Fructose Dehydration Reaction Research Articles

Microwave-Assisted Production of 5-Hydroxymethylfurfural from Fructose Using Sulfamic Acid as a Green Catalyst

The development of safe-by-design synthesis of valuable chemicals from biomass derivatives is a key step towards sustainable chemical transformations in both academia and industry. 5-Hydroxymethylfurfural (5-HMF) is a biomass derivative chemical of high commercial interest due to its wide range of chemical and biofuel applications. In this scenario, the present work contributes to a methodology for producing 5-hydroxymethylfurfural (5-HMF) through fructose dehydration reaction under microwave irradiation. The proposed protocol uses a simple sodium chloride–saturated aqueous-i-PrOH biphasic system and catalysis of sulfamic acid, a low-cost solid Brønsted–Lowry inorganic acid, which presents pivotal features of a sustainable catalyst. A 23 full factorial design was applied to achieve the highest conversion and 5-HMF yield, allowing the identification of the main factors involved in the process. Under the optimized conditions, fructose at the concentration of 120 g L−1 was converted with 91.15 ± 6.98% after 20 min at 180 °C, using 10 mol% of catalyst. 5-HMF was produced in 80.34 ± 8.41% yield and 73.20 ± 8.23% selectivity. Thus, the present contribution discloses a new optimized methodology for converting the biomass derivative fructose to 5-hydroxymethylfurfural (5-HMF).

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.

Intense microwave heating at strongly polarized solid acid/water interface for energy-efficient platform chemical production

A strongly polarized solid/liquid interface is constructed to create a “micro-hydrothermal” environment under microwave and promote reaction energy efficiency. Specifically, TiO2 with open crystal structure was synthesized to maximize the density of surface-active centers and the degrees of interfacial polarization. Acidic groups were grafted on the catalyst surface, which served as catalytically active sites as well as heat-generation spots under microwave irradiation. Benefited by enhanced interfacial polarization, 10 times higher energy efficiency (6.8 mmol (kJ L)−1) than commercial TiO2 can be achieved in fructose dehydration reaction. MD simulation revealed that sulfonic group polarized surface water molecules and acted as “hot-spots” to accelerate fructose dehydration to HMF. Such alignment of site-specific heating and reaction by material design has great potential to shift the energy efficiency for a wide range of chemical reactions.

Effect of the sulphonating agent on the catalytic behavior of activated carbons in the dehydration reaction of fructose in DMSO

A series of -SO3R functionalized activated carbons (R=H, O, aryl) were prepared and applied in fructose dehydration reaction to 5-hydroxymethylfurfural. Different sulphonating methods introduce groups on catalyst surface with distinct donor-acceptor and hydrophilic properties. Their nature influences significantly not only activated carbon’s textural and chemical properties but also the product yields and selectivity in fructose dehydration reaction. The viability of the solvent free reaction was also investigated and compared to the performance of the catalyst series in presence of DMSO, where the best catalytic results were obtained.

Purification of 5‐Hydroxymethyl Furfural from Side Products of Fructose Dehydration Reaction in a Green Solvent

Abstract5‐Hydroxymethyl furfural (5‐HMF) is a most promising biogenic platform molecule with its proven potential for the production of spectrum of fuel and chemical products. Spectrum of heterogeneous catalysts have been reported for converting C6 sugars into 5‐HMF but the separation of side products of fructose dehydration reaction is still a major challenge in the way of its commercialization. The present work reveled adsorptive separation and purification of 5‐HMF from side products such as humins, soluble polymers, degradation, and condensation products, etc. Quaternary ammonium chloride functionalized macroporous resin was employed as an adsorbent at ambient conditions by using isopropyl alcohol (IPA) as a green and low boiling point (LBP) solvent. The use of single adsorbent, solvent and ambient condition provides >98 % assay purity of 5‐HMF.

Fructose dehydration reaction over functionalized nanographitic catalysts in MIBK/H2O biphasic system

A series of functionalized nanographitic carbons is prepared, characterized and tested in fructose dehydration reaction to 5-hydroxymethylfurfural. The functionalization treatment was selected to introduce various Brönsted acid sites and to modify the textural and catalytic properties of the initial carbon material. Within the series, the sulfonated carbons present the most interesting catalytic behavior resulting in important selectivity to the desired product once the reaction variables were properly adjusted.

