Conversion Of Fructose Research Articles

Sulfonated magnetic carbon nanoparticles from eucalyptus oil as a green and sustainable catalyst for converting fructose to 5-HMF

Sulfonated magnetic carbon nanoparticles (SMCNs) were synthesized from eucalyptus oil via co-pyrolysis with ferrocene and sulfonation by H2SO4. Catalytic performance of SMCNs for conversion of fructose to 5-hydroxymethylfurfural was examined within a designated range of reaction temperature (120–180 °C) and time (30–240 min). 84% conversion of fructose and 51.6% yield of 5-hydroxymethylfurfural could be achieved with catalyst-to-fructose mass ratio of 0.167 at 180 °C and the reaction time of 30 min. The magnetic property of SMCNs also facilitated recovery and recycling of the spent catalyst. Additionally, more than 50% yield of 5-hydroxymethylfurfural could be achieved after three cycles.

Microwave-assisted liquefaction of carbohydrates for 5-hydroxymethylfurfural using tungstophosphoric acid encapsulated dendritic fibrous mesoporous silica as a catalyst

Tungstophosphoric acid (TPA) encapsulated dendritic fibrous silica KCC-1 was prepared via a microemulsion system with the simple reflux method using cetyltrimethylammonium bromide as a structure-directing agent. The TPA impregnated on KCC-1 (ITPA-KCC-1) was also prepared for comparative. Various physicochemical techniques were used to characterize the synthesized materials and their activity evaluated in the 5-hydroxymethylfurfural (HMF) formation from carbohydrates derivatives of fructose, glucose and cellulose. The effect of various factors such as catalyst to substrate ratio, different solvents and temperature were investigated on the formation of HMF. The resultant encapsulated catalyst was very active in fructose dehydration with the yield of 92% HMF and full conversion of fructose at 120 °C for 30 min under the microwave heating condition without any salt additive in the THF solvent system as well as 95% in MIBK solvent. The HMF yield was achieved by 58% and 16.2% from glucose and cellulose in the DMSO solvent, respectively. The TPA-KCC-1 can be separated easily after reaction from the reaction mixture and reused atleast five times without substantial loss in catalytic activity. This study provides an easy encapsulation method for TPA in dendritic fibrous silica KCC-1 as a heterogeneous catalyst, and it should have great application potential in other biomass valorization processes.

Preparation of kapa carrageenan-based acidic heterogeneous catalyst for conversion of sugars to high-value added materials

A novel composite based on kappa-Carrageenan (κC) was prepared using N,N-methylene bisacrylamide (MBA) as the crosslinking agent. 5-Hydroxymethylfurfural (5-HMF) was produced by catalytic dehydration of fructose and glucose with MBA grafted κC (κC-g-MBA) as the solid acid catalyst due to sulfonic acid groups in biopolymer skeletons. Various reaction parameters such as optimization of the quantity of the catalyst, temperature, reaction time, and solvent were performed. It was established that for fructose dehydration, the best reaction conditions were the 160 °C as the optimized reaction temperature and 1 h reaction time, respectively. Under these conditions, the HMF yield and fructose conversion were 94.2% and 95.5%, respectively. Furthermore, 160 °C and 2 h were the best reaction temperature and reaction time for glucose dehydration, respectively. Under similar conditions, the HMF yield and glucose conversion are 47% and 93%, respectively. The catalyst was readily prepared from inexpensive materials with considerable reusability and reactivity.

