cas 67-47-0, 5-Hydroxymethylfurfural | Articles data

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Synthesis of hydroxymethylfurfural from sucrose using Br?nsted-Lewis acidic ionic liquid
The synthesis of 5-hydroxymethylfurfural (HMF) from sucrose was investigated in the presence of the Br?nsted-Lewis acidic ionic liquids (ILs). It was concluded that IL 1-(3-sulfonic acid)-propyl-3-methylimidazole chlorochrominate [HO3S-(CH2)3-mim]Cl-CrCl3 (molar fraction of CrCl3 x = 0.55) had a good catalytic performance with 78.8% yield of HMF. The acid type of IL played a significant role in the reaction. Lewis acid site acted more effectively than its Br?nsted counterpart and a synergetic effect of Br?nsted and Lewis acid sites enhanced the IL catalytic performance. The reusability of IL was good.
Yao, Lin,Liu, Shiwei,Li, Lu,Yu, Shitao,Liu, Fusheng,Song, Zhanqian
p. 283 - 288
(2016)
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Practical synthesis of mumefural, a component of Japanese apricot juice concentrate
A practical four-step method for the synthesis of mumefural from malic acid is described. The key step of this method involves the alkylation of acetal-protected malic acid with bromoacetate, followed by condensation with 5-(hydroxymethyl)furfural. Some of the13C NMR data for our products differed from those previously reported, and further analysis indicated that the previously reported assignments were partly erroneous.
Sugimura, Hideyuki,Kikuchi, Mao,Kato, Saori,Sekita, Wataru,Sasaki, Ikuo
p. 7638 - 7641
(2016)
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Efficient catalytic system for the selective production of 5-hydroxymethylfurfural from glucose and fructose
(Chemical Equation Presented) A sweet conversion! A NHC-Cr/ionic liquid system has achieved excellent efficiency and the highest 5-hydroxymethylfurfural (1; see scheme; NHC=N-heterocyclic carbene) yields reported thus far for both fructose and glucose feedstocks. The catalyst and ionic liquid are tolerant of high substrate loading and can be recycled after extraction of the product.
Yong, Gen,Zhang, Yugen,Ying, Jackie Y.
p. 9345 - 9348
(2008)
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Bifunctional polyacrylonitrile fiber-mediated conversion of sucrose to 5-hydroxymethylfurfural in mixed-aqueous systems
A highly efficient catalytic system composed of a bifunctional polyacrylonitrile fiber (PANF-PA[BnBr]) and a metal chloride was employed to produce 5-hydroxyme-thylfurfural (HMF) from sucrose in mixed-aqueous systems. The promoter of PANF-PA[BnBr] incorporates protonic acid groups that promote the hydrolysis of the glycosidic bond to convert sucrose into glucose and fructose, and then catalyzes fructose dehydration to HMF, while the ammonium moiety may promote synergetically with the metal chloride the isomerization of glucose to fructose and transfer HMF from the aqueous to the organic phase. The detailed characterization by elemental analysis, FTIR spectroscopy, and SEM confirmed the rangeability of the fiber promoter during the modification and utilization processes. Excellent results in terms of high yield (72.8%) of HMF, superior recyclability (6 cycles) of the process, and effective scale-up and simple separation procedures of the catalytic system were obtained. Moreover, the prominent features (high strength, good flexibility, etc.) of the fibers are very attractive for fix-bed reactor.
Shi, Xian-Lei,Lin, Huikun,Tao, Minli,Zhang, Wenqin,Zhang, Min,Li, Yongdan
p. 572 - 578
(2015)
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A selective and economic carbon catalyst from waste for aqueous conversion of fructose into 5-hydroxymethylfurfural
It is of vital importance to design stable and selective heterocatalysts for aqueous production of platforms from biomass-derived sugars. This paper describes a selective aqueous conversion of fructose to HMF using carbon catalysts from pulping waste sodium ligninsulfonate (SLS). The effect of carbonization atmospheres (N2 flow, static air and air flow) on the structure, porosity, compositions and acidic properties of carbon catalysts were investigated by thermogravimetry-mass spectrum analysis, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Boehm titrations, N2 adsorption–desorption isotherms and elemental analysis. The carbonization in air flow favored the formation of more oxygen-containing functional groups and micropores, while more sulfonic groups and meso-/macro-pores were formed during carbonization in a static air atmosphere. Both oxygen- and sulfur-containing groups were acid sites, and their total amount was the largest when carbonized in air flow, followed by static air and N2 flow. The positive correlation between the acid amounts and fructose conversion of carbon catalysts clearly demonstrated the catalytic effect of the acid sites. The steric hindrance of micropores in carbon catalysts restricted the formation of humins and promoted the HMF selectivity compared with meso-/macro-pores.
Deng, Tiansheng,Li, Jiangong,Yang, Qiqi,Yang, Yongxing,Lv, Guangqiang,Yao, Ying,Qin, Limin,Zhao, Xianlong,Cui, Xiaojing,Hou, Xianglin
p. 30160 - 30165
(2016)
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Aluminum doped solid acid with suitable ratio of Br?nsted and Lewis acid sites synthesized by electric-flocculation of phosphotungstic acid via hydrothermal treatment for producing 5-hydroxymethylfurfural from glucose
Novel solid acid catalyst PWAl-200 was synthesized by a new green method of electric-flocculation of phosphotungstic acid (PW) with aluminum as electrodes to transform glucose to 5-hydroxymethylfurfural (5-HMF). Through electric-flocculation, PW was deposited in the hydrated aluminum received from electrolysis. Then the obtained floc was treated by hydrothermal process to get solid acid. Characterization results showed that after electric-flocculation, the electron-withdrawing influence of terminal W[dbnd]O in the PW on hydrated aluminum formed Lewis (L) acid sites on these six-coordinated aluminum. The H+ derived from PW could supply Br?nsted (B) acid sites. In the further hydrothermal treatment, hydrated aluminum dehydrated to produce reformed six-coordinated aluminum. It was linked to heteropoly anions ligands through oxygen bridges, producing more L acid center. Besides, four-coordinated aluminum formed from the hydrated aluminum. The positive charge it produced increased L acid sites due to the strong effect of nearby tungsten species, further adjusting to a moderate ratio of Lewis/Br?nsted (L/B) on solid acid for catalytic synthesis 5-HMF from glucose. The highest yield was 61.7% at 170 ℃ for 4 h and the catalyst could be recycled for four times and tend to stabilize.
Wang, Xin,Lv, Tao,Wu, Minghui,Sui, Junwei,Liu, Qing,Liu, Huan,Huang, Jiaojiao,Jia, Lishan
p. 87 - 96
(2019)
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Levulinic Acid as a Catalyst for the Production of 5-Hydroxymethylfurfural and Furfural from Lignocellulose Biomass
Levulinic acid (LA) was used as a catalyst for the first time to produce 5-hydroxymethylfurfural (5-HMF) and furfural (FAL) from pinewood and eucalyptus sawdust in a mono- or biphasic solvent system. 2-Methyltetrahydrofuran was used as a co-solvent with water in different ratios and temperatures (140-200 °C). Highest yields of 5-HMF and FAL were obtained at 180 °C and 2 h reaction time; however, at 160 °C, high yields of C6 and C5 sugars were obtained. Both hydrolysis and dehydration steps were accelerated in the MTHF/water biphasic system compared to pure aqueous phase. In particular, 1:2 w/w ratio of MTHF/water resulted in the highest yield of 5-HMF and FAL, whereas 2:1 w/w ratio showed highest yield of C6 and C5 sugars. Increasing the ratio of MTHF/water resulted in a higher fraction of dehydrated products extracted into the organic phase. LA as a catalyst is beneficial because it is miscible in both the phases and the presence of LA favours the equilibrium towards 5-HMF production.
Seemala, Bhogeswararao,Haritos, Victoria,Tanksale, Akshat
p. 640 - 647
(2016)
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Efficient process for the direct transformation of cellulose and carbohydrates to 5-(hydroxymenthyl)furfural with dual-core sulfonic acid ionic liquids and co-catalysts
The direct transformation of cellulose and carbohydrates into 5-(hydroxymethyl)furfural (HMF) in the solvent [BMIM]Cl using dual-core sulfonic acid ionic liquids (ILs) as catalysts and metal salts as co-catalysts was investigated, aiming at a more environmentally friendly process not involving chromium. From the high throughput screening of various metal salts, a combination of [bi-C3SO3HMIM][CH3SO 3] (IL-2) and manganese chloride (MnCl2) was found to be the most effective catalyst. HMF was directly afforded from cellulose in 66.5% yield. Thus, synthesis of HMF was successfully performed from cellulose using ILs and MnCl2. Following the principles of green engineering, we recycled the catalyst in our system for cellulose hydrolysis and this catalyst maintained its good performance even after four runs. Furthermore, various sugars and lignocellulosic raw materials could be directly converted into HMF in reasonable yields under these conditions. The mechanism that explains the high activity of ILs in combination with MnCl2 is also proposed.
Shi, Jincai,Gao, Haiyan,Xia, Yongmei,Li, Wei,Wang, Haijun,Zheng, Changge
p. 7782 - 7790
(2013)
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Conversion of carbohydrates into 5-hydroxymethylfurfural in an advanced single-phase reaction system consisting of water and 1,2-dimethoxyethane
5-Hydroxymethylfurfural (HMF) is a bio-based platform chemical that may be converted into various chemicals and fuels. In the present study, we developed an advanced low-boiling single-phase reaction system for producing HMF from glucose. It consists of water and 1,2-dimethoxyethane (DMOE) and uses AlCl3 as catalyst. Our results show that introduction of DMOE can substantially enhance HMF production because of the polar aprotic solvent effect provided by DMOE. Under optimal conditions, a high HMF yield (58.56%) was obtained. GC-MS of the liquid-phase products revealed that HMF and furans comprised 80% and ～90% of the detected products. Formation of liquid-phase products, including furans, oxygenated aliphatics, cyclopenten-1-ones, and pyrans is discussed. Further study of the humins formed during glucose conversion showed the effective inhibition of humin formation by DMOE. The structure of humins was characterized by FTIR spectroscopy. Finally, HMF production from disaccharides (sucrose, maltose and cellobiose) and polysaccharide (cellulose) using the water-DMOE system resulted in good yields, demonstrating that our single-phase water-DMOE solvent system has good potential use in HMF production from glucose and complex carbohydrates.
Wang, Shurong,Lin, Haizhou,Chen, Jingping,Zhao, Yuan,Ru, Bin,Qiu, Kunzan,Zhou, Jinsong
p. 84014 - 84021
(2015)
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Synthesis of 5-hydroxymethylfurural from carbohydrates using large-pore mesoporous tin phosphate
A large-pore mesoporous tin phosphate (LPSnP-1) material has been synthesized hydrothermally by using Pluronic P123 as the structure-directing agent. The material is composed of aggregated nanoparticles of 10-15nm in diameter and has a BET surface area of 216m2 g-1 with an average pore diameter of 10.4nm. This pore diameter is twice as large as that of mesoporous tin phosphate materials synthesized through the surfactant- templating pathways reported previously. LPSnP-1 shows excellent catalytic activity for the conversion of fructose, glucose, sucrose, cellobiose, and cellulose to 5-hydroxymethylfurfural (HMF) in a water/methyl isobutyl ketone biphasic solvent to give maximum yields of HMF of 77, 50, 51, 39, and 32mol %, respectively, under microwave-assisted heating at 423K. Under comparable reaction conditions, LPSnP-1 gives 12 % more HMF yield than a small-pore mesoporous tin phosphate catalyst that has an identical framework composition. This confirms the beneficial role of large mesopores and nanoscale particle morphology in catalytic reactions that involve bulky natural carbohydrate molecules. Sugar to fuel: A large-pore mesoporous tin phosphate material is synthesized hydrothermally by using Pluronic triblock copolymer as the template. This material shows high thermal stability and catalyzes naturally abundant carbohydrates in the aqueous phase to 5-hydroxymethylfurfural, which is a potential bio-based platform chemical to produce a broad range of chemicals and liquid transportation fuels.
Dutta, Arghya,Gupta, Dinesh,Patra, Astam K.,Saha, Basudeb,Bhaumik, Asim
p. 925 - 933
(2014)
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Efficient catalytic conversion of the fructose into 5-hydroxymethylfurfural by heteropolyacids in the ionic liquid of 1-butyl-3-methyl imidazolium chloride
The heteropolyacids (HPAs) of H3PW12O40 (PW12) and H4SiW12O40 (SiW 12) have been demonstrated to be effective catalysts for promoting dehydration of the fructose to 5-hydroxymethylfurfural (5-HMF) in the presence of the ionic liquid of 1-butyl-3-methyl imidazolium chloride ([BMIM]Cl) as green solvent. The 5-HMF can be obtained with both the yield and selectivity of 99% at 80 °C in only 5 min. The activation energy of 31.88 kJ mol-1 by applying the [BMIM]Cl/PW12 system for dehydration of the fructose is much lower than those reported in the literature. Moreover, the used ionic liquid of [BMIM]Cl and HPAs could be recycled and reused with only slight decrease of reactivity for at least ten times. Compared with those systems reported so far, the [BMIM]Cl/PW12 and [BMIM]Cl/SiW12 exhibit higher yield, shorter reaction time, lower temperature for catalytic conversion of the fructose to 5-HMF, and they are environmental-friendly green systems.
Xiao, Yaping,Song, Yu-Fei
p. 74 - 78
(2014)
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Facile synthesis of microcellular foam catalysts with adjustable hierarchical porous structure, acid-base strength and wettability for biomass energy conversion
Herein we report a novel synthetic strategy for fabrication of microcellular foam catalysts (MFCs) with hydrophobic, acid-base, and hierarchical porous properties for conversion of one-pot cellulose to a key chemical platform (i.e. 5-hydroxymethylfurfural, HMF) for biofuels. The water-in-oil (W/O) Pickering high internal phase emulsions (HIPEs), stabilized by both amino-functionalized nanoparticles (namely, S-NH2) and Span 80, were used as the template for simultaneous polymerization of oil phase containing 1-octene, divinylbenzene (DVB), and trihydroxymethylpropyl trimethylacrylate (TMPTMA). After subsequent sulfonation process, acid and base sites resulting from grafted -SO3H group of polydivinylbenzene (PDVB) and S-NH2 were both located on the surface of the MFCs. The resultant MFCs composite had a typical hierarchical porous structure, and the macropores with a well-defined open-cell and interconnecting pore throat structure could be controlled via the composition of the oil phase of emulsion, with the mesopore structure closely related to the degree of cross-linking of oil-soluble functional monomer. The representative catalyst MFCs-3 had a hierarchical porous structure (macropores ranging from 1.0 μm to 30 μm and uniform mesopores in 32.1 nm), hydrophobic surface (water contact angle of 125°), 0.735 mmol g-1 of base, and 1.305 mmol g-1 of acid. The HMF yield of 41% for cellulose conversion showed its excellent catalytic performance. This work opens up a route for simple and controlled fabrication of multifunctional polymeric catalysts for biomass energy conversion.
Gao, Heping,Pan, Jianming,Han, Donglai,Zhang, Yunlei,Shi, Weidong,Zeng, Jun,Peng, Yinxian,Yan, Yongsheng
p. 13507 - 13518
(2015)
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Supported ionic liquid silica nanoparticles (SILnPs) as an efficient and recyclable heterogeneous catalyst for the dehydration of fructose to 5-hydroxymethylfurfural
