Biomass into Chemicals: Conversion of Sugars to Furan Derivatives by Catalytic Processes PDF

Applied Catalysis A: General 385 (2010) 1–13 Contents lists available at ScienceDirect Applied Ca...

Applied Catalysis A: General Review Biomass into chemicals: Conversion of sugars to furan derivatives processes Xinli Tong, Yang Ma, Yongdan Li ∗ Tianjin Key Laboratory of Catalysis Science and Technology Tianjin University, Tianjin 300072, China a r t i c l e i n f o Article history: Received 6 March 2010 Received in revised form 26 June 2010 Accepted 28 June 2010 Available online 30 July 2010 Keywords: Sugar Furan derivatives Catalysis 5-Hydroxymethylfurfural Biomass transformation Contents 1. Introduction............................................ 2. Synthesis of 5-hydroxymethylfurfural.................... 2.1. Mineral and organic acid catalysts............... 2.1.1. Production of 5-hydroxymethylfurfural 2.1.2. Production of 5-hydroxymethylfurfural 2.1.3. Production of 5-hydroxymethylfurfural 2.2. Solid acid catalysts............................. 2.2.1. Production of 5-hydroxymethylfurfural 2.2.2. Production of 5-hydroxymethylfurfural 2.3. Metal-containing catalysts....................... 2.4. Other catalytic systems.......................... 2.5. Mechanism of hexoses dehydration................. 3. Synthesis of 5-hydroxymethylfurfural-based furan 3.1. Synthesis of 2,5-diformylfuran................... 3.2. Synthesis of 2,5-furandicarboxylic acid.......... 3.3. Synthesis of 2,5-bis(hydroxymethyl)furan 4. Conclusion and perspectives............................. Acknowledgements........................................ References.............................................. ∗ Corresponding author. Tel.: +86 022 27405613; fax: E-mail address: [email protected] (Y. Li). All rights reserved. et al. / Applied Catalysis A: General 385 (2010) 1–13 structures of the representative hexoses and furans. widely used component in various polyesters such as polyethylene terephthalate (PET) and polybutyleneterephthalate (PBT) [34,35]. 2,5-FDCA can also serve as a starting material for the production of succinic acid, which is consumed at present in a fairly large scale. Thus, 2,5-FDCA has been identiﬁed as one of the 12 building block compounds that can be produced from sugars via biological or chemical processes. Meanwhile, 2,5-DFF has also numer- ous applications, including those as monomers in the synthesis of special polymers [37–39], as intermediates of pharmaceuticals and as antifungal agents. It is also used in the prepara- tion of macrocyclic ligands [42,43] and as a cross-linking agent for poly(vinyl alcohol). Furthermore, 2,5-BHF and 2,5-DMF are produced from the partial or deep hydrogenation of HMF, respec- tively, and can also be generated in the one-pot dehydration and hydrogenation of hexoses. 2,5-DMF is a very promising liquid fuel in the future, with a high energy density, 31.5 MJ/L, which is similar to that of gasoline (35.0 MJ/L), and is 40% higher than that of ethanol (23.0 MJ/L) [45,46]. Moreover, 2,5-DMF (bp 92–94 ◦ C) is less volatile than ethanol (bp 78 ◦ C) and is immiscible with water, so that it is especially suitable to be used as a transportation fuel. In 2007, Corma et al. and Dumesic and coworkers have reviewed the chemical routes for the transformation of biomass into chemicals and fuels, respectively. Considering the rapid progress on the catalytic conversion of biomass, this review concentrates mainly on describing the state-of-the-art and the works reported within the recent few years. In this review, the syn- thesis methods of 5-HMF, 2,5-FDCA, 2,5-DFF, 2,5-BHF and 2,5-DMF from carbohydrates with suitable catalyst systems are discussed in detail. For the production of 5-HMF, various acids, sometimes with the presence of metal ions, are used as catalysts. For the manufac- ture of 2,5-FDCA, there are two routes. One is the direct oxidation of 5-HMF by a suitable oxidant. The other is the one-pot dehydration and oxidation of hexoses, requiring a multi-functional catalyst. 2,5- DFF has been prepared through a partial oxidation of 5-HMF with the function of a catalyst such as Pd/C, V2 O5 /TiO2 or metal/bromine. 