Milder operating parameters for one‐step conversion of fructose to levulinic acid over sulfonated H‐β zeolite in aqueous media

AbstractThe sulfonated H‐β zeolite was successfully prepared and used for the synthesis of levulinic acid (LA) from D‐fructose. The catalyst was characterized by powder X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscope, N2 physisorption, NH3‐temperature programmed desorption and carbon–hydrogen–nitrogen–sulfur analysis. The total acid amount is increased with increase in sulfur loading, confirmed that the sulfonic acid group (SO3‐H) is successfully grafted onto zeolite structure. The various parameters such as different amount of sulfur loading, reaction temperature, time, catalyst loading was studied for selective production of LA. The catalytic activity of sulfonated H‐β (S‐β) zeolite was found to be efficient for synthesis of LA from D‐fructose in aqueous media. Maximum LA yield of 43.5 mol%, low HMF yield (<1%) with 98.15% fructose conversion was obtained with 3% S‐β catalyst at 160°C for 7 hr. The catalyst was reusable for minimum three times by H2O2 regeneration. This study provides the new zeolitic catalyst for the efficient production of LA at shorter reaction time (7 hr) and low catalyst to substrate ratio (0.7:1).

Visible light-induced photo-Fenton dehydration of fructose into 5-hydroxymethylfurfural over ZnFe2O4-coated Ag nanowires

ZnFe2O4-coated Ag nanowires (Ag@ZnFe2O4 NWs) were prepared for the photo-Fenton induced dehydration of fructose into 5-hydroxymethylfurfural (5-HMF) in visible light region. Effects of ZnFe2O4 content, volume ratio of dimethyl sulfoxide (DMSO) to deionized water, reaction temperature, fructose dosage, H2O2 content, pH values, inorganic ions, and quenchers on the fructose conversion, 5-HMF yield, and 5-HMF selectivity were performed in detail. Among these obtained composites, Brønsted acidic Ag@ZnFe2O4 NWs with Ag NWs diameter of around 20 nm and ZnFe2O4 coating of 6.13 wt% exhibit the best photo-Fenton catalytic activity for the conversion of fructose into 5-HMF, and slightly deactivate after five cycle times. The surface plasmon resonance effect of Ag NWs and the synergistic effect between ZnFe2O4 and Ag NWs are favorable for the visible light absorption and the efficient transfer and separation of charge carriers. DMSO as well as OH radical plays the vital role in the photo-Fenton induced dehydration of fructose into 5-HMF.

Energy metabolism

Most animal cells are able to meet their energy needs from the oxidation of various types of compounds: sugars, fatty acids, amino acids, but some tissues and cells of our body depend exclusively on glucose and the brain is the largest consumer of all. That is why the body has mechanisms in order to keep glucose levels stable. As it decreases, the degradation of hepatic glycogen occurs, which maintains the appropriate levels of blood glucose allowing its capture continues by those tissues, even in times of absence of food intake. But this reserve is limited, so another metabolic pathway is triggered for glucose production, which occurs in the kidneys and liver and is called gluconeogenesis, which means the synthesis of glucose from non-glucose compounds such as amino acids, lactate, and glycerol. Most stages of glycolysis use the same enzymes as glycolysis, but it makes the opposite sense and differs in three stages or also called deviations: the first is the conversion of pyruvate to oxaloacetate and oxaloacetate to phosphoenolpyruvate. The second deviation is the conversion of fructose 1,6 biphosphate to fructose 6 phosphate and the third and last deviation is the conversion of glucose 6 phosphate to glucose.

Synthesis and Evaluation of Levulinic Ester as Biodiesel Additives

In this study, the SO42-/TiO2-La2O3-Fe2O3 catalyst was prepared and tested in the conversion of fructose to ethyl levulinate . The catalyst was characterized from the point of view of the textural analysis, FT-IR analysis, acid strength distribution, X-ray powder diffraction and pyridine adsorption IR spectra. The influence of the reaction parameters on the ethyl levulinate yield was study. The maximum yield of 37.95% in levulinate esters was obtained at 180 �C, 2 g catalyst and 4 h reaction time. The effect of ethyl levulinate addition to diesel-biodiesel blend in different rates, i.e, 0.5, 1, 2.5, 5 (w.t %) on density, kinematic viscosity and flash point was evaluated and compared with the European specification.