Supported ionic liquid nanoparticles (SILnPs) having particle size ranging from 293 ± 2 to 610 ± 11 nm have been prepared by immobilization of ionic liquid, 1-(tri-ethoxy silyl-propyl)-3-methyl-imidazolium hydrogen sulfate (IL-HSO4) on the surface of silica nanoparticles. The catalytic activity of the prepared SILnPs was investigated for the dehydration of fructose to 5-hydroxymethylfurfural (HMF) in the presence of dimethylsulfoxide (DMSO) as a solvent. The reaction temperature and amount of catalyst have been optimized for dehydration of fructose over SILnPs using experimental design leading to 99.9% fructose conversion and 63.0% HMF yield using silica SILnPs (d = 610 ± 11) nm at 130.0°C in 30 min reaction time. The SILnPs catalysts developed in this study present improved performances over other zeolites and strong acid ion exchange resin catalysts, and they have been efficiently and very easily recycled over seven times without any significant loss in fructose conversion and HMF yield.
Sidhpuria, Kalpesh B.,Daniel-Da-Silva, Ana L.,Trindade, Tito,Coutinho, Joao A. P.
p. 340 - 349
(2011)
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Electron-withdrawing ability tunable polyphosphazene frameworks as novel heterogeneous catalysts for efficient biomass upgrading
A series of polyphosphazene nano-frameworks with electron-withdrawing capability have been produced and exhibited high activity as non-acidic heterogeneous catalysts for the dehydration of fructose to 5-hydroxymethylfurfural under mild conditions with good stability and recyclability. The unique cyclotriphosphazene unit and electron-withdrawing nature of the polymer backbone are essential for the catalytic performance.
Huang, Zhen,Pan, Yuanjia,Guo, Jia,Chao, Yimin,Shen, Wei,Wang, Changchun,Xu, Hualong
p. 48694 - 48698
(2016)
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Niobium phosphotungstates: Excellent solid acid catalysts for the dehydration of fructose to 5-hydroxymethylfurfural under mild conditions
The efficient conversion of carbohydrates to 5-hydroxymethylfurfural (5-HMF) under mild conditions represents a very attractive and promising method of producing important building blocks. In this work, niobium phosphotungstates, with Nb/P molar ratios of 0.6, 1.0, 2.0 and 4.0 (NbPW-06, NbPW-1, NbPW-2, and NbPW-4, respectively) have been prepared by a facile, one-pot, alcohol-mediated thermal process and used for the direct conversion of fructose to 5-HMF. By adding a certain amount of Nb, the surface of the catalyst became enriched in P, and this enrichment was associated with the presence of surface P-OH groups that offered Br?nsted acid sites that can activate superficial hydrogen species to facilitate 5-HMF generation. Pyridine-FTIR confirmed the presence of Br?nsted and Lewis acid sites, which might play important roles in the dehydration of fructose to 5-HMF. Furthermore, polar aprotic solvents were well-suited for the conversion, and higher yields of 5-HMF were obtained in polar aprotic solvents than in nonpolar solvents. A 5-HMF yield of 96.7% with complete fructose consumption was obtained over NbPW-06 in DMSO at 80 °C after 90 min. In addition, NbPW-06 could be recycled several times without a significant decrease in the catalytic activity. A catalytic mechanism for this reaction was proposed. Moreover, this catalytic system can also be utilized for the dehydration of sucrose and inulin to 5-HMF in satisfactory yields. This study establishes an important platform for the further design of Nb-containing catalysts for the production of 5-HMF from carbohydrates under mild conditions.
Qiu, Guo,Wang, Xincheng,Huang, Chongpin,Li, Yingxia,Chen, Biaohua
p. 32423 - 32433
(2018)
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LiCl-promoted-dehydration of fructose-based carbohydrates into 5-hydroxymethylfurfural in isopropanol
The carbohydrate-derived 5-hydroxymethylfurfural (HMF) is one of the most versatile intermediate chemicals, and is promising to bridge the growing gap between the supply and demand of energy and chemicals. Developing a low-cost catalytic system will be helpful to the production of HMF in industry. Herein, the commercially available lithium chloride (LiCl) and isopropanol (i-PrOH) are used to construct a cost-effective and low-toxic system, viz., LiCl/i-PrOH, for the preparation of HMF from fructose-based carbohydrates, achieving ～80% of HMF yield under the optimum conditions. The excellent promotion effect of LiCl on fructose conversion in i-PrOH could be attributed to the synergistic effect of LiCl with i-PrOH through the LiCl-promoted and i-PrOH-aided dehydration process, and the co-operation of LiCl and i-PrOH for stabilizing the as-formed HMF by hydrogen/coordination bonds, giving a low activation energy of 68.68 kJ mol-1 with a pre-exponential factor value of 1.2 × 104 min-1. The LiCl/i-PrOH system is a substrate-tolerant and scalable catalytic system, fructose (scaled up 10 times), sucrose, and inulin also give 73.6%, 30.3%, and 70.3% HMF yield, respectively. Moreover, this system could be reused 8 times without significant loss of activity. The readily available and low-toxic LiCl, the sustainable solvent (i-PrOH), the renewable starting materials, and the mild reaction conditions make this system promising and sustainable for the industrial production of HMF in future.
Ma, Hao,Li, Zhenzhen,Chen, Lili,Teng, Junjiang
p. 1404 - 1410
(2021)
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Chromium halides mediated production of hydroxymethylfurfural from starch-rich acorn biomass in an acidic ionic liquid
Chromium halides were introduced for the sustainable production of hydroxymethylfurfural (HMF) from raw acorn biomass using an acidic ionic liquid. The free sugars (glucose and maltose) released by the acidic hydrolysis of the biomass were confirmed by the FT-IR absorption bands around 995-1014 cm -1 and HPLC. FESEM analysis showed that the acorn biomass contains various sizes of starch granules and their structures were severely changed by the acidic hydrolysis. An optimal concentration of HCl for the HMF yields was 0.3 M. The highest HMF yield (58.7 + 1.3 dwt %) was achieved in the reaction mixture of 40% [OMIM]Cl + 10% ethyl acetate + 50% 0.3 M HCl extract containing a mix of CrBr3/CrF3. The combined addition of two halide catalysts was more effective in the synthesis of HMF (1.2-fold higher on average) than their single addition. The best productivity of HMF was found at 15% concentration of the biomass and at 50%, its relative productivity declined down to ca. 0.4-fold.
Lee, Jin-Woo,Ha, Myoung-Gyu,Yi, Young-Byung,Chung, Chung-Han
p. 177 - 182
(2011)
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Organic Carbonates: Efficient Extraction Solvents for the Synthesis of HMF in Aqueous Media with Cerium Phosphates as Catalysts
We describe a process for the selective conversion of C6-polyols into 5-hydroxymethylfurfural (5-HMF) in biphasic systems of organic carbonate/water (OC/W), with cerium(IV) phosphates as catalysts. Different reaction parameters such as the OC/W ratio, catalyst loading, reaction time, and temperature, were investigated for the dehydration of fructose. Under the best reaction conditions, a yield of 67.7 % with a selectivity of 93.2 % was achieved at 423 K after 6 h of reaction using [(Ce(PO4)1.5(H2O)(H3O)0.5(H2O)0.5)] as the catalyst. A maximum yield of 70 % with the same selectivity was achieved after 12 h. At the end of the reaction, the catalyst was removed by centrifugation, the organic phase was separated from water and evaporated in vacuo (with solvent recovery), and solid 5-HMF was isolated (purity >99 %). The recovery and reuse of the catalyst and the relationship between the structure of the OC and the efficiency of the extraction are discussed. The OC/W system influences the lifetime of the catalysts positively compared to only water.
Dibenedetto, Angela,Aresta, Michele,Di Bitonto, Luigi,Pastore, Carlo
p. 118 - 125
(2016)
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One-pot formation of furfural from xylose via isomerization and successive dehydration reactions over heterogeneous acid and base catalysts
An efficient furfural formation from xylose, a major pentose in hemicellulose of biomass, was demonstrated using a pair of solid acid and base in one-pot. High furfural yield was obtained in polar aprotic solvents including N,N-dimethylformamide using Amberlyst-15 and hydrotalcite under moderate conditions. This efficient production of furfural was performed via aldoseketose isomerization of xylose to xylulose by solid base and successive dehydration of xylulose to furfural by solid acid.
Takagaki, Atsushi,Ohara, Mika,Nishimura, Shun,Ebitani, Kohki
p. 838 - 840
(2010)
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Synthesis of 5-hydroxymethylfurfural from monosaccharides catalyzed by superacid VNU-11-SO4in 1-ethyl-3-methylimidazolium chloride ionic liquid
Superacid VNU-11-SO4, a modified metal-organic framework by post-synthetic treatment with a sulfuric acid solution, has been considered as a promising heterogeneous catalyst in the isomerization of glucose to fructose and further dehydration to form 5-hydroxymethylfurfural (HMF) due to its possession of both Lewis and Br?nsted acid sites. In this work, we focused on using VNU-11-SO4 for the optimization of the conversion of fructose and glucose into HMF using an ionic liquid as a green solvent. The highest yields of HMF from glucose and fructose could be obtained in 28% (140 °C, 8 h) and 86% (110 °C, 3 h), respectively, with the use of VNU-11-SO4 catalyst in 1-ethyl-3-methylimidazolium chloride ionic liquid. Recycling examination of the catalyst showed only a slight decrease in the HMF yield, implying its potential industrial application in biomass transformation.
Dinh Dang, Minh Huy,Le Hoang Doan, Tan,Phan, Ha Bich,Thuy Nguyen, Linh Ho,Tran, Phuong Hoang,Vo, Huong Thi
p. 39687 - 39692
(2020)
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Conversion of highly concentrated fructose into 5-hydroxymethylfurfural by acid-base bifunctional HPA nanocatalysts induced by choline chloride
A series of acid-base bifunctional heteropolyacids (HPAs) (C6H15O2N2)3-xHxPW12O40 (abbreviated as Ly3-xHxPW) have been designed using different ratios of HPAs with amino acid lysine in order to control their acid-base properties. The amino acid group facilitated the HPAs forming micellar assemblies in choline chloride-fructose deep eutectic solvents. In the dehydration of fructose to 5-hydroxymethylfurfural (HMF), Ly3-xHxPW exhibited different catalytic activities because of their different acid-base properties. Among all the HPA catalysts, Ly2HPW gave the best results with 93.3% conversion and 92.3% HMF yield within a very short time, i.e. 1 min under the conventional temperature of 110 °C using choline chloride (ChCl) as solvent, and this was almost the best result by far. The highest activity and selectivity of Ly2HPW came from the synergistic effect between certain acidic and basic capacities, which provides ready accessibility to the nucleophilic (-NH2) and electrophilic (H) sites. Moreover, this catalyst was tolerant to highly concentrated feedstock (～66.7 wt%) with the additive ChCl. Ly2HPW performed as a heterogeneous catalyst in the ChCl system and could be recycled by simple washing treatment.
Zhao, Qian,Sun, Zhong,Wang, Shengtian,Huang, Guohui,Wang, Xiaohong,Jiang, Zijiang
p. 63055 - 63061
(2014)
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Direct conversion of mono- and polysaccharides into 5-hydroxymethylfurfural using ionic-liquid mixtures
Platform chemicals are usually derived from petrochemical feedstocks. A sustainable alternative commences with lignocel-lulosic biomass, a renewable feedstock, but one that is highly challenging to process. Ionic liquids (ILs) are able to solubilize biomass and, in the presence of catalysts, convert the biomass into useful platform chemicals. Herein, we demonstrate that mixtures of ILs are powerful systems for the selective catalytic transformation of cellulose into 5-hydroxymethylfurfural (HM. Combining ILs with continuous HMF extraction into methyl-isobutyl ketone or 1,2-dimethoxyethane, which form a biphase with the IL mixture, allows the online separation of HMF in high yield. This one-step process is operated under relatively mild conditions and represents a significant step forward towards sustainable HMF production.
Siankevich, Sviatlana,Fei, Zhaofu,Scopelliti, Rosario,Jessop, Philip G.,Zhang, Jiaguang,Yan, Ning,Dyson, Paul J.
p. 2089 - 2096
(2016)
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Bifunctional Imidazole-Benzenesulfonic Acid Deep Eutectic Solvent for Fructose Dehydration to 5-Hydroxymethylfurfural
Abstract: Imidazole (Im) and benzenesulfonic acid (BSA) formed deep eutectic solvents (DESs) were used as acidic catalyst and solvent for the dehydration of fructose to 5-hydroxymethylfurfural (5-HMF). The DES formation involved an acid–base neutralization to produce equimolar salt from BSA and Im, and subsequent interaction between equimolar salt as hydrogen bond acceptor and excessive BSA as hydrogen bond donor. The BSA-rich DES [Im:1.5BSA] with a 1:1.5 molar ratio of Im:BSA and 10% dosage exhibited high catalytic activity for fructose dehydration with a 5-HMF yield of 90.1% at 100?°C after a very short reaction time (3?min). The bifunctionality of [Im:1.5BSA] for promoting reaction rates and catalytic activity of fructose dehydration has been identified by tuned acidity of DESs and hydrogen bond interaction among fructose, 5-HMF, and DESs demonstrated by conductor-like screening model for real solvents (COSMO-RS) theory. Graphic Abstract: [Figure not available: see fulltext.]
Ruan, Chencong,Mo, Fan,Qin, Hao,Cheng, Hongye,Chen, Lifang,Qi, Zhiwen
p. 445 - 453
(2021)
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Production of 5-hydroxymethylfurfural from fructose by a thermo-regulated and recyclable Br?nsted acidic ionic liquid catalyst
In this work, a thermo-regulated recyclable catalytic system using ionic liquid [HO2CMMIm]Cl as the catalyst and isopropanol as the solvent has been demonstrated to be effective for the dehydration of fructose to synthesize 5-hydroxymethylfurfural (HMF). The solubility of [HO2CMMIm]Cl ionic liquid in isopropanol is temperature-dependent, being miscible with isopropanol at a temperature range suitable for fructose dehydration (e.g., above 80 °C) while not soluble at lower temperatures such as room temperature. Temperature-responsive solubilization/precipitation of [HO2CMMIm]Cl in isopropanol renders the acidic ionic liquid an appealing thermo-regulated phase-switchable catalyst. Furthermore, the effects of various parameters including catalyst loading, fructose concentration, reaction time and temperature on the catalytic performance of fructose dehydration have been studied systematically. Under optimized reaction conditions, up to 91.2 mol% HMF yield could be obtained. Additionally, when the ionic liquid catalyst precipitated out after the reaction, the solvent can be simply decanted and [HO2CMMIm]Cl could be directly reused for the next run with freshly added solvent and substrate. It was found that [HO2CMMIm]Cl could be reused at least five times without considerable loss of activity. Furthermore, a kinetic analysis was carried out, indicating the activation energy for the reaction to be 62.1 kJ mol-1. This catalytic system can be envisioned to find applications in a wide range of acid-catalyzed reactions with facile, thermo-regulated catalyst recovery features.
Ma, Yubo,Qing, Shaojun,Wang, Lei,Islam, Nurali,Guan, Shuzhe,Gao, Zhixian,Mamat, Xamxikamar,Li, Hongyi,Eli, Wumanjiang,Wang, Tianfu
p. 47377 - 47383
(2015)
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Sulfonated lignin-derived ordered mesoporous carbon with highly selective and recyclable catalysis for the conversion of fructose into 5-hydroxymethylfurfural