2,5-BHF and 2,5-DMF have been synthesized from selective hydro- genation of 5-HMF, which is originally formed from hexoses in a special media or a biphasic reactor. formed from 2. Synthesis of 5-hydroxymethylfurfural From the commercial point of view, 5-HMF is a versatile and multi-functional compound. It is a good starting point for the syn- thesis of precursors of pharmaceuticals, thermoresistant polymers, and macrocyclic compounds, and particularly for the synthesis of dialdehydes, ethers, amino alcohols, and other organic interme- diates. These may lead to the possibility of numerous chemical X. Tong et al. / Applied Catalysis A: General 385 (2010) 1–13 3 sis of 5-HMF can be suppressed. However, the cross-polymerization reactions occur under all circumstances, which lead to the produc- tion of colored soluble polymers and insoluble brown humins. In order to prevent the side reactions and obtain a high yield of 5-HMF, one can design and employ a suitable catalyst tuned to the formation of 5-HMF, while not promoting the consecutive reac- tions or alternatively the continuous removal of 5-HMF from the reaction mixture. The production of 5-HMF and the kinetic studies of the dehy- dration reaction had been reviewed by Kuster in 1990 and Lewkowski in 2001. The following sections emphasize the recent research developments and summarize the efﬁcient catalyst system for the synthesis of 5-HMF. The catalysts used are generally classiﬁed as mineral acid, organic acid and solid acid catalysts, and metal-containing catalysts. of oxalic 2.1. Mineral and organic acid catalysts 2.1.1. Production of 5-hydroxymethylfurfural from fructose The dehydration of d-fructose can generally be catalyzed by a protonic acid as well as by a Lewis acid [61,62]. From the ﬁrst oxalic acid-catalyzed synthesis of 5-HMF, nearly one hundred inorganic and organic acidic compounds have been positively identiﬁed as catalysts for the synthesis of 5-HMF. The most commonly used inexpensive acids have been H2 SO4 , H3 PO4 and hydrochloric acid (HCl) [63–65]. Moreover, hydroiodic acid (HI) has also been found to exhibit catalytic action in the iodine-catalyzed dehydration of hex- oses. The reported organic acids also include the oxalic acid, levulinic acid, and p-toluenesulfonic acid [56,67–70]. Antal et al. [60,71] reported the dehydration of d-fructose with H2 SO4 as a catalyst in sub-critical water at 250 ◦ C, and gained a yield of 5-HMF as high as 53%. Bicker et al. investigated the synthesis of 5-HMF in the presence of H2 SO4 when sub-critical or supercritical acetone–water mixture was employed as a reac- tion medium. It was found that the carbon atom efﬁciency is quite good and that no solid impurities are formed. In the supercriti- cal acetone–water mixture, the maximum yield of 5-HMF reached 78% at 180 ◦ C. Recently, a two-phase reactor system with HCl as the catalyst was reported by Roman-Leshkov et al.. As shown in Fig. 2, d-fructose is dehydrated to 5-HMF in the aqueous phase with HCl as a catalyst. In this process, dimethylsulfoxide (DMSO) countercurrent extraction and evaporation steps (The aqueous phase contains fructose, DMSO, PVP, and this ﬁgure is modiﬁed and taken from Ref. with permission of the American Association for the Advancement X. Tong et al. / Applied Catalysis A: General 385 (2010) 1–13 with typical solid acid catalysts. T (◦ C) Time (min) Conv. (%) 5-HMF yield (%) Ref. 165 60 76.0 69.2 50 60 50.2 41.9 100 120 61.4 21.6 100 30 44.4 44.3 80 180 – 52 150 15 95.1 73.4 150 10 96.4 82.1 200 5 83.6 38.1 100 180 >99 73 100 180 57 21 2.1.3. Production of 5-hydroxymethylfurfural from polysaccharides and biomass feedstocks Employing polysaccharides, cellulose and lignocellulose directly as feedstocks for the production of 5-HMF is more promising com- mercially. Recently, Chheda et al. got good selectivities for 5-HMF at high conversions from polysaccharides such as sucrose, starch, cellobiose and xylan using a mineral acid (HCl, H2 SO4 or H3 PO4 ) as a catalyst in a biphasic reactor. The reactor system com- posed of a reactive aqueous phase modiﬁed with DMSO and an organic extracting phase consisting of a 7: 3 (w/w) MIBK–2-butanol mixture. Moreover, Ilgen et al. reported that 25 and 57% yields of 5-HMF are obtained respectively from inulin and sucrose using p-toluenesulfonic acid as catalyst in a melt system consisting of choline chloride (ChCl) and up to 50 wt.