Rational production of highly acidic sulfonated carbons from kraft lignins employing a fractionation process combined with acid-assisted hydrothermal carbonization

Highly acidic lignin-derived sulfonated carbons (LDSCs) were produced from hardwood and softwood kraft lignins under mild conditions by applying fractionation and/or pre-carbonization treatments combined with acid-assisted hydrothermal carbonization. The use of lignin fraction with higher amount oxygen, obtained from the fractionation process, resulted in carbon with the highest density of surface acid groups and improved catalytic activity. The LDSCs were successful tested in the dehydration reaction of fructose to obtain 5-hydroxymethylfurfural, and the best catalyst can be recycled without loss in its catalytic activity after perform a simple regeneration process. In contrast, the pre-carbonization step, commonly performed in several works, resulted in LDSCs with low acidity. A simple and optimized methodology for obtaining LDSCs under mild conditions was developed, and the correlations between the preparation method and the physicochemical and catalytic properties established in this work may be extendible to other starting materials for rational sulfonated carbons production.

Structure-properties relationship in the hydronium-containing pyrochlores (H3O)1+pSb1+pTe1-pO6 with catalytic activity in the fructose dehydration reaction.

A series of defect pyrochlores of the composition (H3O)1+pSb1+pTe1-pO6 have been prepared by ion exchange from K-containing pyrochlores K1+pSb1+pTe1-pO6 in sulfuric acid at 280 °C for 24 h. The structural characterization of the hydronium-containing pyrochlores, including the location of the H3O+ units within the three-dimensional framework, was possible from neutron powder diffraction data in undeuterated samples. The crystal structure for all the compounds is defined in the Fd3[combining macron]m space group, and consists of a covalent framework of SbVO6 and TeVIO6 octahedra distributed at random and connected by their vertices with (Sb,Te)-O1-(Sb,Te) angles close to 136°, conforming to large cages where the hydronium species are located off-center. The absence of K+ ions in the ion-exchanged pyrochlores was confirmed by inductively coupled plasma optical emission spectroscopy and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy. The shape and size of the hydronium units evolve along with the series, becoming more compact as the framework covalence and Lewis-basicity decrease upon Sb enrichment of the structure (for greater p values). The amount and lability of the H3O+ species also increase throughout the series, as wanted: a straightforward correlation of the catalytic activity in the fructose dehydration reaction to 5-hydroxymethylfurfural has been observed, reaching conversion rates up to 88.5% of concentrated fructose solution for the p = 0.25 catalyst. Moreover, a pseudo-first-order kinetic mechanism was simulated, and the kinetic constants obtained from diluted and concentrated enhanced reaction systems were determined and compared.

Synthesis 5-hydroxymethylfurfural (5-HMF) from fructose over cetyl trimethylammonium bromide-directed mesoporous alumina catalyst: effect of cetyl trimethylammonium bromide amount and calcination temperature

In this study, mesoporous alumina was synthesized using aluminium isopropoxide as Al precursor and cationic surfactant cetyl trimethylammonium bromide (CTAB) as structure directing agent and it was tested in the dehydration reaction of fructose into 5-HMF. The experiments were carried out in a microwave reactor at 200 °C for 5 min. The various ratio of CTAB/Al2O3 and calcination temperature between 400 and 700 °C were selected as synthesis parameters. The synthesized samples were analyzed by BET and XRD. The highest surface area was obtained as 602.22 m2/g with the weight ratio of CTAB to Al2O3 of 1.00 at the calcination temperature of 400 °C. When calcination temperature increased from 400 to 700 °C, surface area decreased into 286.14 m2/g. N2 adsorption/desorption isotherms of samples showed characteristic mesoporous type IV according to IUPAC classification. According to XRD patterns, all catalysts were in the amorphous structure. The maximum 5-HMF yield of 51% was achieved with the alumina catalyst calcined at 400 °C and CTAB/Al2O3 ratio of 1.0. Although the surface area decreased by rising the calcination temperature from 400 to 550 °C, the fructose conversion reached the highest value (97.54%).

