Microwave-assisted dehydration of fructose and inulin to HMF catalyzed by niobium and zirconium phosphate catalysts

Antonetti, Claudia; Melloni, Mattia; Licursi, Domenico; Fulignati, Sara; Ribechini, Erika; Rivas, Sandra; Parajó, Juan Carlos; Cavani, Fabrizio; Galletti, Anna Maria Raspolli

doi:10.1016/j.apcatb.2017.01.056

Cited by 117 publications

(117 citation statements)

References 72 publications

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“…This might be attributed to the production of large quantities of soluble polymers and/or humins catalyzed by excessive amounts of surface acid sites . Another proposed reason for the decrease of 5‐HMF selectivity and yield could be that 5‐HMF formed in fructose dehydration was then partially converted into levulinic and formic acid by‐products, which was in good agreement with the previous report . In addition, the oligomerization, self‐polymerization, cross‐polymerization etc of produced 5‐HMF with other by‐products could also ultimately result in the decline of 5‐HMF selectivity and yield.…”

Section: Resultssupporting

confidence: 86%

“…Alternatively, heterogeneous catalysts such as solid acids are becoming more and more attractive due to their stronger acidity and easier regeneration as well as less corrosivity, which accelerate their wide application in production of 5‐HMF from fructose ,,. Currently, various types of solid acid catalysts have been designed for the preparation of 5‐HMF, such as heteropoly acids, tungstated zirconias, cerium phosphates, zirconium phosphates, niobium phosphates, zirconium hydrogen phosphates, carbon catalysts etc. Among these various candidates, carbonaceous solid acids have attracted considerable attentions as efficient catalysts because of their relatively strong Brönsted acidity of oxygen‐ and sulfur‐containing functional groups together with the green, convenient and stable natures .…”

Section: Introductionmentioning

confidence: 99%

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An Excellent Solid Acid Catalyst Derived from Microalgae Residue for Fructose Dehydration into 5‐Hydroxymethylfurural

et al. 2019

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An environmentally benign carbonaceous solid acid was synthesized from microalgae residue discarded after biodiesel production. Thereafter, the as‐synthesized carbonaceous solid acid was used for catalytic dehydration of fructose into 5‐hydroxymethylfurural (5‐HMF). Various techniques such as X‐ray diffraction, N2 adsorption‐desorption, scanning electron microscopy, Fourier transform infrared, Raman, X‐ray photoelectron spectroscopy and pyridine adsorption etc were conducted to elucidate the structural and acidic properties of the solid acid so as to build the structure‐performance relationship. The results suggested that large amounts of ‐SO3H, phenolic ‐OH and ‐COOH groups were grafted onto the investigated material and most of the surface acid sites were assigned to strong Brönsted acid sites. In screening tests with other commercial catalysts, the as‐prepared sample presented excellent catalytic activity with 76.65±2.53% yield of 5‐HMF under aqueous conditions. The dehydration of fructose in dimethyl sulfoxide‐water biphasic system was also tested, affording the 5‐HMF yield as high as 93.84±1.12%. This work provides an efficient and selective solid acid from biodiesel waste and might shed light on an alternative catalyst for highly efficient production of 5‐HMF instead of homogeneous catalysts.

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Section: Resultssupporting

confidence: 86%

Section: Introductionmentioning

confidence: 99%

An Excellent Solid Acid Catalyst Derived from Microalgae Residue for Fructose Dehydration into 5‐Hydroxymethylfurural

et al. 2019

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“…As shown in Figure , full conversion of fructose was achieved over the three catalysts, however, the highest HMF yield of 56.3% for ZrP (P/Zr = 2) was observed just because of its strongest L acidity (Figure ) and B acidity (Table ) compared to those of the other ZrP. Moreover, this result shows advantages than some reported works (Table ), which involved with microwave assistant or sub‐critical water with critical reaction conditions, as well as a lower fructose conversion (52.8%) . For example, the difference can be explained by the fact that ZrP (P/Zr = 2) had larger surface area and more acidic sites, which promotes the dehydration of fructose .…”