Organic acid catalyzed production of platform chemical 5-hydroxymethylfurfural from fructose: Process comparison and evaluation based on kinetic modeling

Fructose was converted to 5-hydroxymethylfurfural (HMF), an important biomass-derived platform chemical, under mild conditions (100–130 °C) with several organic acids including p-toluene sulfonic (pTSA), oxalic, maleic, malonic and succinic acids as the catalysts. The process kinetics was compared considering fructose dehydration to HMF as the objective reaction and condensation of fructose and HMF to humin and rehydration of HMF as the main side reactions. DMSO was found to be the most effective solvent reaction medium to obtain high fructose conversion and HMF yield. Observed kinetic modeling illustrated that the rehydration and condensation of HMF in DMSO actually could be neglected, especially for the oxalic acid catalyzed system. The determined observed activation energy for fructose conversion to HMF and humin in DMSO medium was 33.75 and 24.94 kJ/mol for pTSA catalyzed system, and 96.51 and 78.39 kJ/mol for oxalic acid-catalyzed system, respectively. HMF yields of 90.2% and 84.1% were obtained for pTSA and oxalic acid catalyzed systems, respectively.

Efficient and environmentally-friendly dehydration of fructose and treatments of bagasse under the supercritical CO2 system

The ability of supercritical/subcritical carbon dioxide (SC/Sub-CO2) to catalyze the production of 5-hydroxymethylfurfural (5-HMF) from fructose was studied in this paper. The optimal conditions for the conversion in SC/Sub-CO2 systems were determined, and sugarcane bagasse (SCB) was pretreated with SC-CO2 using 1-butyl-3-methylimidazolium acetate ([Bmim]OAc). Structural analysis of SCB samples was done by Fourier transform infrared (FT-IR), X-ray Diffractometer (XRD), Thermal gravimetric (TG), Solid state nuclear magnetic resonance (13C NMR) and scanning electron microscope (SEM) analyses. The contents of sugars in the acid and enzymatic hydrolysates were measured. The results showed that the optimum fructose conversion conditions of the SC-CO2/[Bmim]Cl system were 9 MPa, 120 °C and 0.5 h and the Sub-CO2/H2O system were 6 MPa, 180 °C and 2 h. Besides, SC-CO2/[Bmim]OAc was the most effective pretreatment process, with the lignin and hemicellulose removal rates in SCB being 8.78 and 4.83% respectively. FT-IR, SEM, XRD and TG analysis indicated that the SC-CO2/[Bmim]OAc pretreatment changed surface morphology, increased crystallinity and decreased thermal stability of SCB. Moreover, the yield of reducing sugars obtained by enzymatic and acid hydrolysis increased by 12.57 and 22.04%, respectively. The energy balance showed that SC-CO2/[Bmim]OAc pretreatment was efficient to increase the energy output of SCB.

A Robust and Highly Selective Catalytic System of Copper-Silica Nanocomposite and 1-Butanol in Fructose Hydrogenation to Mannitol.

We report for the first time the selective production of mannitol, a low-calorie sweetener and an important pharmaceutical ingredient, from fructose using Cu-SiO2 nanocomposite as catalyst and 1-butanol as solvent. When compared with water and ethanol, a lower fructose solubility was achieved in 1-butanol, which caused a lower fructose conversion and higher mannitol selectivity by reducing formation of side products. Among various Cu-based catalysts in 1-butanol, Cu(80)-SiO2 nanocomposite gave an unprecedented mannitol (83 %) and sorbitol (15 %) yield at 120 °C, 35 bar H2 , and 10 h reaction time. More importantly, this catalyst did not show any Cu leaching and its physicochemical properties were maintained after liquid-phase fructose hydrogenation whereas other Cu-based catalysts such as Cu(32)-Cr2 O and Cu(66)-ZnO did show significant leaching of Cu and Cr. Thus, Cu(80)-SiO2 nanocomposite and 1-butanol are regarded as a robust and highly efficient catalytic system for the selective hydrogenation of fructose to mannitol. Also, density functional theory calculations supported that in addition to the stable initial structure of adsorbed fructose, the mannitol pathway was more thermodynamically favorable than the sorbitol pathway. Notably, the highly pure mannitol (99 %) could be recovered from the sorbitol-containing 1-butanol solution by simple filtration. Therefore, the present protocol is a novel and effective method to produce pure mannitol from fructose in both an environmental and an industrial context.