% of carbohydrates. Remark- ably, Binder and Raines found that N,N-dimethylacetamide (DMAc) containing alkali metal halide is a privileged solvent that enables the synthesis of 5-HMF from lignocellulosic biomass, as well as from cellulose, glucose, and fructose, with the mineral acid as the catalyst. For instance, a 92% yield of 5-HMF was obtained from lignocellulosic biomass using 6.0 mol% H2 SO4 as the catalyst in DMAc-KI solvent at 100 ◦ C for 5 h. 2.2. Solid acid catalysts obtained Solid acid catalysts have several advantages over liquid acid catalysts: (a) they facilitate the separation of product and can be recycled; (b) they can work at high temperatures, thus shorten- ing the reaction time and favoring the formation of 5-HMF instead of its decomposition during a prolonged reaction period; (c) they are capable of adjusting the surface acidity to improve the selec- tivity of 5-HMF, which will be very useful to the conversion of polysaccharides and biomass feedstocks. In the dehydration of car- bohydrates, the reported solid acid catalysts generally included H-form zeolites, ion-exchange resins, vanadyl phosphate, and ZrO2. DMSO) 2.2.1. Production of 5-hydroxymethylfurfural from fructose The reaction results of d-fructose dehydration are summarized in Table 1. Moreau et al. [79,80] studied the dehydration of d-fructose in the presence of the dealuminated H-form mordenite at 165 ◦ C in a solvent consisting of water and MIBK. A d-fructose conversion of 76% and a 5-HMF selectivity of 92% were achieved at the same time. In addition, the conversion of d-fructose and the selectivity of 5-HMF are found to be related to the kind of acid and the struc- tural properties of the acid, as well as to its micropore vs. mesopore volume distribution. The maximum reaction rate of d-fructose was observed on the H-mordenite with a Si/A1 ratio of 11, and a sig- niﬁcant increase (ca. 10%) of the selectivity of 5-HMF was obtained by the simultaneous extraction of 5-HMF with MIBK circulating et al. / Applied Catalysis A: General 385 (2010) 1–13 5 butyl-3-methyl imidazolium tetraﬂuoroborate ([BMIM]BF4 ) and a hydrophobic 1-butyl-3-methyl imidazolium hexaﬂuorophosphate ([BMIM]PF6 ). The yield of 5-HMF was 52% after 3 h reaction with [BMIM]BF4 as solvent. Moreover, the ionic liquid allows the reac- tion to proceed more rapidly than in DMSO and the reaction achieves a yield of 5-HMF close to 80% in [BMIM]PF6 solvent. Ilgen et al. reported that a 40% yield of 5-HMF was obtained using Amberlyst-15 as catalyst in the choline chloride (ChCl)/d-fructose system. Furthermore, the effect of co-solvents such as acetone, DMSO, ethanol, methanol, ethyl acetate, and supercritical CO2 in the Amberlyst-15 resin/ionic liquid system was investigated in detail at room temperature. Recently, Qi et al. used an acetone–water reaction medium and got a yield of 5-HMF as high as 73.4% with a 94.0% d-fructose conversion by microwave heating at 150 ◦ C with the presence of a cationic exchange resin (Dowex 50wx8-100) catalyst. Moreover, the catalytic activity and selectiv- ity after reuse of the resin ﬁve times remained nearly unchanged. They also found that the addition of acetone to DMSO solvent fur- ther improved the formation of 5-HMF from d-fructose. Watanabe and coworkers [103,104] examined the production of 5-HMF from d-fructose catalyzed by TiO2 and ZrO2 under microwave irradiation. In the case of TiO2 , the yield of 5-HMF reached 38.1% with a d-fructose conversion of 83.6% at 200 ◦ C after 5 min. Moreover, a 30.5% 5-HMF yield and 65% d-fructose conversion were obtained in the presence of ZrO2 after 5 min. Fur- thermore, Shimizu et al. found that water removal from the reaction mixture by a mild evacuation at 0.97 × 105 Pa increases the yield of 5-HMF for the system with several solid catalysts (heteropoly acid, zeolite, and acidic resin). Also, it was interest- ing to note that the crushed and sieved Amberlyst-15 powder in a size of 0.15–0.053 mm shows 100% 5-HMF yield at high fruc- tose concentration (50 wt.