the synthesis of HMF from glucose, fructose, and cellulose using metal chloride in a [DMSO][CholineCl] deep eutectic solvent, which was easily obtained by combining DMSO and choline chloride. The yields of HMF under optimal conditions from glucose, fructose, and cellulose were 40%, 93%, and 15%, respectively. The HMF product can be isolated from [DMSO][CholineCl] deep eutectic solvent mixture by the liquid-liquid extraction using organic solvents with high purity.

Poly (ionic liquid)s-silica spheres as effective core-shell catalysts for the conversion of glucose and fructose into 5-hydroxymethylfurfural

5-Hydroxymethylfurfural (5-HMF), as a significant, bio-derived platform chemical molecule, has been under extensive research due to its wide application in petrochemical industry. In this work, three kinds of poly (ionic liquid)s-silica spheres (PIL@SiO2) with various lengths of alkyl chains as effective core-shell catalysts were prepared by the polymerization and coating methods, and were used to prepare 5-HMF from glucose and fructose with optimal results. When the alkyl carbon number of PIL monomer was 18, PIL@SiO2-18 displayed good catalytic activity in 5-HMF production, resulting in the highest yields of 77.36% and 72.8% from glucose and fructose in methyl isobutyl ketone (MIBK)/ saturated solution of sodium chloride (Sat.NaCl) biphasic solvent. A possible reaction mechanism was proposed that the core-shell synergistic catalysis effectively promoted the preparation of 5-HMF from monosaccharide, in which Lewis acidic polycationic centers contributed to driving the isomerization process. The promising approach provides an efficient strategy for silica-based core-shell synergistic catalysts in the synthesis of 5-HMF from carbohydrates.

One-Step method for the production of 5-HMF from catalytic conversion of microalgal biomass

One-Step method for the production of 5-HMF from catalytic conversion of microalgal biomass

Optimization Study of Glucose Synthesis to 5-Hydroxymethylfurfural (5-HMF) by Using Low Transition-Temperature Mixtures (LTTM)

5-Hydroxymethylfurfural (5-HMF) is a potential value-added product gaining popularity due to its wide range of applications. Glucose is widely used for 5-HMF production because it is abundant and more cost-effective than other resources. In the current research, a combination of microwave irradiation and low transition-temperature mixture (LTTM) for 5-HMF production was sustainably created. A preliminary study was conducted to derive 5-HMF using LTTM as a green solvent in various ratios of glucose: LTTM (MA/ChCl): water (10:100:15) and (10:48:100) via microwave heating at 90 °C for 10–60 min reaction time. The product analysis revealed that the 10:100:15 combination ratio of glucose: LTTM: water produced more 5-HMF (20.5%) than the 10:48:100 (0.28%) ratio. Following the preliminary results, an optimization study was conducted, focusing on the reaction temperature, LTTM mass, and water to assess the impact on 5-HMF yield and glucose conversion, using CCD in Design-Expert software. The quadratic model fit for 5-HMF yield and the 2FI model for glucose conversion yielded R2 values of 0.9861 and 0.8610, respectively. Both responses had a significant p value of 0.0061 for glucose conversion and <0.0001 for 5-HMF yield. An optimum point was achieved at 100 °C, 100 g of LTTM, and 20 g of water, with an expected 5-HMF yield and glucose conversion of 45.77% and 69.03%, respectively.

Titanium oxide/nickel foam (TiO2/NF) catalyzed the conversion of glucose to 5-hydroxymethylfurfural in subcritical solvothermal liquefaction

The glucose conversion into 5-hydroxymethylfurfural (HMF) typically required Lewis and Brønsted acid catalysts. The mesoporous TiO2 supported on nickel foam (NF) was synthesized using modified sol–gel dip-coating methods. The prepared catalysts were characterized to observe their physical and physicochemical properties. The catalyst characterization showed that TiO2 is successfully incorporated onto the NF surface. Nitrogen adsorption/desorption isotherms and NH3-TPD analysis showed that the TiO2/NF catalysts have a large specific surface area and high surface acidity, which can enhance glucose dehydration. The liquid products from the solvothermal reaction were analyzed using GC–MS analysis. Under the optimal reaction conditions, about 46% of HMF yield was obtained, and the liquid products contained furan derivatives and phenolic compounds. The solid TiO2/NF catalyst allowed easy catalyst recovery from liquid products. The reusability of the TiO2/NF catalysts is still acceptable and shows the TiO2/NF catalyst's potential for usage in HMF production.