Sulfonic acid-functionalized lignin-derived mesoporous carbon (LDM C-S O3H) was prepared using phenolation and evaporation induced self-assembly method followed by sulfonation. The obtained LDM C-S O3H bearing sulfonic acid density of 0.6528 mmol/g possessed a well-ordered two-dimensional hexagonal mesoporous characteristics. A 5-hydroxymethylfurfural (5-HMF) yield of 98.0% with a full fructose conversion was obtained using LDM C-S O3H as catalyst at 140 °C for 2 h in DMSO. Reactive kinetics studies revealed that fructose conversion in DMSO without catalyst or catalyzed by LDMC-SO3H may obey pseudo-first-order kinetics, and the activation energy of latter (72 kJ/mol) was much lower than that of former (114 kJ/mol). Adsorption kinetics studies indicated that almost no 5-HMF adsorbed onto LDM C-S O3H probably had a great contribution to the high selectivity of up to 98.0%, while the fructose adsorption on LDM C-S O3H was a diffusion-controlling adsorption process with more following Bangham kinetic model and Weber-Morris kinetic model owing to the characteristics of ordered mesostructure of LDM C-S O3H. Moreover, LDM C-S O3H exhibited superior reusability and stability in catalytic performance with a 5-HMF yield higher than 88.0% in six runs probably due to the synergistic effect of mesopore structure with a special surface and -SO3H groups with a relatively high content. These research results will contribute to a better understanding of structure-performance relationship of LDM C-S O3H used as an efficient catalyst in the fructose-to-5-HMF transformation as well as the high-value utilization of lignin in the field of catalysis.
Gan, Linhuo,Lyu, Li,Shen, Tianruo,Wang, Shuai
p. 132 - 143
(2019)
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Kinetics of glucose dehydration catalyzed by homogeneous Lewis acidic metal salts in water
Glucose dehydration catalyzed by various Lewis acid metal salts was studied in a biphasic reaction system. The glucose conversion kinetic profile was used to examine the importance of the Lewis acid character for the different metal ions. It was found that the pH value of the aqueous solution played an important role in controlling the Lewis acid activities. For lanthanide chlorides, their Lewis acidities were comparable under the pH values from 2.5 to 5.5. However, the Lewis acid strength of other metal salts, such as aluminum chloride, showed a strong dependence on the solution pH. Apparent activation energies for the Lewis acid salts were calculated for glucose conversion to examine their dependence on the Lewis acid metal salt. Fructose dehydration experiments with the catalyst systems demonstrated that Lewis acids played a role in the dehydration reaction through accelerating fructose conversion but diminishing selectivity to the desired 5-hydroxymethylfurfural (HMF) product.
Wang, Tianfu,Glasper, Justin A.,Shanks, Brent H.
p. 214 - 221
(2015)
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One-pot synthesis of 5-hydroxymethylfurfural from carbohydrates using an inexpensive FePO4 catalyst
Catalytic conversion of carbohydrates to 5-hydroxymethylfurfural (5-HMF) provides a way toward obtaining renewable biomass-based fuels and chemicals. Herein, we use an inexpensive FePO4 catalyst, which is insoluble at low temperature but can be partially dissolved and act as a homogeneous catalyst at high temperature, in a one-vessel biphasic reactor to generate 5-HMF from carbohydrates such as fructose, glucose, sucrose, cellulose, and Camellia oleifera shell (a lignocellulosic feedstock) without the addition of homogeneous acids. The effects of various reaction conditions including reaction temperature, reaction time, feedstock types and the amount of catalyst on fructose conversion and 5-HMF yield were investigated. The highest 5-HMF yield (71.5 mol%) starting from fructose feedstock was achieved using this "one-pot" biphasic water/tetrahydrofuran (THF) reactor system at 140 °C for 15 min. More interestingly, at high temperature, the FePO4 catalyst was also highly active in the conversion of cellulose and Camellia oleifera shell, which are very difficult to convert to 5-HMF without the addition of mineral acids. A high 5-HMF yield of 48 mol% starting from microcrystalline cellulose was also obtained using the biphasic reaction system. Moreover, the FePO4 catalyst could be easily separated and recycled from the aqueous solution via precipitation after cooling to room temperature since it is insoluble at low temperature. Possible dehydration reaction mechanisms of these carbohydrates catalyzed by FePO4 were also proposed. This journal is
Yang, Li,Yan, Xiaopei,Xu, Siquan,Chen, Hao,Xia, Haian,Zuo, Songlin
p. 19900 - 19906
(2015)
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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.
Hattori, Masashi,Kamata, Keigo,Hara, Michikazu
p. 3688 - 3693
(2017)
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Simultaneous dehydration of biomass-derived sugars to 5-hydroxymethyl furfural (HMF) and reduction of graphene oxide in ethyl lactate: One pot dual chemistry
Low yield of chemicals is often identified as a major obstacle for the complete utilization of bioresources as a source of important chemicals and thereby limits their application in industries. The issue of low yield can be partially compensated by integrated processes, i.e., production of two or more chemicals from the same biomass using single or multistep processes. Herein, a simple pathway for simultaneous production of 5-hydroxymethyl furfural (HMF) from biomass-derived sugars by dehydration of fructose (molar yield 76.3%) using graphene oxide (GO) as acid catalyst and choline chloride (ChoCl) as additive in ethyl lactate is demonstrated. Moreover, during the course of reaction GO was reduced to produce six-layered graphene nanosheets (96% recovery). Furthermore, the solvent was recycled after recovery of both products and successfully reused for subsequent production of the two chemicals with high purity.
Mondal, Dibyendu,Chaudhary, Jai Prakash,Sharma, Mukesh,Prasad, Kamalesh
p. 29834 - 29839
(2014)
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Graphene oxide catalyzed dehydration of fructose into 5- hydroxymethylfurfural with isopropanol as cosolvent
The design of green heterogeneous catalysts for the efficient conversion of biomass into platform molecules is a key aim of sustainable chemistry. Graphene oxide prepared from Hummers oxidation of graphite was proven to be a green and efficient carbocatalyst for the dehydration of fructose into 5-hydroxymethylfurfural (HMF) in some three-carbon and four-carbon alcohol mediated solvent systems. HMF was obtained in up to 87 % yield in 90vol % isopropanol-mediated DMSO solvent. Some control experiments and analytical data showed that a small number of sulfonic groups and abundance of oxygen-containing groups (alcohols, epoxides, carboxylates) have an important synergic effect in maintaining the high performance of graphene oxide. GO-ing all the way: Graphene oxide is demonstrated to be a green heterogeneous catalyst for the selective dehydration of fructose into 5-hydroxymethylfurfural (HMF) in a cost efficient and environmentally benign isopropanol-mediated solvent system. A small number of sulfonic groups with the synergic effect of oxygen-containing groups (alcohols, epoxides, carboxylates) make graphene oxide an efficient acid catalyst.
Wang, Hongliang,Kong, Qingqiang,Wang, Yingxiong,Deng, Tiansheng,Chen, Chengmeng,Hou, Xianglin,Zhu, Yulei
p. 728 - 732
(2014)
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Coupling Continuous Flow Microreactors to MicroNIR Spectroscopy: Ultracompact Device for Facile In-Line Reaction Monitoring
In this study, we applied a portable near-infrared spectrophotometer (MicroNIR) for in-line monitoring of the synthesis of 5-hydroxymethylfurfural (5-HMF) in a continuous flow microreactor. Under the best reaction conditions using isopropyl alcohol/dimethyl sulfoxide as the reaction solvent and a fixed-bed reactor packed with solid acid catalyst, total conversion of d-fructose was observed, and 5-HMF was obtained in 95% yield with a residence time of just 11.2 min. Principal component analyses and construction of multivariate control charts based on Hotelling's T2 and Q residuals were also performed and proved the excellent response of the compact MicroNIR device for in-line monitoring of 5-HMF production without variation in the yield over 8 h/day during 5 days. Our results demonstrate the great potential for the application of this compact device in the monitoring of laboratory-scale reactions, which can be extended to industrial scales.
Galaverna, Renan,Ribessi, Rafael L.,Rohwedder, Jarbas J. R.,Pastre, Julio C.
p. 780 - 788
(2018)
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Rapid characterization of complex viscous liquids at the molecular level
Sticky subject: An N2 stream forms bubbles inside bulk viscous liquids, which create an aerosol sample through a microjetting mechanism (see picture). This aerosol is then analyzed by extractive electrospray ionization (EESI) mass spectrometry (MS). EESI-MS reveals the molecular composition of complex liquids and the kinetics of ongoing processes occurring in the highly viscous liquids without any sample pretreatment.
Law, Wai Siang,Chen, Huanwen,Ding, Jianhua,Yang, Shuiping,Zhu, Liang,Gamez, Gerardo,Chingin, Konstantin,Ren, Yulin,Zenobi, Renato
p. 8277 - 8280
(2009)
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Mesoporous porphyrin-silica nanocomposite as solid acid catalyst for high yield synthesis of HMF in water
Solid acid catalysts occupy a special class in heterogeneous catalysis for their efficiency in eco-friendly conversion of biomass into demanding chemicals. We synthesized porphyrin containing porous organic polymers (PorPOPs) using colloidal silica as a support. Post-modification with chloro-sulfonic acid enabled sulfonic acid functionalization, and the resulting material (PorPOPS) showed excellent activity and durability for the conversion of fructose to 5-hydroxymethyl furfural (HMF) in green solvent water. PorPOPS composite was characterized by N2 sorption, FTIR, TGA, CHNS, FESEM, TEM and XPS techniques, justifying the successful synthesis of organic networks and the grafting of sulfonic acid sites (5 wt%). Furthermore, a high surface area (260 m2/g) and the presence of distinct mesopores of ~15 nm were distinctly different from the porphyrin containing sulfonated porous organic polymer (FePOP-1S). Surprisingly the hybrid PorPOPS showed an excellent yield of HMF (85%) and high selectivity (>90%) in water as compared to microporous pristine-FePOP-1S (yield of HMF = 35%). This research demonstrates the requirement of organic modification on silica surfaces to tailor the activity and selectivity of the catalysts. We foresee that this research may inspire further applications of biomass conversion in water in future environmental research.
Bhaumik, Asim,Mankar, Akshay R.,Modak, Arindam,Pant, Kamal Kishore
(2021)
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Synthesis of different structured FePO4 for the enhanced conversion of methyl cellulose to 5-hydroxymethylfurfural
FePO4 catalysts with branch-like, flower-like, and spherical morphologies were synthesized for the conversion of methyl cellulose to 5-hydroxymethylfurfural (5-HMF) via a hydrothermal route. The molar ratio of Fe3+ and H2PO4- ions in the reaction system played a crucial role in the morphology of FePO4. Compared with flower-like, spherical and amorphous FePO4, branch-like FePO4 presented a better catalytic performance in the cellulose conversion and 5-HMF yield. The branch-like FePO4 retained a branch structure after recycling five times in the bi-phasic reaction process. The insolubility of low temperature and partial dissolution of elevated temperature were responsible for the excellent catalytic activity of the FePO4 phase-change catalyst. The combined effect of H+ ions and iron species generated from the hydrolysis of FePO4 can be favorable for the enhanced yield of 5-HMF.
Liu, Yong,Li, Zili,You, Yaohui,Zheng, Xiaogang,Wen, Jing
p. 51281 - 51289
(2017)
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A novel microwave-assisted hydrothermal route for the synthesis of ZnxTPA/γ-Al2O3 for conversion of carbohydrates into 5-hydroxymethylfurfural
Energy-efficient and sustainable processes for the production of 5-hydroxymethylfurfural (HMF) from carbohydrates are in high demand. Bivalent ion-exchanged microwave-synthesized ZnxTPA/γ-Al2O3 was employed for the direct conversion of carbohydrates into HMF. The as-synthesized samples were structurally characterized by FTIR and Raman spectroscopy, UV-Vis diffused reflectance spectroscopy, and X-ray diffraction. Thermal characterization was performed by TG-DTA. The surface morphology was analysed by FE-SEM, and surface area analysis was performed. The surface acidities of the as-synthesized catalysts were elucidated by pyridine FTIR spectra and NH3-TPD. The catalytic performance was thoroughly studied as a function of Zn2+ doping, reaction temperature, catalysts loading, and effect of solvents. Microwave-synthesized Zn0.5TPA/γ-Al2O3 exhibited excellent catalytic fructose dehydration, with 88% HMF yield at 120 °C for 2 h. The surface Br?nsted acidity was found to be crucial for optimum catalytic activity.
Parameswaram,Roy, Sounak
p. 28461 - 28471
(2018)
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Development of a continuous-flow tubular reactor for synthesis of 5-hydroxymethylfurfural from fructose using heterogeneous solid acid catalysts in biphasic reaction medium
5-Hydroxymethylfurfural (5-HMF) is an important biomass-derived platform chemical used to produce polymers, biofuels, and other valuable industrial chemicals. In this work, 5-HMF was synthesized from biomass-derived fructose through a continuous flow process using heterogeneous solid acid catalysts. Different solid acid catalysts, including niobium-based catalysts, Amberlyst 15, and Amberlyst 36, were tested for selective dehydration of fructose to 5-HMF in a biphasic (H2O/MIBK) continuous-flow tubular reactor. The catalysts were characterized using complementary techniques, including BET surface area, XRD, TGA, NH3-TPD, FT-IR, and pyridine-FT-IR. We also studied the effects of different reaction parameters such as the initial fructose concentration, reaction temperature, feeding flow rate, and aqueous-to-organic phase ratio. The optimal conditions were determined to be 150 °C temperature, a 0.25 ml min-1 feeding flow rate, 200 mg ml-1 NaCl concentration, 200 and 400 mg ml-1 fructose concentrations, and aqueous-to-organic phase ratios of 1?:?5 and 1?:?10. In addition, niobium phosphate (NbP), synthetic sulphated niobia (NbS) and Amberlyst 36 (Amb. 36) were active and selective, leading to 5-HMF yields in the range of 54-60% under the optimal operating conditions. Meanwhile, the Amb. 36 catalyst exhibited a 5-HMF selectivity of 70% at 150 °C, and therefore it was selected as the catalyst for the fructose dehydration reaction. Additionally, the Amb. 36 catalyst showed consistent catalytic activity and selectivity during a time-on-stream of 8 h. Furthermore, a reusability test with the used catalyst demonstrated that this catalyst can be recycled and reused without losing its catalytic activity.
Souzanchi, Sadra,Nazari, Laleh,Rao, Kasanneni Tirumala Venkateswara,Yuan, Zhongshun,Tan, Zhongchao,Xu, Chunbao Charles
p. 8479 - 8491
(2021)
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Efficient and selective conversion of hexose to 5-hydroxymethylfurfural with tin-zirconium-containing heterogeneous catalysts
Efficient and selective production of 5-hydroxymethylfurfural (HMF) from the hexose is achieved in the presence of heterogeneous Sn-based catalyst. The mixed SnO2-ZrO2 is prepared from zirconium n-propoxide and different metal Sn precursors using Sol-gel method. The sulfated SnO 2-ZrO2 (SO42 -/SnO 2-ZrO2) is obtained by the impregnation method with H 2SO4 solution. All catalytic materials are detected with XRD, TG, SEM, TEM and BET techniques in order to reveal the physical properties and structures of these materials. When these materials were used in the dehydration of fructose, it was found that the suitable ratio of Sn/Zr is 0.5, and the catalytic activity of SO42 -/SnO 2-ZrO2 is higher than that of SnO2-ZrO 2 where more than 75.0% yield of HMF was obtained for 2.5 h at 120 C. The effects of reaction temperature and reaction time were also investigated. Moreover, the recycling experiment of catalyst shows that the catalytic activity can be almost kept unchanged after being used five times.
Wang, Yanhua,Tong, Xinli,Yan, Yongtao,Xue, Song,Zhang, Yangyang
p. 38 - 43
(2014)
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A facile acidic choline chloride-p-TSA DES-catalysed dehydration of fructose to 5-hydroxymethylfurfural