% in DMSO), which may be due to an improved removal of adsorbed water in the small-sized resin par- ticles. resin was 2.2.2. Production of 5-hydroxymethylfurfural from glucose, polysaccharides and biomass feedstocks Based on the isomerization of glucose and the successive dehy- dration of fructose into 5-HMF over solid acid catalyst, Takagaki et al. found that 42–54% yield of 5-HMF can be produced from glucose and sucrose by a simple one-pot synthesis using a combination of Amberlyst-15 and Mg–Al hydrotalcite (HT) as cat- alyst in N,N-dimethylformamide at 100 ◦ C. Moreover, in the TiO2 and ZrO2 catalyzed conversion of glucose to 5-HMF, TPD measure- ment results and experimental data showed that the amount of the basic sites was the key factor for the isomerization, while the strength of the acidity and basicity was important for the 5-HMF formation from glucose [103,104]. Lourvanij and Rorrer found that the molecular sieves, i.e. HY zeolite, aluminum-pillared mont- morillonite, MCM-20 and MCM-41, also promote the dehydration of glucose; however, formic acid or 4-oxopentanoic acid is easily formed in those processes. Very recently, Hu and coworkers reported that a 47.6% yield of 5-HMF was obtained within 4 h at 403 K over a SO4 2− /ZrO2 –Al2 O3 catalyst with a Zr–Al mole ratio of 1:1. It was also found that the solid acid catalyst with higher acid- ity and moderate basicity was more favorable for the formation of 5-HMF from glucose. Carlini et al. found that a 27 or 31% yield of 5-HMF was obtained from 12.7 wt.% sucrose or 6.0 wt.% inulin with niobium phosphate as catalyst in aqueous medium. Chheda and Dumesic investigated the conversion of inulin and sucrose to 5-HMF in the presence of the Diaion® PK-216 resin; and 69 and 43% yields of HMF were respectively obtained in the biphasic system by adding a certain amount of NMP into aqueous phase (H2 O:NMP = 4:6, w/w). Moreover, with highly concentrated melt systems consisting of ChCl and up to 50 wt.% of carbohydrates, 9, 27 and 54% yields X. Tong et al. / Applied Catalysis A: General 385 (2010) 1–13 (B) in [EMIM]+ Cl− with the presence of MClx catalyst (Reprinted from Ref. with permission of the American Science Publishing). good catalysts for the conversion of glucose to 5-HMF in alkylimi- dazolium chlorides. They postulated that the reaction mechanism on the lanthanides is different from that on the chromium catalysts. Recently, Ilgen et al. obtained 60, 31, 43 and 46% yields of 5- HMF respectively from fructose, glucose, sucrose and inulin using CrCl3 as catalyst in a system consisting of ChCl and up to 50 wt.% of elements carbohydrates. Moreover, a single-step conversion of cellulose to 5-HMF has successfully been performed with a pair of metal chlo- rides (CuCl2 and CrCl2 ) as the catalyst in [EMIM]Cl solvent, and a 55.4 ± 4.0% yield of 5-HMF was obtained. Especially, Zhang et to 5-HMF al. achieved an 89% conversion of cellulose for the production of 5-HMF in the presence of CrCl2 in the [EMIM]Cl–water mixture. and the arc- 2.4. Other catalytic systems revealed that Mednick [121,122] used ammonium phosphate, triethylamine phosphate and pyridinium phosphate for the synthesis of 5-HMF. The highest 5-HMF yield reached 44% in the presence of pyri- dinium phosphate. Fayet and Gelas employed pyridinium triﬂuoroacetate, hydrochloride, hydrobromide, perbromate and p- toluenesulfonate as catalysts for d-fructose dehydration, and a yield close to 70% for 5-HMF was obtained after 30 min at 120 ◦ C. More- over, Smith patented the use of ammonium sulfate or sulﬁte as the catalyst in d-fructose dehydration. A 50% high yield of 5-HMF was obtained at 170 ◦ C and after 12 s with NH4 Al(SO4 )2 as a catalyst 70%. In addition, it was also reported that the yield and selectivity of 5-HMF can be improved with activated carbon as adsorbent in acid-catalyzed dehydration of d-fructose. Nowadays, green chemistry is getting more and more asso- ciated with catalytic processes [127,128]. The ionic liquids as solvents or catalysts have received great attention due to their stability, low vapor pressure and recyclability [129–133]. The merit of ionic liquids as solvents has been mentioned in the dehydration of sugars in the presence of acidic resin and metal chlorides [99,114–117]. Herein, we mainly discuss the reaction systems for the dehydration