Production of furan chemicals from contaminated biomass using hydrothermal-assisted activated persulfate strategy: Exploring the critical role of heavy metals on products

Sustainable disposal of heavy metal contaminated biomass has always been a challenging task. Here, a strategy was proposed for directly producing valuable 5-hydroxymethylfurfural (HMF) and furfural (FF) from contaminated biomass through hydrothermal-assisted persulfate activation strategy. The optimal yields were obtained at 18.6 and 22.5 wt% for HMF and FF, respectively. The hydrothermal process promoted the release of Fe, Mn, Cu, Zn, and Cr from biomass into the liquid phase and then activated peroxymonosulfate (PMS) to destroy the lignocellulose structure and increase the accessible of cellulose and hemicellulose. Meanwhile, the metal and acidic environment provided by the reaction system act as natural catalysts to synergistically promote the production of HMF and FF. The controlled experiments revealed that Fe, Mn, Zn, and Cr played a major role in biomass conversion during this process. Moreover, possible reaction mechanisms and pathways were explored through quenching tests and density functional theory calculations. This study provides a simple pretreatment and promising valorization strategy for the sustainable utilization of heavy metal-contaminated biomass.

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.

Determination of the Anticarcinogenic Activity of 5-Hydroxymethyl-2-furfural Produced from Grape Must Under in vitro Conditions

Every year, millions of tons of food and beverage waste are thrown away unused around the world. The carbohydrates found in food waste create a raw material potential for the production of high value-added products that are used in energy, feed and pharmacology. One of these products, 5-Hydroxymethyl-2-furfural (5-HMF), is a by-product of simple dehydration of carbohydrates. It finds wide use in the field of pharmacy due to its anticancer, antifungal and antimicrobial activities. Many studies have stated that the sugar source with the highest conversion rate in 5-HMF production is fructose. For this reason, in this study, it was aimed to realize the production of 5-HMF in autoclave sterilization carried out under high temperature and pressure using grape must waste, which is known to have high fructose content, and determine the anticarcinogenic activity and cytotoxicity of the produced 5-HMF under in vitro conditions. In this study, it was determined that the medium containing DMSO increased the sugar conversion percentage, 5-HMF efficiency and selectivity in the waste grape must more than the medium containing only water. In the production of 5-HMF, the conversion of sugar in the medium saturated with salt, and the efficiency and selectivity of 5-HMF were determined as 97.04%, 68.61% and 70.82%, respectively, when DMSO organic solvent was used. In addition, it has been determined that 5-HMF produced from waste grape must has a toxic effect on both healthy cells and cancer cells and has anticancer properties.

Some Characteristics of Breakfast Spreadable Cornelian Cherry (Cornus mas L.) Nectar Produced Using Potentially Probiotic Starter Culture

In this study, it was aimed to make a breakfast spreadable Cornelian cherry nectar similar to marmalade. Lactiplantibacillus plantarum DA100 strain, which has potential probiotic properties, was added to this nectar. It was investigated whether this strain has an effect on various sensory properties of nectar. In the study, sensory and various chemical properties of nectar produced without probiotic microorganism were determined. Since the breakfast spreadable Cornelian cherry nectar produced in our study was not exposed to high temperatures for a long time, a very low HMF of 4.290 mg/kg was determined. Vitamin C was determined as 716.800 mg/L and total phenolic content was determined as 3156.64 mg GAE/100g. In the probiotic group, the microorganism viability, which was 1.5×1010 Log CFU/mL initially, was determined below approximately 1.5×106 Log CFU/mL at the end of 5 days. In addition, coliform bacteria and E. coli were not detected in any group during this period. Contrary to the texture score, the difference between the sensory evaluation results of the probiotic-added and the control group of breakfast spreadable Cornelian cherry nectar was significant in taste, bitterness, odor and sourness. An alternative to jams and marmalades, rich in vitamin C and phenolic content, limited HMF production, and a functional product with low sugar content were tried to be obtained, and when the results obtained are evaluated, the product is thought to be promising.

Efficient conversion of glucose to 5-hydroxymethylfurfural by synergetic catalysis of enzymes and chemical catalysts towards potential large-scale continuous operation

A continuous process to efficiently produce 5-hydroxymethylfurfural (HMF) from glucose by synergetic catalysis of enzymes and chemical catalysts was developed in dimethyl sulfoxide (DMSO)/water system under mild conditions. Sweetzyme IT Extra and Amberlyst 36 were used as heterogeneous catalysts for glucose isomerization and fructose dehydration, respectively, in packed bed reactors. Fructose yield of 50.9 % was obtained during glucose isomerization in 1:1 VDMSO/VWater medium at 60 °C and residence time of 30 min. Selective dehydration of fructose in glucose-fructose mixture was achieved in DMSO medium with fructose conversion of higher than 97 % and HMF yield of 87.2 % at 85 °C and a residence time of 40 min, where 93 % glucose unconverted. By adjusting the water content in the reaction system and recycling of water from isomerization and extraction units, the catalysts could keep good stability for 150 batches reuse without loss of activity. Based on the converted glucose, glucose conversion, HMF yield and selectivity reached 100 %, 81.5 %, and 81.5 %, respectively. This process showed great promise for production of HMF from glucose in continuous operation at large scale.