Efficacy of clay catalysts for the dehydration of fructose to 5-hydroxymethyl furfural in biphasic medium

5-Hydroxymethyl furfural (HMF) is one of the important platform chemical obtained from C6 sugars derived from biomass. The efficiency of montmorillonite clay catalysts (K-10, K-20, K-30, and Al pillared clay) has been systematically explored for the synthesis of HMF through dehydration of fructose in a biphasic solvent system. The catalysts were characterized by XRD, N2 sorption, 27Al MAS NMR, 29Si NMR and FT-IR of chemisorbed pyridine. Acid treated K-10 catalyst was found to be the best among the clay catalysts tested. Various reaction parameters such as reaction temperature, catalyst content, solvent were optimized for achieving better yield of HMF. Under optimized reaction conditions, K-10 catalyst affords 80 mol% fructose conversion with HMF yield of 61 mol%. Insight into the type of acid sites essential for such cascade reactions has been furnished. Utilization of clay catalysts for HMF production will be beneficial to improve overall economics for the production of platform chemicals like HMF from biomass-derived raw materials.

Using taurine to increase mesopores in Ce‐based metal–organic framework for enhancing the production of 5‐hydroxymethylfurfural and 5‐ethoxymethylfurfural from fructose

AbstractBACKGROUND5‐hydroxymethylfurfural (HMF) and 5‐ethoxymethylfurfural (EMF) are biomass‐based value‐added chemicals. Various catalytic systems have been studied for converting fructose into HMF and EMF. A more efficient and stable solid acid catalyst is highly desirable for the conversion process.RESULTSIn this study, a novel taurine‐involved Ce metal organic framework material (T‐CeMOF) was synthesized by coordinating Ce to 1,3,5‐benzenetricarboxylic acid (BTC) in the presence of taurine. T‐CeMOF was analyzed with Fourier‐transform infrared (FTIR) spectroscopy, transmission electron microscoy (TEM), and nitrogen adsorption–desorption analysis. Results showed that the presence of taurine makes T‐CeMOF have a much larger specific pore volume than Ce based metal‐organic framwork (CeMOF), which was synthesized by coordinating Ce with the ligand BTC in absence of taurine. It is implied that T‐CeMOF has many more swinging carboxyl groups on the surface than CeMOF. In addition, the sulfonic acid group of taurine is introduced into T‐CeMOF. All of these contribute toward making sure that T‐CeMOF is effective for the conversion of fructose to HMF and EMF in ethanol. Under the catalysis of T‐CeMOF, the total yield of HMF and EMF reached 78.4% within 1 h. T‐CeMOF could be recycled and the catalytic activity of the catalyst was maintained after five cycles.CONCLUSIONT‐CeMOF can be synthesized at room temperature and it achieved a high total yield of HMF and EMF in ethanol within 1 h. T‐CeMOF opens a new route for one‐pot conversion of abundant and cheap fructose‐based biomass into promising biochemicals. © 2020 Society of Chemical Industry (SCI)

Tin, niobium and tin-niobium oxides obtained by the Pechini method using glycerol as a polyol: Synthesis, characterization and use as a catalyst in fructose conversion