The conversion of lignocellulosic biomass to biofuel precursors has recently been a focus of intensive research due to the essential role of biofuels as transport fuels in the future. Specifically, the conversion of fructose to 5-hydroxymethylfurfural (5HMF) has gained momentum, as 5HMF is a versatile bio-based platform molecule that leads to a plethora of high-value chemicals and biofuel molecules, such as DMF. Herein, we report the use of an environmentally friendly, Bronsted acidic, deep eutectic mixture consisting of choline chloride (ChCl) and p-TSA for the dehydration of fructose to 5HMF. Unlike previous systems, the use of ChCl-p-TSA plays a dual role, as both a hydrogen bond donor (HBD) and a catalyst for the dehydration reaction, thus obviating the addition of an external acid. The reaction was examined and optimised in a batch system, where it was found that fructose was readily dehydrated to 5HMF. The best reaction conditions, with the highest 5HMF yield of 90.7%, were obtained at a temperature of 80 °C using a DES molar mixing ratio of 1 : 1 ChCl : p-TSA and feed ratio of 2.5%, and with a reaction time of one hour.
Assanosi, Amhamed A.,Farah, Mohamed M.,Wood, Joseph.,Al-Duri, Bushra
p. 39359 - 39364
(2014)
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Conversion of fructose, glucose, and cellulose to 5-hydroxymethylfurfural by alkaline earth phosphate catalysts in hot compressed water
The phosphates of alkaline earth metals (calcium and strontium) synthesized by precipitation process in acetone-water media system were used as catalysts for converting fructose, glucose, and cellulose to 5-hydroxymethylfurfural (HMF) under hot compressed water condition. It was found that the phosphates of calcium and strontium effectively catalyzed the HMF formation from fructose and glucose dehydration and cellulose hydrolysis/dehydration reaction, as compared with the non-catalytic system. The XRD analysis confirmed the CaP 2O6 and α-Sr(PO3)2 crystalline phases of the catalyst samples, while acid strength of both catalysts was in a range of +3.3 ≤ H0 ≤ +4.8. From the study, CaP 2O6 and α-Sr(PO3)2 showed similar catalytic performance toward the dehydration of sugars, providing the HMF yields of 20-21% and 34-39% from glucose and fructose, respectively; whereas the total yield of glucose and HMF from the hydrolysis/dehydration of cellulose over α-Sr(PO3)2 (34%) was higher than that over CaP2O6 (17.4%).
Daorattanachai, Pornlada,Khemthong, Pongtanawat,Viriya-Empikul, Nawin,Laosiripojana, Navadol,Faungnawakij, Kajornsak
p. 58 - 61
(2012)
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Highly efficient conversion of carbohydrates into 5-hydroxymethylfurfural using the bi-functional CrPO4 catalyst
The highly efficient synthesis of 5-hydroxymethylfurfural (HMF) from carbohydrates was achieved using the inexpensive and bi-functional CrPO4 catalyst in a biphasic system. The effect of various reaction conditions, including reaction temperature, time, and solvent, on HMF yields was explored. A HMF yield of up to 83% was obtained using fructose as the reactant at 140 °C for 15 min. A maximum HMF yield of 63% was also achieved from glucose when the reaction was carried out at 140 °C for 30 min. Among the reported catalysts, CrPO4 was shown to be one of the most effective in the conversion of glucose into HMF, which is comparable to an ionic liquid reaction system. Moreover, the CrPO4 catalyst exhibited high activity to convert microcrystalline and lignocellulosic feedstock to HMF without the need for the addition of homogeneous mineral acids. The possible conversion mechanism of carbohydrates into HMF catalyzed by the bi-functional CrPO4 catalyst is discussed.
Xu, Siquan,Yan, Xiaopei,Bu, Quan,Xia, Haian
p. 8048 - 8052
(2016)
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Conversion of hexose into 5-hydroxymethylfurfural in imidazolium ionic liquids with and without a catalyst
Conversion of fructose and glucose into 5-hydroxymethylfurfural (HMF) was investigated in various imidazolium ionic liquids, including 1-butyl-3-methylimidazolium chloride (BmimCl), 1-hexyl-3-methylimidazolium chloride (HmimCl), 1-octyl-3-methylimidazolium chloride (OmimCl), 1-benzyl-3-methylimidazolium chloride (BemimCl), 1-Butyl-2,3-dimethylimidazolium chloride (BdmimCl), and 1-butyl-3-methylimidazolium p-toluenesulfonate (BmimPS). The acidic C-2 hydrogen of imidazolium cations was shown to play a major role in the dehydration of fructose in the absence of a catalyst, such as sulfuric acid or CrCl3. Both the alkyl groups of imidazolium cations and the type of anions affected the reactivity of the carbohydrates. Although, except BmimCl and BemimCl, other four ionic liquids could only achieve not more than 25% HMF yields without an additional catalyst, 60-80% HMF yields were achieved in HmimCl, BdmimCl, and BmimPS in the presence of sulfuric acid or CrCl3 in sufficient quantities.
Cao, Quan,Guo, Xingcui,Yao, Shengxi,Guan, Jing,Wang, Xiaoyan,Mu, Xindong,Zhang, Dongke
p. 956 - 959
(2011)
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Synthesis and evaluation of stable polymeric solid acid based on halloysite nanotubes for conversion of one-pot cellulose to 5-hydroxymethylfurfural
Based on halloysite nanotubes (HNTs), precipitation polymerization and Pickering emulsion polymerization were firstly adopted to synthesize two composites i.e. HNTs-polystyrene(PSt)-polydivinylbenzene(DVB)(i) and HNTs-PSt-PDVB(ii), respectively. After sulfonation by 98% H2SO 4, two polymeric solid acid catalysts i.e. HNTs-PSt-PDVB-SO 3H(i) and HNTs-PSt-PDVB-SO3H(ii) were successfully prepared for conversion of one-pot cellulose to 5-hydroxymethylfurfural (HMF) in an ionic liquid 1-ethyl-3-methyl-imidazolium chloride ([EMIM]-Cl). Characterization of two catalysts showed that HNTs-PSt-PDVB-SO3H(i) possessed superior hydrophobicity, content of -SO3H groups, and total acidic amounts to those of HNTs-PSt-PDVB-SO3H(ii), but with less very strong acidic sites and non-uniform morphology. Then the amount of the catalysts, reaction time and reaction temperature were optimized for cellulosic conversion over the two catalysts, and a maximum yield of 28.52% for HNTs-PSt-PDVB-SO3H(i) and 32.86% for HNTs-PSt-PDVB-SO 3H(ii) under the optimized conditions was obtained, indicating very strong acidic sites played a key role in cellulose conversion. In addition, the two as-prepared catalysts could be very easily recycled at least five times without significant loss of catalytic activity.
Zhang, Yunlei,Pan, Jianming,Yan, Yongsheng,Shi, Weidong,Yu, Longbao
p. 23797 - 23806
(2014)
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Fermentable sugars by chemical hydrolysis of biomass
Abundant plant biomass has the potential to become a sustainable source of fuels and chemicals. Realizing this potential requires the economical conversion of recalcitrant lignocellulose into useful intermediates, such as sugars. We report a high-yielding chemical process for the hydrolysis of biomass into monosaccharides. Adding water gradually to a chloride ionic liquid-containing catalytic acid leads to a nearly 90% yield of glucose from cellulose and 70-80% yield of sugars from untreated corn stover. Ion-exclusion chromatography allows recovery of the ionic liquid and delivers sugar feedstocks that support the vigorous growth of ethanologenic microbes. This simple chemical process, which requires neither an edible plant nor a cellulase, could enable crude biomass to be the sole source of carbon for a scalable biorefinery.
Binder, Joseph B.,Raines, Ronald T.
p. 4516 - 4521
(2010)
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Self-assembly of mesoporous TiO2 nanospheres via aspartic acid templating pathway and its catalytic application for 5-hydroxymethyl-furfural synthesis
Self-assembled mesoporous TiO2 nanoparticulate material with well-defined nanospherical morphologies was prepared by using dl-aspartic acid as a template. Powder XRD, TEM and SEM techniques were used to characterize the TiO2 nanoparticles. The presence of high acid density in the mesoporous TiO2 was confirmed by pyridine-IR and NH3-TPD studies. This new mesoporous TiO2 nanomaterial efficiently catalyzed the dehydration of d-fructose and d-glucose into 5-hydroxymethylfurfural in DMA-LiCl solvent under microwave assisted heating. The acidic sites of the TiO2 nanomaterial were responsible for the dehydration reaction which produced a maximum 82.3% HMF.
De, Sudipta,Dutta, Saikat,Patra, Astam K.,Bhaumik, Asim,Saha, Basudeb
p. 17505 - 17510
(2011)
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A catalytic system for the selective conversion of cellulose to 5-hydroxymethylfurfural under mild conditions
Conversion of cellulose to 5-hydroxymethylfurfural (5-HMF), one of the most promising products derived by conversion of renewable raw materials, has been studied. When performing the process in ionic liquids, addition of small amounts of Br?nsted acids was found to allow the adaption of the catalytic system to be used under mild conditions, which is particularly important for the industrial processing of cellulose. Highest yield of 5-HMF (44%) was obtained by carrying out the conversion of cellulose at 100 °C for 12 h with a modified catalytic system based on CrCl3·6H2O and H2SO4.
Galkin,Krivodaeva,Ananikov
p. 2954 - 2957
(2015)
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The first molecular level monitoring of carbohydrate conversion to 5-hydroxymethylfurfural in ionic liquids. B2O3-an efficient dual-function metal-free promoter for environmentally benign applications
The mechanistic nature of the conversion of carbohydrates to the sustainable platform chemical 5-hydroxymethylfurfural (5-HMF) was revealed at the molecular level. A detailed study of the key sugar units involved in the biomass conversion process has shown that the simple dissolution of fructose in the ionic liquid 1-butyl-3-methylimidazolium chloride significantly changes the anomeric composition and favors the formation of the open fructoketose form. A special NMR approach was developed for the determination of molecular structures and monitoring of chemical reactions directly in ionic liquids. The transformation of glucose to 5-HMF has been followed in situ through the detection of intermediate species. A new environmentally benign, easily available, metal-free promoter with a dual functionality (B2O 3) was developed for carbohydrate conversion to 5-HMF.
Khokhlova, Elena A.,Kachala, Vadim V.,Ananikov, Valentine P.
p. 783 - 789
(2012)
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Functional networks of organic and coordination polymers: Catalysis of fructose conversion
The creation of functional porous nanoscale networks with enhanced reactive group accessibility provides rich promise for novel designs of composite materials. We present a straightforward strategy for the preparation of porous polymer/MOF hybrids via polymerization of organic monomers and cross-linkers impregnated within the pores of the MOFs followed by functionalization of the resulting composite. A poly(maleimide-co-dibinylbenzene) network was synthesized in the presence of MOF MIL-101(Cr), resulting in stable hybrid composites, which were then brominated to give porous hybrids of cross-linked poly(N-bromomaleimide), a polymeric analogue of N-bromosuccinimide, interconnected with crystalline nanoparticles of the MOF. Due to the large porosity and surface area, the active bromine (halamine) groups in the polymer network enabled high activity of the composites in heterogeneous catalysis of conversion of d-fructose into 5-hydroxymethylfurfural.
Bromberg, Lev,Su, Xiao,Hatton, T. Alan
p. 6257 - 6264
(2014)
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Biomass derived β-cyclodextrin-SO3H carbonaceous solid acid catalyst for catalytic conversion of carbohydrates to 5-hydroxymethylfurfural
A new β-cyclodextrin-SO3H carbonaceous solid acid catalyst was synthesized in an ecofriendly manner and was found efficient for conversion of carbohydrates into 5-hydroxymethylfurfural. Numbers of different solvents systems were screened for efficient formation of HMF. The results showed that the β-cyclodextrin based-SO3H catalyst resulted in 96% 5-hydroxymethylfurfural (HMF) yield from fructose while glucose gave a 47% HMF yield in DMSO in pretty good yields and high selectivity. Polysaccharides such as sucrose and inulin also gave about 85% and 92% yield of HMF. The catalyst was readily recovered and reused for atleast three runs without any significant impact on yields of products. The main advantages of this protocol include practical simplicity, high yields, recyclable catalyst, safety and cheapness of benign solvents.
Thombal, Raju S.,Jadhav, Vrushali H.
p. 213 - 216
(2015)
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Production of 5-hydroxymethylfurfural in ionic liquids under high fructose concentration conditions
Acid-promoted, selective production of 5-hydroxymethylfurfural (HMF) under high fructose concentration conditions was achieved in ionic liquids (ILs) at 80 °C. A HMF yield up to 97% was obtained in 8 min using 1-butyl-3- methylimidazolium chloride ([C4mim]Cl) catalyzed with 9 mol % hydrochloric acid. More significantly, an HMF yield of 51% was observed when fructose was loaded at a high concentration of 67 wt % in [C4mim]Cl. Water content below 15.4% in the system had little effect on HMF yield, whereas a higher water content was detrimental to both reaction rate and HMF yield. In situ NMR analysis suggested that the transformation of fructose to HMF was a highly selective reaction that proceeded through the cyclic fructofuranosyl intermediate pathway. This work increased our capacity to produce HMF, and should be valuable to facilitate cost-efficient conversion of biomass into biofuels and bio-based products.
Li, Changzhi,Zhao, Zongbao K.,Wang, Aiqin,Zheng, Mingyuan,Zhang, Tao
p. 1846 - 1850
(2010)
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An Effective and Inexpensive Hf/ZSM-5 Catalyst for Efficient HMF Formation from Cellulose
Abstract: The production of 5-hydroxymethylfurfural (HMF) from cellulose is of great significance for the high-value utilization of biomass, although this route currently faces the challenge of low efficiency. In the present work, a series of effective (x)Hf/ZSM-5 catalysts were developed for HMF production from cellulose, and analyzed by BET, XRD, SEM, ICP, NH3-TPD, Py-FTIR techniques. Driven by the (5)Hf/ZSM-5 catalyst, HMF with a yield of up to 67.5% and 17.2% of furfural are simultaneously obtained from cellulose in the H2O(NaCl)/THF biphasic system. Moreover, after four consecutive cycles, (5)Hf/ZSM-5 catalyst still maintained part of its catalytic activity. The 67.5% HMF yield achieved herein is one of the highest yields achieved in the conversion reaction using cellulose as a substrate, and the catalytic performance of the H2O(NaCl)/THF system containing the (5)Hf/ZSM-5 catalyst is even comparable to that of the expensive ionic liquid system. This result reflects the application prospect of (5)Hf/ZSM-5 catalyst in the future industrial production process of HMF. Graphic Abstract: [Figure not available: see fulltext.]
Wu, Ningxin,Zhang, Manling,Pan, Xiaomei,Zhang, Jin,Gao, Lijing,Xiao, Guomin
p. 1984 - 1992
(2021)
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Efficient synthesis of 2,5-furandicarboxylic acid from biomass-derived 5-hydroxymethylfurfural in 1,4-dioxane/H2O mixture
The catalytic conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a renewably sourced substitution for petroleum-derived terephthalic acid, at a high concentration is highly demanding but challenging. Herein, the efficient conversion of HMF (10–25 wt%) in 1,4-dioxane/H2O was achieved, and a desirable FDCA yield of 98% was obtained from HMF (10 wt%) over commercial Ru/C (2 Equiv. NaHCO3, 4 MPa O2, 3 h, and 140 ℃). In addition, a two-step cascade reaction was developed for FDCA production, in which FDCA was employed as the acid catalyst to promote the dehydration of fructose (10 wt%) to HMF, followed by oxidation in 1,4-dioxane/H2O to FDCA over Ru/C. As compared to pure water or 1,4-dioxane, the better stability of HMF in 1,4-dioxane/H2O with a weak alkaline environment and the enhancement of superoxide radicals (·O2-) in 1,4-dioxane/H2O could ensure high FDCA yield at high HMF concentration.
Fang, Huayu,Ke, Xixian,Li, Tianyuan,Lin, Lu,Liu, Huai,Sun, Yong,Tang, Xing,Xie, Weizhen,Zeng, Xianhai
(2021/12/17)