Role of reaction adsorption on the production of 5-hydroxymethylfurfural from fructose under microwave hydrothermal process

5-Hydroxymethylfurfural (HMF) has been considered a valuable biomass-derived platform chemical that can be produced by hexose dehydration in the presence of an acid. However, the yield of HMF is always reduced because of side reactions such as rehydration and condensation. In this work, the reactive adsorption process of fructose dehydration to HMF catalyzed by hydrochloric acid under microwave condition was studied. BP2000 has better adsorption capacity than activated carbon (AC) in reactive adsorption, and addition of BP2000 increases the HMF yield. The maximum theoretical yield of HMF was 65 % obtained by adding 39 g L−1 BP2000 and reacting for 4 min at 160 °C under a microwave hydrothermal condition. It was discovered thatmicrowave hydrothermal technology (MHT) could significantly increase efficiency and reduce reaction time. Reactive adsorption could efficiently buffer HMF from side reactions when reaction conditions became severe, thereby increasing the HMF yield. Reactive adsorption provides a more sustainable method for HMF production and separation.

Comparative techno-economic and energy analyses of integrated biorefinery processes of furfural and 5-hydroxymethylfurfural from biomass residue

For efficient feedstock and energy utilization, integrated biorefinery processes are applied to furfural production from bagasse to convert furfural residue into 5-hydroxymethylfurfural (HMF)—an important intermediate building block for the production of various biochemicals. Here, a techno-economic analysis of the integrated processes of furfural and HMF production combined with electricity generation under different scenarios was performed to identify the most suitable process design. Simulations revealed that using the whole bagasse in the biorefinery plant and recycling 50% waste from the HMF production to recover unreacted sugar (scenario 2) achieved the maximum furfural and HMF production with minimum CO2 emission, compared with integrated processes without sugar recycling (scenario 1), with 80% (scenario 3) and 60% biomass (scenario 4) bypassed to the biorefinery, and with a standalone combined heat and power system (scenario 5). Moreover, heat integration improved the efficiency of biorefinery plant (scenario 2), with an energy recovery potential of 71%, leading to the maximum profit at 11% internal rate of return. However, the high operating cost associated with the requirement of solvents and catalysts for HMF production represents the largest cost distribution in the proposed integrated processes. Sensitivity analysis revealed that solvent cost was the most important parameter for economic benefit. In addition, improving technological efficiency in the pretreatment and HMF production phases can enhance product yield, thereby benefiting the profitability of this process.

NiFe Layered Double Hydroxide-Derived Catalysts with Remarkable Selectivity for the Oxidation of 5-Hydroxymethylfurfural to 2,5-Furanedicarboxylic Acid under Base-Free Conditions

In this work, we report the exciting discovery of inexpensive and durable catalysts for the selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furanedicarboxylic acid (FDCA) under base-free conditions. A nickel-iron layered double hydroxide (NiFe-LDH) precursor was first prepared then subjected to hydrothermal sulfidation with thioacetamide at 120 °C or thermal phosphidation with sodium hypophosphite at 400 °C to produce NiFeS and NiFeP-400 catalysts, respectively. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) showed these catalysts to contain FeNi2S4 and FeNi2P, respectively, as the dominant phases. The catalytic activity of each catalyst was optimized by studying the effect of the solvent, reaction temperature, oxidant, and reaction time on HMF conversions and product distributions. Under optimized conditions (acetonitrile solvent, 120 °C, tert-butanol peroxide as an oxidant, 12 h, respectively), the NiFeS catalyst afforded 100% HMF conversion with an 83.2% FDCA selectivity with the performance of the NiFeP-400 catalyst being almost identical (HMF conversion of 100%; FDCA selectivity of 82.7%). Both catalysts showed excellent stability over five cycles of catalyst tests with the catalysts able to be easily collected after use with a magnet. Based on the experimental findings, the similar reaction mechanisms used are to be proposed for HMF oxidation to FDCA over the two catalysts. Results show that metal sulfide-based and metal phosphide-based catalysts are promising alternatives to traditional noble metal-based catalyst for the valorization of bio-derived HMF.

