67-47-0Relevant articles and documents
Synthesis of hydroxymethylfurfural from sucrose using Br?nsted-Lewis acidic ionic liquid
Yao, Lin,Liu, Shiwei,Li, Lu,Yu, Shitao,Liu, Fusheng,Song, Zhanqian
, p. 283 - 288 (2016)
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.
Efficient catalytic system for the selective production of 5-hydroxymethylfurfural from glucose and fructose
Yong, Gen,Zhang, Yugen,Ying, Jackie Y.
, p. 9345 - 9348 (2008)
(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.
A selective and economic carbon catalyst from waste for aqueous conversion of fructose into 5-hydroxymethylfurfural
Deng, Tiansheng,Li, Jiangong,Yang, Qiqi,Yang, Yongxing,Lv, Guangqiang,Yao, Ying,Qin, Limin,Zhao, Xianlong,Cui, Xiaojing,Hou, Xianglin
, p. 30160 - 30165 (2016)
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.
Levulinic Acid as a Catalyst for the Production of 5-Hydroxymethylfurfural and Furfural from Lignocellulose Biomass
Seemala, Bhogeswararao,Haritos, Victoria,Tanksale, Akshat
, p. 640 - 647 (2016)
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.
Conversion of carbohydrates into 5-hydroxymethylfurfural in an advanced single-phase reaction system consisting of water and 1,2-dimethoxyethane
Wang, Shurong,Lin, Haizhou,Chen, Jingping,Zhao, Yuan,Ru, Bin,Qiu, Kunzan,Zhou, Jinsong
, p. 84014 - 84021 (2015)
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.
Efficient catalytic conversion of the fructose into 5-hydroxymethylfurfural by heteropolyacids in the ionic liquid of 1-butyl-3-methyl imidazolium chloride
Xiao, Yaping,Song, Yu-Fei
, p. 74 - 78 (2014)
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.
Supported ionic liquid silica nanoparticles (SILnPs) as an efficient and recyclable heterogeneous catalyst for the dehydration of fructose to 5-hydroxymethylfurfural
Sidhpuria, Kalpesh B.,Daniel-Da-Silva, Ana L.,Trindade, Tito,Coutinho, Joao A. P.
, p. 340 - 349 (2011)
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.
Niobium phosphotungstates: Excellent solid acid catalysts for the dehydration of fructose to 5-hydroxymethylfurfural under mild conditions
Qiu, Guo,Wang, Xincheng,Huang, Chongpin,Li, Yingxia,Chen, Biaohua
, p. 32423 - 32433 (2018)
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.
Chromium halides mediated production of hydroxymethylfurfural from starch-rich acorn biomass in an acidic ionic liquid
Lee, Jin-Woo,Ha, Myoung-Gyu,Yi, Young-Byung,Chung, Chung-Han
, p. 177 - 182 (2011)
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.
One-pot formation of furfural from xylose via isomerization and successive dehydration reactions over heterogeneous acid and base catalysts
Takagaki, Atsushi,Ohara, Mika,Nishimura, Shun,Ebitani, Kohki
, p. 838 - 840 (2010)
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.
Conversion of highly concentrated fructose into 5-hydroxymethylfurfural by acid-base bifunctional HPA nanocatalysts induced by choline chloride
Zhao, Qian,Sun, Zhong,Wang, Shengtian,Huang, Guohui,Wang, Xiaohong,Jiang, Zijiang
, p. 63055 - 63061 (2014)
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.
Bifunctional Imidazole-Benzenesulfonic Acid Deep Eutectic Solvent for Fructose Dehydration to 5-Hydroxymethylfurfural
Ruan, Chencong,Mo, Fan,Qin, Hao,Cheng, Hongye,Chen, Lifang,Qi, Zhiwen
, p. 445 - 453 (2021)
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.]
Sulfonated lignin-derived ordered mesoporous carbon with highly selective and recyclable catalysis for the conversion of fructose into 5-hydroxymethylfurfural
Gan, Linhuo,Lyu, Li,Shen, Tianruo,Wang, Shuai
, p. 132 - 143 (2019)
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.