Polystyrene immobilized Br?nsted acid ionic liquid as an efficient and recyclable catalyst for the synthesis of 5-hydroxymethylfurfural from fructose
5-Hydroxymethylfurfural (5-HMF) is one of the compounds, which has attracted a lot of attention due to its multi-functional nature and many applications in the industry. In this experimental study, 5-HMF has been synthesized using a polystyrene-supported Br?nsted acid ionic liquid catalyst. This heterogonous catalyst has been synthesized via the decoration of 5-amino-1H-tetrazole-bonded sulfonic acid onto the surface of chloromethylated polystyrene (PS-Tet-SO3H). The prepared PS-Tet-SO3H is was characterized by Fourier transform infrared (FT-IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetry–differential scanning calorimetry (TG-DSC), and Scanning electron microscopy (SEM). PS-Tet-SO3H catalyst for has then been used in the synthesis of 5-HMF from fructose via an acid hydrolysis reaction. Finally, the prepared PS-Tet-SO3H can be recycled and reused for 4 cycles with no significant loss of performance.
Momenbeik, Fariborz,Nasrollahzadeh, Mahmoud,Nezafat, Zahra,Orooji, Yasin
(2021/10/26)

Catalytic wet air oxidation of D-glucose by perovskite type oxides (Fe, Co, Mn) for the synthesis of value-added chemicals
The conversion of common biomasses derived, as D-glucose, into value-added chemicals has received highest attention in the last few years. Among all processes, the catalytic wet air oxidation (CWAO) of derived biomasses using noble metal-based heterogeneo
Geobaldo, Francesco,Pirone, Raffaele,Russo, Nunzio,Scelfo, Simone
(2022/03/15)

Bifunctional heterogeneous catalysts derived from the coordination of adenosine monophosphate to Sn(iv) for effective conversion of sucrose to 5-hydroxymethylfurfural
Adenosine 5′-monophosphate (AMP) with multiple functional groups can bind to various metal ions. In this work, AMP has been used as a ligand to coordinate Sn(iv) for the synthesis of porous coordination polymers (Sn-AMPs). The Sn-AMPs have both Br?nsted acid (BA) and Lewis acid (LA) sites and have been used as bifunctional heterogeneous catalysts for catalyzing the conversion of sucrose to 5-hydroxymethylfurfural (HMF), involving hydrolysis of sucrose to glucose and fructose, isomerization of glucose to fructose, and dehydration of fructose to HMF. The protonated N1 and OH–P of the coordinated AMP can form hydrogen bonds with glucose and fructose. This can promote the conversion of the sugars. Sn-AMP has exhibited a superior capability for the conversion of biomass-derived sugars into HMF. The HMF yields of 76.1%, 67.5% and 62.9% were achieved from fructose, glucose, and sucrose, respectively.
Ji, Peijun,Jiao, Lutong,Meng, Han,Wang, Chenyu
p. 630 - 640
(2022/02/09)

Ethanolysis of selected catalysis by functionalized acidic ionic liquids: An unexpected effect of ILs structural functionalization on selectivity phenomena
A series of functionalized hydrogen sulfate imidazolium ILs were synthesized and applied as catalysts in the reaction of glucose, xylose and fructose with ethanol. In this research, an unexpected selectivity phenomenon was observed. It showed that in this reaction functionalized ILs should be considered as a special type of catalyst. Functionalization of alkyl imidazolium ILs, especially the addition of electronegative OH groups, causes a clear and unexpected effect manifested via visible changes in the selectivity of the reaction studied. In the case of fructose, an increase in the number of OH groups affects an increase in the selectivity towards ethyl levulinate from 14.2% for [bmim]HSO4 to 20.1% for [glymim]HSO4 with an additional increase in selectivity to 5-hydroxymethyfurfural. In turn, for xylose, the introduction of OH groups to the alkyl chain was manifested by a decrease in selectivity to furfural as its ethyl acetal and an increase in selectivity to ethylxylosides. This journal is
Nowakowska-Bogdan, Ewa,Nowicki, Janusz
p. 1857 - 1866
(2022/02/05)

Aqueous-Natural Deep Eutectic Solvent-Enhanced 5-Hydroxymethylfurfural Production from Glucose, Starch, and Food Wastes
5-Hydroxymethylfurfural (HMF) has been regarded as an essential building block for synthesizing chemicals and biofuels, but the direct conversion of biomass to HMF is still a critical challenge. In this study, a cheap and green aqueous-natural deep eutectic solvent (A-NADES) was used to efficiently produce HMF from various carbohydrates, with a low amount of SnCl4 as the catalyst. High HMF yields of 64.3, 64.0, 61.3, and 54.5 % were obtained from glucose, starch, rice waste, and bread waste at 130 °C in the A-NADES/MIBK (methyl isobutyl ketone) biphasic system, respectively. Mechanistic study results revealed that the water in A-NADES was the key factor in facilitating the conversion of Sn atom existent forms and promoted the HMF production. The choline chloride in NADES stabilized the HMF product with the cooperation of extraction solvent MIBK and inhibited the side reactions of HMF. This study investigated the multiple interaction functions of A-NADES to feedstocks and proposed a practical application of novel solvents to facilitate biomass and food waste conversion with a green method.
Lin, Lu,Wang, Qian,Wang, Xinyu,Zeng, Xianhai,Zuo, Miao
(2021/12/09)

From useless humins by-product to Nb@graphite-like carbon catalysts highly efficient in HMF synthesis
Highly dispersed supported NbOx species were prepared via a deposition precipitation-carbonization (DPC)-like method. As precursors for niobium species and carrier ammonium niobate(V) oxalate hydrate and humins were used. Characterization of the resulted catalysts indicated bi-functional acid-base niobium species anchored onto a highly hydrophobic graphite-like carbon structure. These catalysts were investigated in the one-pot conversion of glucose to 5-hydroxymethylfurfural (HMF) in a biphasic system consisting of a mixture of a 20 wt% NaCl aqueous solution phase and an organic extracting phase (methyl-isobutyl-ketone (MIBK), 2-tert-butylphenol (TBP) or 2-sec-butylphenol (SBP)). The optimization conditions afforded the highest yield to HMF (96 %) for the GHNb1.2 catalyst (with 2.5 wt%Nb), the base/acid sites ratio of 1.76, in biphasic TBP/water system, at 180 °C after 8 h.
El Fergani, Magdi,Candu, Natalia,Tudorache, Madalina,Bucur, Cristina,Djelal, Nora,Granger, Pascal,Coman, Simona M.
(2021/04/19)

Tuning Br?nsted and Lewis acidity on phosphated titanium dioxides for efficient conversion of glucose to 5-hydroxymethylfurfural
5-Hydroxymethylfurfural (HMF) derived from cellulosic sugars has become increasingly important as a platform chemical for the biorefinery industry because of its versatility in the conversion to other chemicals. Although HMF can be produced in high yield from fructose dehydration, fructose is rather expensive because it requires multiple processing steps. On the other hand, HMF can be produced directly from highly abundant glucose, which could reduce time and cost. However, an effective and multifunctional catalyst is needed to selectively promote the glucose-to-HMF reaction. In this work, we report a bifunctional phosphated titanium dioxide as an efficient catalyst for such a reaction. The best catalyst exhibits excellent catalytic performance for the glucose conversion to HMF with 72% yield and 83% selectivity in the biphasic system. We achieve this by tuning the solvent system, controlling the amount of Br?nsted and Lewis acid sites on the catalyst, and modification of the reaction setup. From the analysis of acid sites, we found that the addition of phosphate group (Br?nsted acid site) onto the surface of TiO2(Lewis acid site) significantly enhanced the HMF yield and selectivity when the optimum ratio of Br?nsted and Lewis acid sites is reached. The high catalytic activity, good reusability, and simple preparation method of the catalyst show a promise for the potential use of this catalytic system on an industrial scale.
Songtawee, Siripit,Rungtaweevoranit, Bunyarat,Klaysom, Chalida,Faungnawakij, Kajornsak
p. 29196 - 29206
(2021/10/08)