Direct conversion of glucose to 5-hydroxymethylfurfural over niobium oxide/phosphate-carbon composites derived from hydrothermal carbonization of cyclodextrins

Direct conversion of glucose to 5-hydroxymethylfurfural was studied in a biphasic system, with phosphated niobium oxide-carbon catalysts. We developed a facile approach to generate Nb-based composites with high metal loadings (∼ 20 %) through hydrothermal carbonization (HTC), followed by calcination and H3PO4 adsorption. Attention has been paid to the nature of oligosaccharide and amount of water used upon HTC. Catalysts were characterized by XRD, N2 adsorption, NH3-TPD, SEM-EDS and XPS. NbP@C-RB30 and NbP@C-RB15 prepared from randomly methylated β-CD in low volumes were found to be more efficient for HMF production, with yields of 32-34 % attained after 3 h in biphasic NaCl-water/methyl isobutyl ketone media. Notably, HTC route provided appropriate conditions for forming acidic Nb2O5 nanoparticles, dispersed and maintained over carbon microspheres, and enriched with surface P–OH. These features played an important role for an adequate distribution of the catalyst in the reaction medium composed of two immiscible solvents.

Efficient conversion of chitin into 5-hydroxymethylfurfural via a simple formylation step under mild conditions

A novel, sustainable, and efficient HMF production route from chitin was achieved via a simple formylation step under mild conditions.

PolyE-IL Is an Efficient and Recyclable Homogeneous Catalyst for the Synthesis of 5-Hydroxymethyl Furfural in a Green Solvent.

5-Hydroxymethyl furfural (5-HMF) is a potential platform molecule with multidimensional applications and can be produced from biomass-based hexose sugars. In the present article, polyethyleneimine (PEI)-functionalized polymeric Bronsted acid ionic liquid (PolyE-IL) catalyst has been explored for fructose dehydration in the presence of isopropyl alcohol (IPA) as a green and low-boiling-point (LBP) organic solvent. The use of homogeneous PolyE-IL catalyst provides several specific advantages in terms of high yield, conversion, selectivity, ease of catalyst separation, recycle and reuse, and so forth. PEI with various Bronsted acid counterions such as H2SO4, H3PO4, TsOH, TfOH, and TFA provides the corresponding variables of PolyE-IL such as [PEI]+[HSO3]-, [PEI]+[H2PO4]-, [PEI]+[CF3CO2]-, [PEI]+[TfO]-, and [PEI]+[TsO]-, which are tested for fructose dehydration in the presence of IPA. Of the tested catalysts, only PolyE-IL with [HSO4]-, [CF3CO2]-, [TfO]-, and [TsO]- counterions showed the formation of 5-HMF. [PEI]+[HSO4]- showed the maximum yield of 5-HMF (61%) and selectivity (70%) with (87%) fructose conversion. Thus, further process optimization study was conducted to obtain the maximum yield, conversion, and selectivity. The intensified process provides a maximum yield of 5-HMF of 75% with 85% fructose conversion and 90% selectivity. The catalyst recyclability study showed the consistency in 5-HMF yield (75%), conversion (85%), and selectivity (90%) for five consecutive recycle runs. However, the study of reaction kinetics showed the first-order kinetics with an activation energy of 12.4 kJ/mole by using [PEI]+[HSO4]- catalyst. Thus, the use of an easily recyclable and robust catalyst provides an efficient route for production of 5-HMF in the presence of a green solvent.

Temperature-Responsive Deep Eutectic Solvents for Highly Selective Separation of 5-Hydroxymethylfurfural from Reaction Mixture

5-Hydroxymethylfurfural (HMF) is a key biobased platform compound for the production of high-value chemicals and fuels. However, separation and purification of HMF is currently the bottleneck for HMF production. In this work, a novel class of temperature-responsive deep eutectic solvent (DES)–water systems have been explored to selectively separate HMF from reaction mixtures. The fructose dehydration reaction was conducted in homogeneous DES–H2O systems, and then, the produced HMF was migrated to the DES-rich phase while the unreacted fructose was retained in the H2O-rich phase upon cooling. Thus, selective separation of HMF was realized. It was found that water–water and DES–DES interactions predominate over DES–water interactions during cooling, thus resulting in upper critical solution temperature phase separation. Under optimal conditions, the partition coefficient and separation factor of HMF could reach up to 78 and 609, respectively, which is about 5 and 13 times those reported in ionic liquid-based aqueous biphasic systems. Furthermore, HMF could be removed from the DES-rich phase, giving a high recovery efficiency of 69%, which is much higher than the best value reported in the literature. At the same time, DES was regenerated and reused in the next process, and no obvious decrease in partition coefficient of HMF was observed after six cycles.