One-pot synthesis of 5-hydroxymethylfurfural from carbohydrates using an inexpensive FePO4 catalyst
Yang, Li,Yan, Xiaopei,Xu, Siquan,Chen, Hao,Xia, Haian,Zuo, Songlin
, p. 19900 - 19906 (2015)
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
Simultaneous dehydration of biomass-derived sugars to 5-hydroxymethyl furfural (HMF) and reduction of graphene oxide in ethyl lactate: One pot dual chemistry
Mondal, Dibyendu,Chaudhary, Jai Prakash,Sharma, Mukesh,Prasad, Kamalesh
, p. 29834 - 29839 (2014)
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.
Coupling Continuous Flow Microreactors to MicroNIR Spectroscopy: Ultracompact Device for Facile In-Line Reaction Monitoring
Galaverna, Renan,Ribessi, Rafael L.,Rohwedder, Jarbas J. R.,Pastre, Julio C.
, p. 780 - 788 (2018)
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.
Mesoporous porphyrin-silica nanocomposite as solid acid catalyst for high yield synthesis of HMF in water
Bhaumik, Asim,Mankar, Akshay R.,Modak, Arindam,Pant, Kamal Kishore
, (2021)
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.
A novel microwave-assisted hydrothermal route for the synthesis of ZnxTPA/γ-Al2O3 for conversion of carbohydrates into 5-hydroxymethylfurfural
Parameswaram,Roy, Sounak
, p. 28461 - 28471 (2018)
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.
Efficient and selective conversion of hexose to 5-hydroxymethylfurfural with tin-zirconium-containing heterogeneous catalysts
Wang, Yanhua,Tong, Xinli,Yan, Yongtao,Xue, Song,Zhang, Yangyang
, p. 38 - 43 (2014)
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.
Conversion of fructose, glucose, and cellulose to 5-hydroxymethylfurfural by alkaline earth phosphate catalysts in hot compressed water
Daorattanachai, Pornlada,Khemthong, Pongtanawat,Viriya-Empikul, Nawin,Laosiripojana, Navadol,Faungnawakij, Kajornsak
, p. 58 - 61 (2012)
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%).
Conversion of hexose into 5-hydroxymethylfurfural in imidazolium ionic liquids with and without a catalyst
Cao, Quan,Guo, Xingcui,Yao, Shengxi,Guan, Jing,Wang, Xiaoyan,Mu, Xindong,Zhang, Dongke
, p. 956 - 959 (2011)
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.
Fermentable sugars by chemical hydrolysis of biomass
Binder, Joseph B.,Raines, Ronald T.
, p. 4516 - 4521 (2010)
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.
A catalytic system for the selective conversion of cellulose to 5-hydroxymethylfurfural under mild conditions
Galkin,Krivodaeva,Ananikov
, p. 2954 - 2957 (2015)
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.
Functional networks of organic and coordination polymers: Catalysis of fructose conversion
Bromberg, Lev,Su, Xiao,Hatton, T. Alan
, p. 6257 - 6264 (2014)
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.
Production of 5-hydroxymethylfurfural in ionic liquids under high fructose concentration conditions
Li, Changzhi,Zhao, Zongbao K.,Wang, Aiqin,Zheng, Mingyuan,Zhang, Tao
, p. 1846 - 1850 (2010)
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.
Polystyrene immobilized Br?nsted acid ionic liquid as an efficient and recyclable catalyst for the synthesis of 5-hydroxymethylfurfural from fructose
Momenbeik, Fariborz,Nasrollahzadeh, Mahmoud,Nezafat, Zahra,Orooji, Yasin
, (2021/10/26)
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.
Ethanolysis of selected catalysis by functionalized acidic ionic liquids: An unexpected effect of ILs structural functionalization on selectivity phenomena
Nowakowska-Bogdan, Ewa,Nowicki, Janusz
, p. 1857 - 1866 (2022/02/05)
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
Catalytic wet air oxidation of D-glucose by perovskite type oxides (Fe, Co, Mn) for the synthesis of value-added chemicals
Geobaldo, Francesco,Pirone, Raffaele,Russo, Nunzio,Scelfo, Simone
, (2022/03/15)
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