Application of vanadyl hydrogen phosphate/KIT-6 composites as a catalyst for dehydration of sucrose
In this research work, the synthesis of well-ordered mesoporous structure KIT-6 silica-supported vanadyl hydrogen phosphate hemihydrate (VHP/KIT-6) catalysts possessing varying surface area was carried out, followed by being utilized in the dehydration of sucrose to 5-hydroxymethylfurfural (5-HMF) as a solid acid catalyst. The fabrication of two different VHP/KIT-6 catalysts was conducted using the impregnation approach through V2O5 reduction in alcoholic media. Then, the catalytic behavior presented by the prepared VHP/KIT-6 samples was compared with unsupported VHP and unsupported vanadyl pyrophosphate (VPP), which was prepared through the calcination of VHP precursor at 400?°C for 24?h. The prepared catalysts were characterized by different analyses, including ICP-OES, BET, XRD, NH3-TPD analysis, FT-IR spectroscopy, as well as SEM and TEM techniques. Furthermore, important parameters, including the catalyst type and weight, sucrose amount, time, temperature, and the type of solvent on sucrose dehydration, were also studied. It was observed that the highest catalytic activity in the dehydration reaction (5-HMF yield: 67%, sucrose conversion: > 94%) could be provided by the catalyst possessing the highest surface area. Moreover, the catalyst reusability was examined for consecutive four times, based on which no considerable change in the catalytic activity was observed.
Najafi Sarpiri, Jaleh,Najafi Chermahini, Alireza,Saraji, Mohammad,Shahvar, Ali
p. 2291 - 2302
(2021/02/26)

Synthesis of 5-hydroxymethylfurfural from cassava (Manihot utilissima pohl) peels through dehydration reaction using deep eutectic solvent based on choline chloride/citric acid
The high cellulose content in cassava peel has an opportunity to produce bio-based chemical products in 5-hydroxymethylfurfural (5-HMF) form. This study aimed to determine the optimum conditions of glucose dehydration reaction as a result of hydrolysis of the best cassava peel cellulose. The variables observed in this study were H2SO4 catalyst concentrations in the hydrolysis reaction, temperature and amount of deep eutectic solvents based on choline chloride/citric acid. The optimum dehydration reaction conditions in this study was the glucose:deep eutectic solvents mass ratio of 1:6 at the reaction temperature of 80 oC. The highest yield of 64.50% at an initial glucose concentration of 5.70% using a 1.5% H2SO4 catalyst during the hydrolysis of cassava peel cellulose. The results obtained in this study indicated that addition of choline chloride/citric acid as deep eutectic solvent can increase the yield of 5-HMF.
Manurung,Silalahi,Winda,Siregar
p. 1115 - 1119
(2021/05/10)

Incorporation of Al3+ Sites on Br?nsted Acid Metal–Organic Frameworks for Glucose-to-Hydroxylmethylfurfural Transformation
5-hydroxylmethylfurfural (HMF) is a bio-based chemical that can be prepared from natural abundant glucose by using combined Br?nsted–Lewis acid catalysts. In this work, Al3+ catalytic site has been grafted on Br?nsted metal–organic frameworks (MOFs) to enhance Br?nsted–Lewis acidity of MOF catalysts for a one-pot glucose-to-HMF transformation. The uniform porous structure of zirconium-based MOFs allows the optimization of both acid strength and density of acid sites in MOF-based catalysts by incorporating the desired amount of Al3+ catalytic sites at the organic linker. Al3+ sites generated via a post-synthetic modification act as Lewis acid sites located adjacent to the Br?nsted sulfonated sites of MOF structure. The local structure of the Al3+ sites incorporated in MOFs has been elucidated by X-ray absorption near-edge structure (XANES) combined with density functional theory (DFT) calculations. The cooperative effect from Br?nsted and Lewis acids located in close proximity and the high acid density is demonstrated as an important factor to achieve high yield of HMF.
Tangsermvit, Vitsarut,Pila, Taweesak,Boekfa, Bundet,Somjit, Vetiga,Klysubun, Wantana,Limtrakul, Jumras,Horike, Satoshi,Kongpatpanich, Kanokwan
(2021/03/29)

CaCl2molten salt hydrate-promoted conversion of carbohydrates to 5-hydroxymethylfurfural: an experimental and theoretical study
Alkaline earth metal salts are environmentally friendly and economical. They have attracted much attention in the process of biomass conversion, especially for isomerization and dehydration. However, the lack of understanding of the alkaline earth metal-mediated catalytic mechanism prevents the achievement of high HMF yields from glucose or fructose. Herein, we performed experimental and theoretical studies on CaCl2-catalyzed glucose-to-fructose isomerization and fructose-to-HMF dehydration. In CaCl2solution, the highest fructose yield (33.6%) from glucose can be achieved at 80 °C. Meanwhile, the presence of CaCl2in fructose-to-HMF dehydration notably improved fructose conversion. A “one-pot” isomerization-dehydration of glucose to prepare HMF was designed and 100% conversion and 52.1% HMF yield were obtained. The CaCl2solution can be reused for five runs while maintaining catalytic activity without regeneration. Through1H NMR,13C NMR, DOSY-NMR and DFT calculations, we concluded that the coordination between the C1/C2 sites of the β-glucopyranose tautomer and CaCl2promoted the 1,2-intramolecular hydride shift of glucose, thus rapidly converting glucose into fructose. Similarly, Ca2+can complex with the C2/C6-OH of β-d-fructofuranose and stabilize this tautomer, which easily forms HMF. This is the main reason that CaCl2can promote the preparation of HMF from fructose.
Lin, Changqu,Chai, Chaoqun,Li, Yuanzhang,Chen, Jiao,Lu, Yanyu,Wu, Hongli,Zhao, Lili,Cao, Fei,Chen, Kequan,Wei, Ping,Ouyang, Pingkai
supporting information
p. 2058 - 2068
(2021/03/29)

Highly Efficient Zirconium Based Carbonaceous Solid Acid Catalyst for Selective Synthesis of 5-HMF from Fructose and Glucose in Isopropanol as a Solvent
A new zirconium based carbonaceous solid acid catalyst Zr@CC-PA with both Lewis and Bronsted acidic sites was prepared by simultaneous carbonization and phosphonation of glucose followed by incorporation of zirconium metal on the surface of the catalyst. The catalyst was easy to prepare and the synthesized catalyst was well characterized using different techniques such as FT-IR, P-XRD, EDAX, SEM, TEM and XPS analysis. The catalytic activity was evaluated for synthesis of a very important platform chemical 5-HMF from fructose to glucose using isopropanol as a solvent. The catalyst was found to be highly efficient giving 86% yield of 5-HMF from fructose and 45% yield from glucose with high selectively. The catalyst can be reused at least four times without depreciation in its catalytic activity. The catalytic method developed is efficient, green and economical. Graphic abstract: [Figure not available: see fulltext.]
Jadhav, Vrushali H.,Jori, Popat K.
(2021/08/12)

Effect of molecular structure of cation and anions of ionic liquids and co-solvents on selectivity of 5-hydroxymethylfurfural from sugars, cellulose and real biomass
The concept of biorefinery still requires advancements in process development for energy and materials. Ionic liquids have been successfully used for several biorefinery applications including high yield synthesis of biofuels and value added platform chemicals. Designing suitable ionic liquid that is efficient in terms of cost as well as product selectivity is still highly needed. This study is carried out to check the effect of different anions of Bronsted acidic ionic liquids (BAILs), Bronsted Lewis acidic ionic liquids (BLAILs), Lewis acidic ionic liquids (LAILs) as well as organic electrolyte solutions (OES) for 5-HMF selectivities from monosaccharides, polysaccharides as well as lignocellulosic composite. Different variables and parameters such as Lewis acidity of anions, alkyl side chain of ionic liquid, metal chloride type and loading, time, temperature, substrate loading, polar protic and aprotic solvents are thoroughly studied for process optimization. Polar protic solvents added in [C1C4SO3HPy] based ionic liquids with CH3COO? and Cl? anions yielded 94 and 80% 5-HMF from fructose and glucose respectively in the presence of AlCl3 as Lewis acid. C4SO3H side chain yielding high from fructose and glucose is inefficient for conversion of cellulose and lignocellulose. High product selectivity from these biopolymers is achieved using butyl side chain with 3-methylpyridinium cation and chlorochromate anion.
Muhammad, Nawshad,Naz, Sadia,Uroos, Maliha
(2021/06/07)

Solid acid catalyst prepared via one-step microwave-assisted hydrothermal carbonization: Enhanced stability towards intensified production of 5-hydroxymethylfurfural in water/γ-valerolactone/NaCl
In this study, carbon-based catalysts prepared via one-step microwave (MW)-assisted hydrothermal carbonization, functionalized with 2-hydroxyethylsulfonic acid (HESA) and hydrochloric acid (HCl), were tested on the intensified production of HMF from dehydration of glucose in biphasic system, consisting of water/γ-valerolactone/NaCl. The highest HMF yield (51.61%) was obtained when using 40/60 %v/v of water/ γ-valerolactone (GVL), C-SO3H catalyst loading at 0.5% by weight (%wt) of glucose, at 180°C for 45 min. In addition, the one-step preparation applying MW irradiation provided the catalyst with excellent reusability up to at least five times.
Boonnoun, Panatpong,Kida, Tetsuya,Laosiripojana, Navadol,Quitain, Armando T.,Shotipruk, Artiwan,Siabbamrung, Phornwimol
(2021/08/03)

Sn Doping on Ta2O5 Facilitates Glucose Isomerization for Enriched 5-Hydroxymethylfurfural Production and its True Response Prediction using a Neural Network Model
Here, we describe the maximum production of 5-HMF using glucose over Sn doped Ta2O5 in a binary solvent system. The analytical characterizations established that Sn4+ in the catalyst interacts with Ta2O5 and offers the Lewis acid sites favorable for glucose isomerization to fructose. Similarly, the Ta2O5 support offers both the Lewis and Br?nsted acid sites to promote fructose dehydration to 5-HMF. The catalyst provided favorable conditions for the sequential sugar(s) transformation, i. e., glucose isomerization followed by fructose dehydration, which resulted in a 5-HMF yield as high as 57 % wt. and 80 % selectivity under modest reaction conditions in a water-DMSO system using ST1 (1 % Sn on Ta2O5). The separate fructose to 5-HMF conversion study verified the negligible influence of Sn on the dehydration reaction. Moreover, the catalyst's systematic sugar conversion enabled a >65 % fructose formation, which accounts for the enriched 5-HMF synthesis. The neural network model best represented the 5-HMF data (4 % MAE for glucose and fructose conversions).
Mahala, Sangeeta,Arumugam, Senthil M.,Kumar, Sandeep,Singh, Dalwinder,Sharma, Shelja,Devi, Bhawana,Yadav, Sudesh K.,Elumalai, Sasikumar
p. 4787 - 4798
(2021/10/01)

Bifunctional crystalline microporous organic polymers: Efficient heterogeneous catalysts for the synthesis of 5-hydroxymethylfurfural
Developing efficient catalysts for the synthesis of 5-hydroxymethylfurfural (HMF) from biomass resources is very demanding as it is an important renewable platform chemical for the synthesis of biofuels, polymers and fine chemicals. Here, we have designed two new crystalline microporous bi-functional porous organic polymers through the extended aromatic substitution reaction under refluxing conditions. Porous polymers containing sulfonic acid and secondary amine groups are two reactive catalytic centres for carrying out the bi-functional heterogeneously catalysed reactions. Bifunctionalized porous polymers POPDS and POPSDS are synthesized through the reaction of 2,2′-benzidinedisulfonic acid and 4,4′-diaminostilbene-2,2′-disulfonic acid with cyanuric chloride, respectively. The materials were characterized thoroughly using powder X-ray diffraction, N2 sorption, FTIR, solid state 13C CP MAS NMR spectroscopy, FE-SEM, HR-TEM, XPS and TG/DTA analysis. These two crystalline porous polymers possesses good surface acidic and basic sites, and having flower-like and spherical particle morphologies. POPDS and POPSDS exhibited superior catalytic activity for the conversion of different small carbohydrates to 5-hydroxymethylfurfural (HMF) under microwave irradiation. Moreover, the recyclability tests of these catalysts revealed good durability up to sixth consecutive reaction cycles, suggesting the future potential of these catalysts in the sustainable synthesis of HMF.
Bhanja, Piyali,Sharma, Sachin Kumar,Chongdar, Sayantan,Paul, Bappi,Bhaumik, Asim
(2021/09/20)

Green synthesis of heterogeneous copper-alumina catalyst for selective hydrogenation of pure and biomass-derived 5-hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan
In this work novel copper-alumina catalysts were prepared through a solvent-free solid-state grinding method ― a low cost and green catalyst preparation method for selective hydrogenation of 5-hydroxymethylfurfural (5-HMF) into 2,5-bis(hydroxymethyl)furan (BHMF). Under the optimized reaction conditions (3 MPa H2, 130 °C, 1 h), >99 % 5-HMF conversion and 93 % BHMF yield were obtained by using a 20CA (20 mol%Cu-Al2O3) catalyst. The catalyst characterization results could reveal that the high catalytic activity and selectivity could be attributed to the presence of both metallic and electrophilic copper (Cu°/Cu2+) species and the uniformly distributed copper nanoparticles. Furthermore, an integrated catalytic process was demonstrated for the first time for direct conversion of mono, di, and polysaccharides into the corresponding BHMF, obtained overall BHMF yield in the range of 25 %–48 %.
Hu, Yulin,Rao, Kasanneni Tirumala Venkateswara,Xu, Chunbao Charles,Yuan, Zhongsun,Zhang, Yongsheng
(2020/11/26)

Method for preparing 2, 5-furandicarboxylic acid by 5-chloromethylfurfural hydrolysis and oxidation two-step method
The invention discloses a method for preparing 2, 5-furandicarboxylic acid by a 5-chloromethylfurfural hydrolysis and oxidation two-step method, which comprises the following steps of 1) mixing sodiumhydrosulfite, an alkali neutralizer and a solvent, and putting the mixture into a container, heating to a specified temperature, and then adding 5-chloromethylfurfural, keeping the specified temperature, carrying out hydrolysis reaction under a stirring condition, extracting reaction liquid by using an organic solvent after the reaction is finished, and carrying out rotary evaporation and recovery on an extracting agent to obtain a 5-hydroxymethylfurfural crude product, and 2) mixing the 5-hydroxymethylfurfural crude product, an alkali neutralizer and a solvent, placing the mixture in a reaction container, adding a catalyst, carrying out a reaction under a closed condition by using air or oxygen as an oxygen source, adjusting the pH value of the reaction solution after the reaction is completed to obtain a 2, 5-furandicarboxylic acid precipitate, and filtering to obtain the 2, 5-furandicarboxylic acid product. The 5-hydroxymethylfurfural in the hydrolysate does not need high-energy-consumption refining and purification, and the obtained 5-hydroxymethylfurfural crude product can be directly used for efficient catalytic oxidation reaction to synthesize the 2, 5-furandicarboxylic acid.
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Paragraph 0022-0033; 0036-0037

