Production Of 5-hydroxymethylfurfural Research Articles

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.

Recent advancements in the production of hydroxymethylfurfural

Lignocellulosic materials can be utilized in the production of platform chemicals such as hydroxymethylfurfural (HMF). HMF production has been investigated in various aqueous, solvent, biphasic and ionic liquid systems. Aqueous medium usually suffers from a low HMF yield (usually 50 to 60% while using fructose as feedstock) due to the production of by-products and the decomposition of HMF. A higher HMF production was achieved by applying biphasic systems, however, these systems face some technical challenges including solvent recovery, process complexity and environmental issues, which prevent its practical implementations at industrial scales. The unique properties of ionic liquids (IL)s make them promising solvents for producing HMF from polysaccharides. In this review, the effects of various parameters such as catalysts, solvents, and process conditions on the production of HMF from various lignocellulosic feedstocks as well as systems developed for purifying HMF after production are discussed. Generally, the yield of HMF production in the IL systems was higher than 80% when fructose was used as the raw material, but was less than 50% when cellulose or other polysaccharides were used. However, the IL system is complicated and has a challenging recovery process. The proposed IL systems are also not environmentally friendly. The main emphasis of this paper is on the industrial applicability of proposed processes for producing HMF.

Advances in 5-hydroxymethylfurfural production from biomass in biphasic solvents

Biomass derived 5-hydroxymethylfurfural (HMF) has emerged as an important platform chemical for the production of value added chemicals and liquid fuels that are currently obtained from petroleum. Although a significant amount of research has been performed over the past decade, the high production cost of HMF is still a bottleneck for its sustainable utilization for making other value added chemicals and fuels on a commercial scale. Among several factors, low product selectivity and high purification cost are major constraints. To address these drawbacks, HMF production methodology in recent years has been directed towards utilization of biphasic media for concurrent extraction of HMF into an organic phase immediately after its formation in the reactive phase. As a result, several dozens of journal and patent articles have appeared, demonstrating the benefit of biphasic media for effective HMF extraction. This review article summarizes the findings of the most recent research articles with critical discussion on the factors that enhance the performance of biphasic media. Particular emphasis has been given to the development of more effective extracting solvents and their beneficial effect in enhancing HMF yield and selectivity, improvement of partition coefficient, mechanistic role of the bi-functional acid catalysts and factors that control high HMF selectivity for solid catalysts.

Hydroxymethylfurfural production from bioresources: past, present and future

5-Hydroxymethylfurfural (HMF) has been known as a product from hexose dehydration for over 100 years and is considered to be one of the most promising platform molecules that can be converted into a variety of interesting chemicals. HMF, together with furfural and 2,5-furandicarboxylic acid (FDCA) are derivatives of furan compounds, which were listed as the top 10 value-added bio-based chemicals by the US Department of Energy. The great and increasing interest in the production of furan derivatives from biomass resources is due to the great potential of furan derivatives as feedstock for bulk chemicals and fuels. HMF can be synthesized by dehydration of all types of C6 carbohydrates, including monomeric and polymeric carbohydrates, such as fructose, glucose, sucrose, starch, inulin, cellulose, and raw biomass. Numerous improvements and milestones have been made in the dehydration process during the past 130 years. The big challenge for the process of HMF production is its suitability for industrial scale yet being cost efficient. This perspective article will review the HMF development timeline, focusing on the important events, landmark contributions, engineering and practical challenges of HMF production.

Catalytic dehydration of C6carbohydrates for the production of hydroxymethylfurfural (HMF) as a versatile platform chemical

Interest in utilizing biorenewable feedstocks to produce fuels and chemicals has risen greatly in the past decade due to the economic, political and environmental concerns associated with diminishing petroleum reserves. A fundamental challenge lying ahead in the development of efficient processes to utilize biomass feedstock is that, unlike their petroleum counterparts, biomass contains an excess amount of oxygen. Therefore, catalytic strategies such as dehydration and hydrogenolysis amongst others have been extensively studied as platform technologies for deoxygenation. In this review, we primarily discuss the catalytic dehydration of C6 carbohydrates to 5-hydroxymethylfurfural, which has attracted much attention due to the versatility of using furanic compounds as an important platform intermediate to synthesize various chemicals. The emphasis is on the fundamental mechanistic chemistry so as to provide insights for further catalyst/catalytic system design. After separately discussing fructose and glucose dehydration, this review summarizes recent progress with bi-functional catalyst systems for tandem glucose/fructose isomerization and subsequent fructose dehydration, thereby realizing highly selective HMF production directly from the more abundant and cheaper C6 sugar feedstock, glucose.

An ionic liquid reaction and separation process for production of hydroxymethylfurfural from sugars

Hydroxymethylfurfural (HMF) is viewed as a potential platform material to make a variety of chemicals and products out of renewable resources. In this work, a complete ionic liquid reaction and separation process is presented for nearly stoichiometric conversion of fructose into HMF. The silicalite adsorbent material is demonstrated for separation of 99% pure HMF out of ionic liquid reaction mixtures through a packed column and for recovery of the unconverted sugars and reaction intermediates along with the ionic liquid. Membrane‐coated silicalite particles are prepared and studied for a practical adsorption process with separation performances comparable to or better than the powder material. It is discovered that nearly all the fresh fructose feed could be converted into HMF with the recycled ionic liquid under suitable reaction conditions. These research results lead to a new HMF production process much simpler than the current paraxylene manufacturing process from petroleum oil. © 2013 American Institute of Chemical Engineers AIChE J, 60: 300–314, 2014

Elucidating structure–properties relations for the design of highly selective carbon-based HMF sorbents

5-Hydroxymethyl furfural (HMF) production from fructose dehydration in DMSO with various catalytic systems has shown superior selectivity and high yields. Yet, the subsequent need for energy-intensive separation of HMF from HMF/fructose/DMSO mixtures challenges the practical feasibility of this process. Microporous carbon materials have shown promise as substrates for alternative adsorption-based separations, but the origin of HMF selectivity and adsorption capacity, and thereby structure–properties relations enabling rational design of enhanced sorbents, has remained elusive. Through systematic quantification of the functionality and texture of various commercial (BP2000, Norit1240) and synthetic carbons (three-dimensionally ordered macroporous carbons; mesoporous carbons), we link, for the first time, adsorption capacity and HMF adsorption selectivity to two tunable materials properties of the carbon sorbents: microporosity and oxygenate functionality (i.e., carbon polarity). In the process, we exploit these newly elucidated structure–properties relations for realizing a class of synthetic carbons with sub-micron particulate morphology that achieve more than 60% higher selectivity and more than 20% higher capacity for HMF over fructose as compared to the best performing commercial product, BP2000.