Synthesis of Porous Organic Polymer-Based Solid-Acid Catalysts for 5-Hydroxymethylfurfural Production from Fructose

Herein, we report the synthesis of nanoporous polytriphenylamine polymers (PPTPA) by a simple one-step oxidative polymerization pathway and the materials were sulfonated with chlorosulfonic acid to introduce acidic sulfonic groups to the polymers to form solid acid catalysts (SPPTPA). Magnetic properties were added to SPPTPA catalysts by depositing Fe3O4 nanoparticles to develop (FeSPPTPA) solid acid catalysts, for performing dehydration of fructose to 5-hydroxymethylfurfural (HMF), which is regarded as a sustainable source for liquid fuels and commodity chemicals. XRD, FTIR spectroscopy, SEM, TGA, and N2 sorption techniques were used to characterize synthesized materials. The FeSPPTPA80 nanocatalyst showed superior catalytic activities in comparison to other catalysts due to the nanorods that formed after sulfonation of the PPTPA polymeric material which gave the catalyst enough catalytic centers for dehydration reaction of fructose. The recyclability tests revealed that the magnetic solid acid catalysts could be reused for four consecutive catalytic runs, which made FeSPPTPA a potential nanocatalyst for production of HMF.

P-Sulfonic acid calix[4]arene: A highly efficient organocatalyst for dehydration of fructose to 5-hydroxymethylfurfural

Biomass is an attractive renewable source of carbon since it has a huge potential as a substituent of the scarce fossil fuels and has been widely exploited to obtain important chemicals such as 5-hydroxymethylfurfural (HMF). Fructose, one of the main components of biomass, has been widely explored as precursor for obtaining HMF. Several efforts have been expended in the search for efficient and reproducible methodologies for the synthesis of HMF, a chemical platform important in the production of fuels and other value-added chemicals. In this work, the organocatalyst p-sulfonic acid calix[4]arene (CX4SO3H) was for the first time employed as a catalyst for fructose dehydration reaction to produce HMF. Various parameters such as temperature, reaction time, catalyst load, fructose concentration and catalytic efficiency of other Brønsted acids were investigated. 1H NMR spectroscopy was successfully used as qualitative and quantitative method in all steps of optimization. Using only 1 mol% of CX4SO3H as the catalyst (DMSO-i-PrOH 20% V/V, 140 °C, 50 mg mL−1 of fructose), 92% yield HMF could be obtained in a relatively short time (45 min). Thus, the present work was able to produce HMF from fructose with high efficiency and metal-free conditions.

Preparation of hydrothermal carbon as catalyst support for conversion of biomass to 5-hydroxymethylfurfural

Suitable hydrothermal carbonization conditions including temperature (180–250°C) and time (6–24h) were determined for the preparation of glucose derived carbon material, used as a catalyst support for sugar and cellulose conversions. While hydrothermal carbons (HTCs) prepared at various conditions exhibited similar chemical and structural characteristics, examination of liquid fractions from hydrothermal carbonization provided additional evidence on the stability of the HTCs. The suitable hydrothermal carbonization condition was found to be 220°C and 6h, providing a stable carbon support that after sulfonation, yielded carbon-based acid catalyst (HTC220-6-SO3H) that exhibit relatively high catalytic activities for cellulose hydrolysis and fructose dehydration reaction, giving glucose and HMF yields of 43.63±1.62wt.% and 20.29±1.09wt.%, respectively.

Dehydration of fructose and glucose to 5-hydroxymethylfurfural over Al-KCC-1 silica

In this research, the influence of several factors such as reaction time, catalyst weight, temperature and different solvents on dehydration reaction of fructose and glucose to 5-hydroxymethylfurfural (HMF) was surveyed. Nanosphere Al-KCC-1 silica with fibrous morphology was manufactured and used as proficient and recyclable catalyst for this reaction. SEM, TEM, BET, XRD, EDX, elemental mapping, ICP and FT-IR spectroscopy methods were applied for characterization of the Al-KCC-1 (molar ratio Si/Al= 5, 40) catalysts. 162°C and 1h are the best conditions for the fructose dehydration. Under this situation HMF yield and selectivity are 92.9% and 94.5% respectively and fructose conversion is 98.4%. Also 170°C and 2h are the best conditions for the glucose dehydration. In this situation HMF yield and selectivity are 39.0% and 39.9% respectively and glucose conversion is 97.8%.