(2021/02/10)

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.
Arunaditya, Kantapong,Chaipojjana, Kawisa,Charinpanitkul, Tawatchai,Faungnawakij, Kajornsak,Le, Giang T. T.,Panichpol, Jamekorn,Rodruangnon, Tanapat,Thongratkaew, Sutarat
(2020/11/27)

Conversion of glucose to levulinic acid and upgradation to γ-valerolactone on Ru/TiO2catalysts
Combining glucose dehydration and the subsequent hydrogenation in one pot is a preferable approach for process development as such a method allows in situ generation of the reactive intermediate to undergo further reaction without extra energy-intensive separation. Herein, phosphotungstic acid and various types of titania (anatase, rutile, P25) supported Ru-based catalysts were considered as the dehydration and hydrogenation catalysts, respectively. Modulating the different reactant media (N2, H2), various products were obtained with GBL-H2O as the solvent. A considerable yield (42%) of levulinic acid (LA) and γ-valerolactone (GVL) (40%) were obtained in nitrogen and subsequent hydrogen. Ru/TiO2 (rutile) was the favorable hydrogenation catalyst among the three types of Ru/TiO2. Meanwhile, a certain amount of sorbitol (36%) was obtained in pure hydrogen. The hydrogenation of glucose is more likely to occur than the glucose dehydration. The physicochemical properties of the catalysts were characterized by XRD, BET, TPR, STEM and in situ CO/FT-IR, and the results show that well-dispersed Ru particles are located on the rutile crystallites, which facilitated the hydrogenation of LA. A strong metal support interaction (SMSI) was responsible for the various microstructure properties and the different hydrogenation reactivity. This work allows a better understanding of the reaction paths of glucose conversion.
Ding, Guoqiang,Liu, Yubo,She, Haohao,Yang, Yong,Zhao, Guoping,Zhu, Yulei
p. 14406 - 14413
(2021/08/23)

Method for preparing 5-hydroxymethylfurfural
The invention discloses a method for preparing 5-hydroxymethylfurfural. The method comprises the following steps: mixing materials containing a salt solution, a carbohydrate and a catalyst, and performing reaction I to obtain the 5-hydroxymethylfurfural, wherein the pressure of the reaction I is (-0.1)-(-0.015) Mpa. According to the preparation method disclosed by the invention, the HMF yield of 99% can be obtained, and meanwhile, the pressure of a reaction system is adjusted, so that relatively high reactant conversion rate and reaction product selectivity can be obtained.
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Paragraph 0052; 0059-0082

(2022/01/10)

Hydroxyapatite-Supported Polyoxometalates for the Highly Selective Aerobic Oxidation of 5-Hydroxymethylfurfural or Glucose to 2,5-Diformylfuran under Atmospheric Pressure
(NH4)5H6PV8Mo4O40 supported on hydroxyapatite (HAP) (PMo4V8/HAP (n)) was prepared through the ion exchange of hydroxy groups. This ion exchange favored the oxidative conversion of 5-hydroxymethylfurfural (5-HMF) to 2,5-diformylfuran (DFF) in a one-pot cascade reaction with 96.0 % conversion and 83.8 % yield under 10 mL/min of O2 flow. PMo4V8/HAP (31) was used to explore the production of DFF directly from glucose with the highest yield of 47.9 % so far under atmospheric oxygen, whereas the yield of DFF increased to 54.7 % in a one-pot and two-step reaction. These results indicated that the active sites in PMo4V8/HAP (31) retained their activities without any interference toward one another, which enabled the production of DFF in a more cost-saving way by only using oxygen and one catalyst in a one-step reaction. Meanwhile, the rigid structure of HAP and strong interaction in PMo4V8/HAP (31) allowed this catalyst to be reused for at least six times with high stability and duration.
Guan, Hongyu,Li, Ying,Wang, Qiwen,Wang, Xiaohong,Yu, Hang
p. 997 - 1005
(2021/08/06)

A PROCESS FOR THE SYNTHESIS OF FURANDICARBOXYLIC ACID
The present invention provides a process for the synthesis of FDC A comprising heating a mixture of fructose, aqueous NaCl or KC1, solvent, methyl isobutyl ketone (MIBK) and a catalyst at a temperature in the range of 150 to 200°C in a sealed vessel for a time period in the range of 2 to 5 hours to yield crude 5-HMF. The crude HMF further reacts with a biocatalyst at a temperature in a range of 20 to 50°C for a period at a range of 24 to 96 hours to yield Furandicarboxylic acid (FDCA) ), wherein the conversion of 5- HMF to FDCA is in the range of 90 to 100%.
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Paragraph 00050

(2021/06/26)

Exploring the Electronic Properties of Extended Benzofuran-Cyanovinyl Derivatives Obtained from Lignocellulosic and Carbohydrate Platforms Raw Materials
Two series of linear extended benzofuran derivatives associating cyanovinyl unit and phenyl or furan moieties obtained from benzaldehyde-lignocellulosic (Be series) or furaldehyde –saccharide (Fu series) platforms were prepared in order to investigate their emission and electrochemical properties. For the fluorescence in solution and solid states, contrasting results between the two series were demonstrated. For Be series a net aggregation induced emission effect was observed with high fluorescence quantum yield for the solid state. A [2+2] cycloaddition under irradiation at 350 nm was also revealed for one derivative of Be series. In contrast, for Fu series the fluorescence in solution is higher than in the solid state. The X-ray crystallography studies for the compounds reveal the formation of strong π-π stacking for the derivatives without emissive property in the solid state and the presence of essentially lateral contacts for emissive compounds. Taking advantage of the propensity to develop 2D π-stacking mode for the more extended derivative with a central furan cycle, organic field effect transistors presenting hole mobility have been made.
Ibrahim, Nagham,Moussallem, Chady,Allain, Magali,Segut, Olivier,Gohier, Frédéric,Frère, Pierre
p. 475 - 482
(2021/03/31)

Synthesis of 5-(hydroxy-, chloro-, bromomethyl)furan-2-enones Based on Fructose and their Antioxidant Activity
New enones were synthesized from 5-hydroxymethylfurfurol (5-HMF) and its derivatives using Wittig reactions of various phosphoranes. The synthesized enones were observed to affect free-radical oxidation in model systems, in particular, to suppress generat
Sakhautdinova,Malikova,Bortsova, Yu. L.,Mochalov,Muratov,Galimova,Sakhautdinov,Mustafin
p. 869 - 874
(2021/09/20)

A green and highly efficient synthesis of 5-hydroxymethylfurfural from monosaccharides using a novel binary ionic liquid mixture
We reported the development of 5-hydroxymethylfurfural (HMF) synthesis from monosaccharides using a binary ionic liquid as a reaction medium. Br?nsted–Lewis acidic ionic liquid (BLAIL) was synthesized from DABCO, 1,4-butane sultone, and AlCl3 under mild conditions. The BLAIL was found to be a suitable catalyst for the synthesis of HMF from monosaccharides in [Emim]Cl as a solvent. Under the optimized conditions, the yields of the HMF from glucose and fructose were 30.5 % and 96.5 %, respectively. The in?uence of time, temperature, catalytic loading, and substrate on the reaction was systematically investigated. The binary ionic liquid mixture could be reused three times without a noticeable drop in the activity. The isolation of HMF was easily performed through a liquid-liquid extraction method, which could be applied to the industrial process.
Phan, Ha Bich,Thi Nguyen, Quyen Bich,Luong, Cam Manh,Tran, Kim Nguyen,Tran, Phuong Hoang
(2021/02/12)

Niobium phosphates as bifunctional catalysts for the conversion of biomass-derived monosaccharides
The direct conversion of glucose and xylose into HMF and furfural is more efficient using a combination of Lewis and Br?nsted acids. Herein, niobium phosphates were prepared with different compositions, which affect its surface acidity and, consequently, the catalytic activity. The catalysts with a high P/Nb molar ratio presented a low molar ratio between Lewis and Br?nsted acid sites (L/B ratio), while those with low P/Nb molar ratio displayed a high L/B ratio. NbP-2, the sample with the highest L/B ratio, showed the highest reaction rate for both HMF and furfural formation. It was found, indeed, that the reaction rate for monosaccharides conversion and furans formation correlate linearly with the L/B ratio. The results presented not only introduce niobium phosphates with a high L/B molar ratio as promising catalysts for HMF and furfural production but also provide fundamental knowledge that will guide the design of other bifunctional heterogeneous catalysts.
Vieira, José Lucas,Paul, Geo,Iga, Gustavo D.,Cabral, Natalia M.,Bueno, José Maria C.,Bisio, Chiara,Gallo, Jean Marcel R.
(2021/03/30)

Zn(II)/Cd(II)-Based Metal-Organic Frameworks as Bifunctional Materials for Dye Scavenging and Catalysis of Fructose/Glucose to 5-Hydroxymethylfurfural
Functional neutral metal-organic frameworks (MOFs) {[M(5OH-IP)(L)]}n [M = Zn(II) for ADES-4; Cd(II) for ADES-5; 5OH-IP = 5-hydroxyisophthalate; L = (E)-N′-(pyridin-3-ylmethylene)nicotinohydrazide) have been synthesized by a diffusion/conventional reflux/mechanochemical method and characterized by various analytical techniques. Crystals were harvested by a diffusion method, and single-crystal X-ray diffraction (SXRD) analysis revealed that an adjacent [M2(COO)2]n ladder chain generates isostructural two-dimensional network motifs by doubly pillaring via L. The bulk-phase purity of ADES-4 and ADES-5 synthesized by a versatile synthetic approach has been recognized by the decent match of powder X-ray diffraction patterns with the simulated one. Both ADES-4 and ADES-5 showed selective adsorption of cationic dyes methylene blue (MB), methyl violet (MV), and rhodamine B (RhB) over anionic dye methyl orange (MO) from water with good uptake and rapid adsorption. Utilization of ADES-4 as a chromatographic column filler for adsorptive removal of individual cationic dyes as well as a mixture of dyes has been demonstrated from the aqueous phase. Interestingly, ADES-4 is reusable with good stability, and it showed a dye desorption phenomenon in methanol. The probable mechanism of cationic dye removal based on insight from structural information and plausible supramolecular interactions has also been explored. Both MOFs also showed efficient catalytic transformation of fructose and glucose into the high-value chemical intermediate 5-hydroxymethylfurfural of industrial significance.
Patel, Unnati,Parmar, Bhavesh,Dadhania, Abhishek,Suresh, Eringathodi
supporting information
p. 9181 - 9191
(2021/06/28)

Highly efficient and tunable visible-light-catalytic synthesis of 2,5-diformylfuran using HBr and molecular oxygen
This paper discloses that inexpensive hydrobromic acid (HBr) is active and highly selective to the photo-oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) with dioxygen (O2) or even with water under visible light illumination, which can achieve the highest 89.1% DFF yield in DMSO at 80 °C under pure O2atmosphere. More importantly, under bifunctional acid-photooxidation catalysis of HBr, fructose can be directly converted to DFF and its two-step cascade conversion in DMSO provides a far higher DFF yield (80.2%) than the one-step cascade conversion in MeCN (42.1%). The results of HMF photooxidation catalyzed by hydrohalic acids, free radical quenching tests and EPR spectrum support that the Br atom and superoxide (O2?˙) anion radicals generated by HBr photolysis in O2are active species for the oxidation of HMF to DFF and their activities are adjusted by the reaction medium. This photo-synthetic protocol is very simple and practical, especially with low operating costs, showing a good industrial application prospect.
Fu, Zaihui,Hu, Wenwei,Jiang, Dabo,She, Jialuo,Yang, Bo,Zhang, Huanhuan
p. 23365 - 23373
(2021/07/13)

Assessment of ion exchange resins as catalysts for the direct transformation of fructose into butyl levulinate
The transformation of fructose into butyl levulinate in aqueous 1-butanol (initial molar ratio 1-butanol/fructose 79, and butanol/water 1.19) has been studied in a discontinuous reactor at 80?120 °C and 2.0 MPa over 8 sulfonic polystyrene-DVB ion exchange resins as catalysts (catalyst loading 0.85–3.4 %). Resins swell greatly in the reaction medium and the reaction takes place mainly in the swollen gel-phase. Swollen resins in water have been characterized by analysis of ISEC data, and spaces originated in the gel phase upon swelling are described in terms of zones of different polymer density. A relationship has been found between the morphology of swollen resins and ester production. Swollen resins with low polymer density show the highest butyl levulinate yield. Dowex 50Wx2 was the most effective because it creates the largest and widest spaces in the gel-phase when swelling. Consequently, it better accommodates the proton-transfer-reaction mechanisms.
Ramírez, Eliana,Bringué, Roger,Fité, Carles,Iborra, Montserrat,Tejero, Javier,Cunill, Fidel
(2021/01/25)

Method for preparing 5-hydroxymethylfurfural
The invention discloses a method for preparing 5-hydroxymethylfurfural. The method comprises directly mixing a hexose compound, an ionic liquid and an acid catalyst to obtain a mixture, and vacuumizing in the reaction process to take away water to obtain the 5-hydroxymethylfurfural. According to the method, the HMF is prepared by taking the ionic liquid as a solvent under a mild condition, and due to the fact that the reaction temperature is low, no side reaction occurs basically, and the solution is clear and transparent after the reaction, possibility is provided for catalyzing the reaction through the molecular sieve.
-
Paragraph 0065-0066; 0071-0076; 0081; 0082

(2021/05/26)

Synthesis and characterization of an α-MoO3nanobelt catalyst and its application in one-step conversion of fructose to 2,5-diformylfuran
In this study, α-MoO3nanobelts were successfully synthesized by a simple, green and economic hydrothermal method and applied as a bifunctional catalyst for one-step conversion of fructose to DFF under atmospheric air. The structure of the as-prepared α-MoO3catalyst was characterized in detail by SEM, TEM, EDS, XRD, XPS, H2-TPR and NH3-TPD to better understand the relationship between structure and performance. α-MoO3nanobelts exhibited high catalytic activities for production of DFF from HMF and fructose in atmospheric air. Under optimized reaction conditions, high DFF yields of 97.2% and 78.3% were obtained by using HMF and fructose as raw materials, respectively. Furthermore, a plausible reaction pathway was proposed for the selective oxidation of HMF to DFF according to the experimental and catalyst characterization results. Importantly, α-MoO3is a robust catalyst that can be used at least five times without obvious loss in its catalytic activity. In brief, α-MoO3is an easily-prepared, eco-friendly, low cost and highly effective catalyst which has potential application in one-step conversion of fructose to DFF under atmospheric air.
Cui, Peng,He, Jianbo,He, Yuhan,Yang, Zhenzhen,Zhang, Genlei,Zhu, Bangchong
supporting information
p. 16482 - 16489
(2021/09/28)