Section: Resultsmentioning

confidence: 72%

Continuous Production of 5‐Hydroxymethylfurfural from Monosaccharide over Zirconium Phosphates

et al. 2018

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5‐hydroxymethylfurfural (HMF), an important platform compound produced from lignocellulosic biomass, is widely applied in petrochemical industry for downstream synthesis of medical supplies or intermediate of the other important chemicals by the typical catalytic processes. A continuous production route was developed to yield HMF from monosaccharides by using zirconium phosphate (ZrP) with different Zr/P ratios as catalysts. Its physicochemical properties were then characterized by Brunauer‐Emmett‐Teller (BET), X‐ray powder diffraction (XRD), X‐ray photoelectron spectra (XPS), Fourier transform infrared spectroscopy (FT‐IR), pyridine adsorbed Fourier transform infrared spectroscopy (Py‐FT‐IR), X‐ray fluorescence (XRF) and temperature programmed desorption of ammonia (NH3‐TPD) techniques. A mixed phase containing monosaccharide in aqueous and dimethyl sulfoxide (DMSO) phase was applied in the fixed bed to keep the continuous production. The optimized reaction conditions were applied to maximized HMF yield by varying the processing parameters. The highest HMF yield of 56.3% was obtained when using fructose as the feedstock under the reaction condition of 120 °C, 180 min, N2 pressure 2 MPa and DMSO: fructose solution of 9:1 over ZrP with the P/Zr with molar ratio of 2. Comparatively, the glucose conversion of 72% with the HMF yield of 32% were gained under the same conditions using glucose as the feedstock. It is deduced that the ZrP catalysts simultaneously possessing Brönsted/Lewis acid showed synergy in glucose dehydration to HMF. The ZrP catalyst showed good stability and no obvious deactivation was observed after 30 h of time‐on‐stream, due to the primary structure and acidic properties of catalyst can be kept during the reaction. Finally, it is generally efficient for some C6 sugars dehydration to HMF with the Brönsted/Lewis acid synergy of ZrP.

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“…After three times of recycle experiments, the fresh catalyst changed from white to light brown in color after using, and the yield of EL decreased slightly from 97.8% to 91.3%. Therefore, the EDS and FTIR analyses were used to characterize the used catalyst (see Supporting Information), which found that organic deposits in the catalyst surface and a small loss of P element ,. After calcination, the organic deposition was removed, and the catalytic activity of used catalyst got partial recovery.…”

Section: Resultsmentioning

confidence: 99%

“…Antonetti et al. obtained a high yield in the biomass direct alcoholysis of fructose to 5‐hydroxymethyl‐2‐furaldehyde by using ZPs . Jain et al.…”

Section: Introductionmentioning

confidence: 99%

Efficient Production of Ethyl Levulinate from Furfuryl Alcohol Catalyzed by Modified Zirconium Phosphate

et al. 2019

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The catalytic activities of various solid acid catalysts were investigated via the reaction of the direct alcoholysis from furfuryl alcohol to ethyl levulinate. The modified zirconium phosphate with sulfuric acid, prepared via a sol-gel method, exhibited excellent catalytic performance. By controlling the S/ Zr mole ratio of 0.5 at the catalyst preparation, the modified zirconium phosphate catalyst obtained catalytic activity of 97.8% EL yield and 100% FA conversion. The mechanism of enhancing catalytic activity of modified zirconium phosphate was investigated. Owing to the higher specific surface area and more Lewis and Brønsted acid sites, the modified zirconium phosphate catalyst displayed higher catalytic activity in comparison to unmodified zirconium phosphate. In addition, the modified zirconium phosphate catalyst was suitable for a broad temperature range. This modification method can provide a new way to enhance Lewis and Brønsted acidity of zirconium phosphate by adjusting S/Zr ratio rather than the P/ Zr ratio.

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Microwave-assisted dehydration of fructose and inulin to HMF catalyzed by niobium and zirconium phosphate catalysts

Cited by 117 publications

References 72 publications

An Excellent Solid Acid Catalyst Derived from Microalgae Residue for Fructose Dehydration into 5‐Hydroxymethylfurural

An Excellent Solid Acid Catalyst Derived from Microalgae Residue for Fructose Dehydration into 5‐Hydroxymethylfurural

Continuous Production of 5‐Hydroxymethylfurfural from Monosaccharide over Zirconium Phosphates

Efficient Production of Ethyl Levulinate from Furfuryl Alcohol Catalyzed by Modified Zirconium Phosphate

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