Synthesis and characterization of functionalized alumina catalysts with thiol and sulfonic groups and their performance in producing 5-hydroxymethylfurfural from fructose

5-Hydroxymethylfurfural (HMF) has been identified as a potential candidate for biofuels and a high-potential intermediate chemical compound. The obtention of HMF from fructose is efficiently carried out using acid catalysts. In this work, a new catalyst of alumina synthesized by sol-gel as support was bifunctionalized with thiol (SH) and sulfonic (SO3−) groups by the grafting method and compared with other supports, i.e., synthesized boehmite and commercial alumina. The 3-mercaptopropyl-trimethoxysilane was utilized as a source of the thiol group to promote fructose tautomerization to its furanose form. The sulfonic group was obtained from 1,3-propanesultone, which carries out the dehydration of the fructose molecule. The prepared bifunctionalized catalysts were tested in the fructose dehydration reaction. The functional groups were identified through Fourier transform infrared spectroscopy (FTIR) as the primary characterization. The type of acid site was identified by Fourier transform infrared spectroscopy (–pyridine (FTIR-py)) and quantified by temperature-programmed desorption of ammonia (TPD-NH3). The molecular structures of thiol and the sulfonic groups anchored on the supports were resolved by nuclear magnetic resonance with cross-polarization (CP) and magic angle spinning (MAS) (CP-MAS-NMR). The bifunctionalized catalyst of alumina synthesized by sol-gel, being a very competitive material, reached a 55% selectivity to HMF at a 72% conversion at 453K.

Enhanced catalytic activity for fructose conversion on nanostructured niobium oxide after hydrothermal treatment: Effect of morphology and porous structure

This paper reports the synthesis of a new class of catalysts based on niobium using Filter Cake (FC) as precursor, which is more affordable economically than other niobium sources commonly used. FC is obtained before the necessary purification to obtain niobic acid (Nb2O5∙nH2O), making the catalyst synthesis process less costly. Its modification by hydrothermal treatment in the presence of different agents (oxalic acid or hydrogen peroxide) allowed the obtention of nanostructured materials in the form of rods or spheres with larger BET area, crystallinity and acidity than the precursor. Their catalytic potential were evaluated in fructose dehydration reaction in aqueous media, aiming the obtention of 5-hydroxymethylfurfural (5-HMF). The production of furan compounds from sugars has become a process of great interest in recent years because it is related to the search for more sustainable sources of energy, since carbohydrates are the predominant part of biomass. In optimum conditions, it was possible to obtain 22% yield of 5-HMF in aqueous medium and 47% yield of 5-HMF using DMSO as solvent.

Fructose dehydration to 5HMF in a green self-catalysed DES composed of N,N-diethylethanolammonium chloride and p-toluenesulfonic acid monohydrate (p-TSA)

Due to the increasing concerns about the availability and accessibility of fossil fuel reserves, and the subsequent effect of using them on climate change, production of green energy has recently become a hot area of interest in the research field. As a renewable energy source, biomass conversion to biofuels has shown a great potential towards green fuel production; particularly fructose conversion to 5-hydroxymethylfurfural (5HMF) as a building block material and source of green fuels and other high value chemicals. Herein, we investigate fructose dehydration to 5-hydroxymethylfurfural (5HMF) as a green fuel precursor, using a green self-catalysed environmentally friendly Deep Eutectic Solvent (DES), composed of inexpensive N,N -diethylethanolammonium chloride as organic salt and p -toluenesulfonic acid monohydrate ( p -TSA) as a hydrogen bond donor (HBD) and novel medium for the fructose dehydration reaction. The advantage of using this DES is its ability to act as a solvent and catalyst simultaneously. It has shown to actively catalyse the dehydration reaction of fructose under moderate reaction conditions with a high 5HMF yield of 84.8% at a reaction temperature of 80 °C, reaction time of 1 h, DES mixing ratio of 1:0.5 salt to p -TSA (w/w), and initial fructose ratio of 5.

Novel Ordered Mesoporous Carbon Based Sulfonic Acid as an Efficient Catalyst in the Selective Dehydration of Fructose into 5-HMF: the Role of Solvent and Surface Chemistry.