The selective and efficient conversion of fructose into chemicals has been extensively explored, especially from the perspective of a more sustainable industry based on renewable inputs together with a more environmentally friendly process. In this study, mixed metal oxides based on tin and niobium were synthesized by the Pechini method, replacing ethylene glycol with glycerol, a renewable chemical. This replacement allows the use of pure or mixed oxides exhibiting high specific surface areas but did not lead to significant differences in the amount and nature of the acid sites present in each case. Furthermore, the mixed oxides had increased numbers of Lewis acid sites, while the number of Bronsted acid sites decreased. Catalytic tests performed at 150 °C demonstrated that the use of these materials leads to conversion results higher than those observed for pure oxides (SnO2 (EG) = 48.3 %, Nb2O5 (EG) = 51.6 % and SnO2 (G) = 56.8 %, Nb2O5 (G) = 59.6 %) because 78.5 and 75.7 % consumption of fructose for SnNb (EG) and SnNb (G) was attained at 2 h, respectively. In addition, the catalysts show promising 5-hydroxymethylfurfural (5-HMF) selectivity, and the presence of lactic acid was also detected. In addition, recycling experiments were performed, and stability was observed for 4 cycles without structural change in the catalysts.

Unfolding the role of molybdenum disulfide as a catalyst to produce platform chemicals from biorenewable resources

Catalytic application of molybdenum disulfide (MoS2) for the production of high-value chemicals from the lignocellulosic biomass is investigated for the first time. In particular, the synthesis of 5-ethoxymethylfurfural (EMF), and 5-hydroxymethylfurfural (HMF) from biomass-derived resources in the presence of inexpensive and readily available MoS2 catalyst via microwave-assisted heating has been studied. The experiments were performed at 100 to 160 °C temperature for 2 to 30 min reaction time in a microwave reactor. Accordingly, the experimental conditions such as reaction temperature, reaction time, catalyst concentration, and feed concentration were optimized for the maximum yield of EMF from the fructose. As a result, maximum 93.3 mol% EMF yield was measured at 160 °C reaction temperature in 30 min when experiments were performed in the presence of 0.3 mmol MoS2 for fructose conversion. It was also observed that the molybdenum disulfide selectively produces EMF in a higher amount with negligible byproducts under optimum operating conditions. Post this, a range of alcohols such as methanol, 1-propanol, 1-butanol, and 1-pentanol were tested for the production of different alkoxymethylfurfurals, which showed more than 95% fructose conversion in all cases. Similarly, a wide range of substrates such as glucose, galactose, mannose, and cellulose were tested, which resulted in significant production of EMF. Notably, the EMFs obtained from the experiments can be used as a precursor to producing a vast range of chemicals like polymers, fragrance, plasticizer, resins, fuel additives, and fuel.

Nb/HUSY as a highly active catalyst for the direct transformation of fructose to methyl lactate

One-pot conversion of biomass-based carbohydrates to methyl lactate (MLA), a versatile platform chemical for the production of food additives as well as the starting material of pharmaceutical industry, is an attractive green process. In this study, the Nb/HUSY catalysts with highly catalytic performance are successfully synthesized and used for the production of MLA from fructose. Remarkably, when using 2%Nb/HUSY as catalyst, the highest MLA yield of 56.1% is obtained with complete conversion of fructose under optimal conditions (140 °C for 6 h). The introduction of niobium into HUSY enhances the Lewis acid properties, which facilitates the stepwise process, involving the retro-aldol condensation and dehydration reactions. The as-prepared catalysts have shown promising potential for conversion of fructose to MLA and effectively inhibited the formation of by-products. More importantly, the catalyst exhibits superior stability and could be reused for at least four cycles.

Catalytic conversion of fructose to 1,3-dihydroxyacetone under mild conditions

A novel zwitterionic catalyst containing imidazole, carboxyl and amino functional groups was synthesized to catalyze the retro-aldol condensation of fructose. The catalyst displayed efficiently catalytic activity for the conversion of fructose to 1,3-dihydroxyacetone (DHA). The yield of DHA and selectivity of DHA achieved 27.9% and 46.5% after reaction 2 h, respectively, at pH 9.5, 85 °C. A possible catalytic mechanism was suggested. The charged functional groups on the catalyst exhibited synergistic effect and played role in electron induction and proton transfer, which leaded to a good selectivity of DHA in the conversion of fructose under mild conditions.

The small intestine shields the liver from fructose-induced steatosis.