Waste Polyethylene?terephthalate Derived Carbon Dots for Separable Production of 5-Hydroxymethylfurfural at Low Temperature
Abstract: Waste Polyethylene terephthalate plastic bottles were used as precursors to fabricate carbon dots (CDs) via air oxidation and sulfuric acid hydrothermal treatment. Owing to the nano-size effect and abundant acidic groups, CDs allowed their application as a novel solid acid for quasi-homogeneous catalytic dehydration of fructose to 5-hydroxymethylfurfural (HMF). Under the optimal condition, an ultra-high yield of HMF was 97.4% along with 100% fructose conversion at low temperature of 50?°C when [BMIM]Cl/ethanol was used as solvent. The CDs catalyst also displayed a prominent recyclability and was used for six recycles without massive loss in catalytic activity. Furthermore, 98.6% of HMF could be obtained from final products. The findings provide a novel sustainable route using recyclable plastics to synthesize carbon dots with a superior catalytic performance for conversion of biomass to important bio-based platform chemicals. Graphic Abstract: [Figure not available: see fulltext.]
Hu, Yaoping,Li, Mingfu,Gao, Zhijin,Wang, Lei,Zhang, Jian
p. 2436 - 2444
(2021/01/04)

Method and system for continuously synthesizing furandicarboxylic acid
The invention discloses a method for continuously synthesizing furandicarboxylic acid. The method comprises the following steps: (1) dissolving sugars into an organic solvent to prepare a sugar solution with the mass concentration of 5 percent to 50 percent; reacting at 60 to 140 DEG C for 0.5 to 12h under the action of a solid acid dehydration catalyst; (2) adding an alkaline water solution and an oxidant into effluent liquid of step (1); reacting for 2 to 12h under the action of a loading type oxidization catalyst and under the conditions of 60 to 110 DEG C and 0.1 to 1MPa; (3) evaporating the effluent liquid of step (2) to remove a solvent; then adding an acidifying agent and adjusting the pH (Potential of Hydrogen) to be less than 2; precipitating to obtain a furandicarboxylic acid crude product; filtering, washing and recrystallizing to obtain the furandicarboxylic acid. The invention further discloses a system for continuously synthesizing the furandicarboxylic acid. According tothe method disclosed by the invention, an intermediate 5-hydroxymethylfurfural does not need to be separated and purified and the furandicarboxylic acid is synthesized in a high-yield manner under moderate conditions; the method can be continuously operated and has an important application prospect.
-
Paragraph 0047-0072

(2021/01/24)

Synthesis of a sulfated-group-riched carbonaceous catalyst and its application in the esterification of succinic acid and fructose dehydration to form HMF
A novel sulfated-group-riched sulfonated carbonaceous catalyst with high acidic strength and adjustable ratio of acidic groups was designed in the paper, where glucose and benzyl chloride were hydrothermally carbonized first followed by sulfonation treatment. Various physicochemical techniques were used to characterize the catalyst such as IR, 13C MAS NMR and XPS spectra, NH3-TPD, XRD patterns and TG curve. Then, it was applied in the esterification of succinic acid and fructose dehydration to form HMF. Compared to commercial Amberlyst-15 catalyst, such carbonaceous solid acid exhibited excellent catalytic activity and thermal stability, which was attributed to its higher amount of sulfonic acid group.
Liu, Huihui,Peng, Qian,Ren, Jiawen,Shi, Bianfang,Wang, Yanqin
p. 2649 - 2656
(2021/04/09)

Preparation and separation method for preparing 5-hydroxymethylfurfural through fructose dehydration
The invention discloses a preparation and separation method for preparing 5-hydroxymethylfurfural through fructose dehydration, which comprises the following steps: mixing fructose, a catalyst and an organic solvent to obtain a raw material solution, and carrying out a dehydration reaction to obtain a 5-hydroxymethylfurfural reaction solution; adding a hydrosulfite/saturated sodium chloride solution into the reaction liquid, and conducting extracting and separating to obtain an alpha-hydroxyl sulfonate water phase; and adjusting the pH value of the alpha-hydroxyl sulfonate water phase to be alkaline, adding an organic extraction agent, and carrying out extraction treatment to obtain the 5-hydroxymethylfurfural. According to the preparation and separation method, high-concentration fructose is taken as a raw material, the 5-hydroxymethylfurfural reaction liquid is prepared at high yield through one-step dehydration reaction, and the highest yield can reach 84.2%; the 5-hydroxymethylfurfural is rapidly separated and purified at room temperature through a subsequent specific separation process, the highest purity can reach 95.1%, and the total yield of the process is 83.4%; and the water phase used in the separation process can be recycled, so that the production cost is further reduced.
-
Paragraph 0049-0053

(2021/08/11)

Facile synthesis and isolation of 5-hydroxymethylfurfural from diphenyl sulfoxide
We report diphenyl sulfoxide (DPhSO) as an active, cheap and environmentally friendly solvent to facilely synthesize 5-hydroxymethylfurfural (HMF) from fructose. It acts as both the catalyst and solvent to afford nearly 100% conversion of fructose and 68.4% yield of HMF. In particular, HMF was easily extracted using water and DPhSO froze into an insoluble solid at low temperature. DPhSO was reused 6 times without significant loss of activity. The reaction mechanism of DPhSO-catalyzed HMF formation was analyzed by NMR and ESI-MS experiments and theoretical calculations.
Gao, Zhijin,Hu, Yaoping,Huai, Liyuan,Zhang, Jian,Zhang, Tongtong
supporting information
p. 3241 - 3245
(2021/05/21)

Method for synthesizing 5-hydroxymethylfurfural
The invention relates to the field of synthesis of 5-hydroxymethylfurfural, and discloses a method for synthesizing 5-hydroxymethylfurfural. The method comprises the step of in the presence of an ionic liquid as shown in a formula (I) defined in the description, carrying out dehydration reaction on a sugar source to obtain 5-hydroxymethylfurfural. According to the technical scheme, the problems that a conventional acid catalyst is complex in follow-up treatment, serious in equipment corrosion, large in industrial wastewater discharge and the like are solved, the used catalyst shows good heat-resistant stability and efficient catalytic activity (the maximum mass yield can reach 61%) in the reaction for preparing 5-HMF, the reaction condition is mild at the same time, the pollution of an acid catalyst to the environment and the corrosion of the acid catalyst to equipment are overcome, the production process is simplified, and the production cost is saved.
-
Paragraph 0047-0066

(2021/06/06)

HMF PREPARATION CATALYSED BY ANOLYTE FRACTION
The present invention relates to a method for the production of 5-hydroxymethylfurfural (HMF), which converts a fructose-containing component using a catalytically active anolyte fraction, which has been produced by electrolysis of water, at a temperature of 90 to 200° C. and for obtaining an HMF-containing product mixture, wherein advantageously a high HMF selectivity is achieved with significantly lower by-product formation.
-
Page/Page column 12-15

(2021/07/17)

Method For Manufacturing 2,5-Furan dicarboxylic acid using 5-Acetoxymethyl-2-furaldehyde
The present invention relates to a method for producing fructose acetoxymethyl 5 - furfuraldehyde (5-2 -2-acetoxymethyl, furaldehyde) using an intermediate produced through a dehydration reaction of fructosins (AMF). And/or) of 5 - acetoxymethyl -2 - furfuraldehyde (AMF) to prepare 2, 5 - furandicarboxylic acid (2, 5-Furan dicarboxylic acid, FDCA). A method for preparing 5 -furandicarboxylic acid (-2 -) using AMF acetoxymethyl 2, 5 - furfuraldehyde (FDCA) is provided.
-
Paragraph 0090-0092; 0097; 0106; 0110; 0117

(2021/07/01)

Enhanced conversion of α-cellulose to 5-HMF in aqueous biphasic system catalyzed by FeCl3-CuCl2
This study was to investigate the optimal additions of the cellulose decomposition reaction to obtain the most yield of 5-HMF and other furan derivatives in various biphasic systems with FeCl3-CuCl2 mixed catalysts, and explore its depolymerization kinetics. A series of controllable reactions have been performed under mild environmentally friendly atmosphere. The experiment results showed that 49.13 wt% of 5-HMF was the maximum production along with 2.98 wt% other furan derivatives catalyzed by mixed Lewis acid FeCl3-CuCl2 under the two phases which included high concentration NaCl aqueous phase and n-butanol organic phase at 190 °C for 45 min. The conclusion suggested that two-phase systems benefited the yield of 5-HMF, furan derivatives via extracting the target products from reaction phase to organic phase to avoid rehydration of 5-HMF. The kinetic calculation revealed the conversion with mixed catalysts had lower reaction apparent activation energy (21.65 kJ/mol, 190-230 °C) and the reaction rate was faster than that with acid-based catalysts. Based on experiment exploration, the probable mechanism of cellulose decomposition with FeCl3-CuCl2 was proposed.
Zhang, Lilin,Tian, Yinbing,Wang, Yuanyuan,Dai, Liyi
p. 2233 - 2238
(2021/03/22)

Cellulose conversion to biofuel precursors using conjugated ionic liquid catalyst: An experimental and DFT study?
In this study, an efficient catalytic system has been developed for the single step conversion of microcrystalline cellulose into 5-hydroxymethyl furfural and levulinic acid using Br?nsted acidic ionic liquid (IL) catalysts which have large conjugated structure. The IL catalysts used in this study comprising of different anions ([CF3SO3]?, [HSO4]?, [CF3COO]?, and [Cl]?) with a common cation 1-butyl sulfonic acid-2-phenylimidazolinium ([2-PhIm-SO3H]+), were synthesized in laboratory and characterized. The MCC conversion was carried out in a biphasic reaction medium and yields of 70 % for 5-HMF and 23 % for LA were achieved at 150 °C and 5 h reaction time. Furthermore, density functional theory (DFT) was performed to identify the key interactions in the stable configurations of the ion-pairs of ILs. The electronic properties and chemical reactivity of the individual ions and ion-pairs of ILs were investigated by performing natural bond orbital (NBO) and second order perturbation theory analysis.
Kashyap, Hemant K.,Khatri, Vikas,Kumar, Komal,Upadhyayula, Sreedevi
(2020/12/21)

PREPARATION OF HMF CATALYZED BY A MIXTURE OF SALT AND ACID
The present invention relates to a method for the production of 5-hydroxymethylfurfural (HMF), which converts a fructose-containing component using a catalyst system comprising a solution of a salt and acid mixture at a temperature of 90 to 200° C. and leads to obtaining an HMF-containing product mixture, wherein advantageously a high HMF selectivity with significantly lower by-product formation is achieved at the same time.
-
Paragraph 0174-0194

(2021/07/17)

Efficient and chemoselective hydrogenation of aldehydes catalyzed by well-defined PN3-pincer manganese(ii) catalyst precursors: An application in furfural conversion
Well-defined and air-stable PN3-pincer manganese(ii) complexes were synthesized and used for the hydrogenation of aldehydes into alcohols under mild conditions using MeOH as a solvent. This protocol is applicable for a wide range of aldehydes containing various functional groups. Importantly, α,β-unsaturated aldehydes, including ynals, are hydrogenated with the CC double bond/CC triple bond intact. Our methodology was demonstrated for the conversion of biomass derived feedstocks such as furfural and 5-formylfurfural to furfuryl alcohol and 5-(hydroxymethyl)furfuryl alcohol respectively.
Gholap, Sandeep Suryabhan,Dakhil, Abdullah Al,Chakraborty, Priyanka,Li, Huaifeng,Dutta, Indranil,Das, Pradip K.,Huang, Kuo-Wei
supporting information
p. 11815 - 11818
(2021/11/30)

Chemical Properties

Appearance/Colour :Beige coloured crystalline solid
Melting Point: 30-34 °C
Boiling Point: 291.5 °C at 760 mmHg
Flash Point:79.4 °C
Density: 1.29 g/cm³
Solubility:Chloroform (Slightly), Ethyl Acetate (Slightly), Methanol (Slightly)
Storage Temp.:2-8°C
Vapor Pressure: 0.000891mmHg at 25°C
Refractive Index: n20/D 1.562(lit.)
PKA: 12.82±0.10(Predicted)
Sensitive: Air & Light Sensitive
Merck: 14,4832
BRN: 110889
PSA: 50.44000
LogP: 0.58440

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Chemical Properties

Appearance/Colour :Beige coloured crystalline solid

Melting Point: 30-34 °C

Boiling Point: 291.5 °C at 760 mmHg

Flash Point:79.4 °C

Density: 1.29 g/cm³

Solubility:Chloroform (Slightly), Ethyl Acetate (Slightly), Methanol (Slightly)

Storage Temp.:2-8°C

Vapor Pressure: 0.000891mmHg at 25°C

Refractive Index: n20/D 1.562(lit.)

PKA: 12.82±0.10(Predicted)

Sensitive: Air & Light Sensitive

Merck: 14,4832

BRN: 110889

PSA: 50.44000

LogP: 0.58440

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67-47-0

Articles about 67-47-0Total 834 be found

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Chemical Properties

Appearance/Colour :Beige coloured crystalline solid

Melting Point: 30-34 °C

Boiling Point: 291.5 °C at 760 mmHg

Flash Point:79.4 °C

Density: 1.29 g/cm3

Solubility:Chloroform (Slightly), Ethyl Acetate (Slightly), Methanol (Slightly)

Storage Temp.:2-8°C

Vapor Pressure: 0.000891mmHg at 25°C

Refractive Index: n20/D 1.562(lit.)

PKA: 12.82±0.10(Predicted)

Sensitive: Air & Light Sensitive

Merck: 14,4832

BRN: 110889

PSA: 50.44000

LogP: 0.58440

Global suppliers and manufacturers of 67-47-0total 210 suppliers on LookChem

Density: 1.29 g/cm³