Novel ionic liquid derived ordered mesoporous carbons functionalized with sulfonic acid groups IOMC-ArSO3H and GIOMC-ArSO3H were prepared, characterized, and examined in the dehydration reaction of fructose into 5-hydroxymethylfurfural (5-HMF) both in aqueous and nonaqueous systems. To study and correlate the surface properties of these carbocatalysts and some other SBA-15 typed solid acids with 5-HMF yield, hydrophilicity index (H-index) were employed in the fructose dehydration. Our study systematically declared that almost a criterion may be expected for application of solid acids in which by increasing H-index value up to 0.8 the HMF yield enhances accordingly. More increase in H-index up to 1.3 did not change the HMF yield profoundly. Although, it has been shown that the catalyst with larger H-index (∼1.3) resulted in higher activity both in aqueous and 2-propanol systems, during the recycling process deactivation occurs because of more water uptake and the catalysts with optimum amount of H-index (∼0.8) is more robust in the dehydration of fructose.

Dehydration of fructose into 5-hydroxymethylfurfural by high stable ordered mesoporous zirconium phosphate

In this paper, a series of ordered mesoporous zirconium oxophosphate with different P/Zr molar ratios (M-ZrPO-x) were prepared via one-pot evaporation induced self-assembly strategy (EISA). The catalytic performance of M-ZrPO-x for the dehydration reaction of fructose to produce 5-hydroxymethylfurfural (5-HMF) was also studied. With high concentration of Brönsted and Lewis acid sites measured through NH3-TPD and pyridine-IR, M-ZrPO-0.75 performed high catalytic activity (up to 97.4%) and selectivity (79.6%) of 5-HMF under relatively mild conditions. Furthermore, M-ZrPO-0.75 performed excellent catalytic stability. Based on detailed analyses of XRD, SEM, TEM, BET and XRF, the structural, surface and textural properties of M-ZrPO-0.75 after reaction were investigated. Obtained results demonstrated that the mesostructure still retained even after twelve cycles, which may be ascribed to the “ordered” mesoporous properties and high thermal stability. In addition, a lower activation energy was obtained in this M-ZrPO catalytic system using dimethyl sulfoxide as solvent.

Tuning the acidity of niobia: Characterization and catalytic activity of Nb2O5–MeO2 (Me = Ti, Zr, Ce) mesoporous mixed oxides

Mesoporous Nb2O5–MeO2 (Me = Ti, Zr, Ce) mixed oxides were successfully prepared using evaporation-induced self-assembly (EISA) method. The structural and textural properties of these materials have been fully characterized using appropriate techniques (low-temperature adsorption–desorption of nitrogen, thermogravimetric analysis, X-ray diffraction analysis (XRD) transmission electron microscopy (TEM), scanning electron microscopy (SEM) and Raman spectroscopy). Acid–base properties were estimated by adsorption microcalorimetry of NH3 and SO2 molecules in order to determine the population, strength and strength distribution of acidic or basic sites. Formation of mesoporous structure was confirmed by the results of XRD, TEM and BET techniques. Results of adsorption microcalorimetry technique showed that the type of transition metal oxide added to niobia has a decisive role for acidic-basic character of investigated mixed oxides. Among the investigated mixed oxide formulations only Nb2O5–CeO2 was amphoteric, while the other samples showed prominent acidic character. All the investigated materials are catalytically active in fructose dehydration; conversion of fructose and selectivity to 5-hydroxymethylfurfural (5-HMF) and levulinic acid (LA) are proved to be dependant on the number of acidic sites on the surface of catalysts. Furthermore, presence of the basic sites on the surface of the catalyst decreases the activity in the fructose dehydration reaction, as in the case of Nb2O5–CeO2 sample.

Hierarchical ZSM-5, Beta and USY zeolites: Acidity assessment by gas and aqueous phase calorimetry and catalytic activity in fructose dehydration reaction

The acidity of hierarchical USY, Beta and ZSM-5 zeolites obtained by alkaline treatment was investigated. Samples were characterized by low temperature nitrogen adsorption, X ray diffraction and solid-state 27Al MAS NMR. Acidity of parent and mesoporous samples was estimated through the adsorption of typical probe molecules – measurements were conducted in both gas phase (microcalorimetry/volumetry of ammonia adsorption, FTIR spectrometry of pyridine adsorption/desorption) and aqueous phase (calorimetry of phenylethylamine adsorption). Quantitative distributions in strength of the acid sites were determined, as well as acid sites concentrations. No significant changes in total acidity were detected for ZSM-5. Acid sites strength was decreased in modified Beta and USY zeolites. The samples were probed as catalysts for the dehydration of fructose. Higher selectivities towards 5-hydroxymethylfurfural were detected for all modified zeolites, compared to the parent ones.