Per capita fructose consumption has increased 100-fold over the last century1. Epidemiological studies suggest that excessive fructose consumption, and especially consumption of sweet drinks, is associated with hyperlipidaemia, non-alcoholic fatty liver disease, obesity and diabetes2-7. Fructose metabolism begins with its phosphorylation by the enzyme ketohexokinase (KHK), which exists in two alternatively spliced forms8. The more active isozyme, KHK-C, is expressed most strongly in the liver, but also substantially in the small intestine9,10 where it drives dietary fructose absorption and conversion into other metabolites before fructose reaches the liver11-13. It is unclear whether intestinal fructose metabolism prevents or contributes to fructose-induced lipogenesis and liver pathology. Here we show that intestinal fructose catabolism mitigates fructose-induced hepatic lipogenesis. In mice, intestine-specific KHK-C deletion increases dietary fructose transit to the liver and gut microbiota and sensitizes mice to fructose's hyperlipidaemic effects and hepatic steatosis. In contrast, intestine-specific KHK-C overexpression promotes intestinal fructose clearance and decreases fructose-induced lipogenesis. Thus, intestinal fructose clearance capacity controls the rate at which fructose can be safely ingested. Consistent with this, we show that the same amount of fructose is more strongly lipogenic when drunk than eaten, or when administered as a single gavage, as opposed to multiple doses spread over 45 min. Collectively, these data demonstrate that fructose induces lipogenesis when its dietary intake rate exceeds the intestinal clearance capacity. In the modern context of ready food availability, the resulting fructose spillover drives metabolic syndrome. Slower fructose intake, tailored to intestinal capacity, can mitigate these consequences.

High-Efficiency Synthesis of 5-Hydroxymethylfurfural from Fructose over Highly Sulfonated Organocatalyst

The high-efficiency conversion of fructose to 5-hydroxymethylfurfural (HMF) with approving yields is challenging in biorefinery. In this work, we develop an efficient method of preparing HMF from f...

Synthesis of sulfonated chitosan-derived carbon-based catalysts and their applications in the production of 5-hydroxymethylfurfural

A novel sulfonated chitosan-derived carbon-based catalyst was successfully prepared via isoamyl nitrite-assisted sulfanilic acid sulfonation, and its catalytic activity was examined using dehydration of fructose. The structural and chemical properties of sulfonated chitosan-derived carbon were characterized by SEM, FTIR, XRD, XPS, element analysis, N2 adsorption-desorption experiment, and acid-base titration experiment. KOH was used as activating agent in the synthesizing of carbon supports, and it was found that properly increasing the dose of KOH during activation stage had a positive effect on the subsequent sulfonation of prepared activated carbon. 4KSCC, with the highest sulfonation degree (2.04 mmol/g), exhibited high performance for the conversion of fructose to HMF in various solvent, and an optimal HMF yield of 80.9% was obtained at 140 °C in 40 min. In addition, the reusability of 4KSCC for fructose dehydration was fairly good.

Influence of Dimethylsulfoxide and Dioxygen in the Fructose Conversion to 5-Hydroxymethylfurfural Mediated by Glycerol's Acidic Carbon.

Both the catalytic production of 5-hydroxymethylfurfural (5-HMF) from carbohydrates and the use of a catalyst obtained from residues stand out for adding value to by-products and wastes. These processes contribute to the circular economy. In this work it was evaluated optimized conditions for 5-HMF production from fructose with high yield and selectivity. The reaction was catalyzed by an acidic carbon obtained from glycerol, a byproduct of the biodiesel industry. Special attention has been given to the use of dimethyl sulfoxide (DMSO) as a solvent and its influence on system activity, both in the presence and absence of O2. Glycerol's carbon with acidic properties can be effectively used as catalyst in fructose dehydration, allowed achieving conversions close to 100% with 5-HMF selectivities higher than 90%. The catalyst can be reused in consecutive batch runs. The influence of DMSO in the presence of O2 should be considered in the catalytic activity, as the stabilization of a reaction intermediate by the [O2:DMSO] complex is favored and, both fructose conversion and 5-HMF yield increase.