of hexoses with ionic liquids as cat- alysts. The pyridinium-based ionic liquids were ﬁrstly proved to be efﬁcient for the dehydration of d-fructose. Moreau et al. investigated the dehydration of d-fructose at 90 ◦ C using 1-H-3-methyl imidazolium chloride ([HMIM]+ Cl− ) acting as solvent and catalyst. As a result, a 92% yield of 5-HMF was obtained after 15–45 min. Furthermore, Bao et al. reported the preparation of 5-HMF by the dehydration of d-fructose in the presence of the ionic liquids, 3-allyl-1-(4-sulfobutyl)imidazolium triﬂuoromethanesulfonate ([ASBI][Tf]), as well as its Lewis acid derivative, 3-allyl-1-(4-sulfurylchloride butyl)imidazolium triﬂu- et al. / Applied Catalysis A: General 385 (2010) 1–13 7 possible mechanism for the dehydration of hexoses. 2.5. Mechanism of hexoses dehydration Haworth and Jones proposed the ﬁrst mechanism for the dehydration of fructose to 5-HMF. In the following works, van Dam et al. , Kuster and Antal et al. assumed that the dehy- dration of hexoses goes through one of the two possible pathways: one includes the transformation of ring structures, while the other path is based on the acyclic compounds (Fig. 4). In general, the reaction pathways for the production of 5-HMF from hexoses are composed of isomerization, dehydration, fragmentation, reversion, and condensation steps. Several works have suggested that 5-HMF formation takes place through an open-chain 1, 2-enediol mech- anism or through a fructofuranosyl intermediate [80,144,145]. However, Antal et al. and Newth proposed that the for- mation of 5-HMF from d-fructose proceeds via cyclic intermediates. They gave the evidence as: (1) facile conversion of 2,5-anhydro-d- mannose (an intermediate enol in cyclic mechanism) to HMF; (2) facile formation of 5-HMF from d-fructose but difﬁcult from glu- cose, which could be concluded from the dehydration of sucrose; (3) lack of carbon–deuterium bond formation in 5-HMF due to keto- enol tautomerism in the open-chain mechanism when the reaction was carried out in D2 O solvent. Furthermore, Amarasekara et al. identiﬁed two key intermediates as (4R, 5R)-4-hydroxy-5- hydroxymethyl-4,5-dihydrofuran-2-carbaldehyde in the reaction based on the data of 1 H and 13 C NMR spectra. In the dehydration of glucose catalyzed by metal halide, the mutarotation and isomerization steps are necessary [114,117]. Fig. 5 presents the mutarotation leading to interconversion of ␣- and ␤-glucopyranose anomers and the isomerization of glucopy- ranose to fructofuranose, in which the mutarotation leading to an equilibrium mixture of anomers is rapid in the presence of a catalytic amount of CrCl2. It promotes the isomerization of glucopy- ranose to fructofuranose, and the further dehydration to 5-HMF. Similarly, the results from theoretical simulations solidiﬁed the conclusion that cyclic reaction pathways are dominant during the formation of 5-HMF from glucose. Very recently, the research of Pidko et al. showed that, in the presence of CrCl2 , the facile reactions of sugar ring opening and closure involve coordination to a single Cr center. The rate-controlling H-shift reaction can be facilitated by the transient self-organization of the Lewis acidic Cr2+ centers into a binuclear complex with the open form of glu- X. Tong et al. / Applied Catalysis A: General 385 (2010) 1–13 glucose in [EMIM]Cl (Reprinted from Ref. with permission of the American Association for the Advancement of omy and sustainability, the catalytic routes for 2,5-DFF production are promising in the future. In the early works, hydrogen peroxide was used as the oxidant and the synthetic titanium silicalite (TS1) was used as a recyclable catalyst. However, the oxidation of 5-HMF over TS1 cata- lyst with 30 wt.% aqueous hydrogen peroxide solution in methanol or water was unsatisfactory because the maximum yield for 2,5- DFF obtained was only 25%. Moreover, chloroperoxidase-catalyzed oxidation of 5-HMF with hydrogen peroxide as the oxidant was also investigated , and it was found that the reaction pro- ceeded with 60–74% selectivity for 2,5-DFF. Moreau and coworkers [158,159] investigated the oxidation of 5-HMF into 2,5-DFF with a supported V2 O5 /TiO2 catalyst using air as the oxidant and toluene or MIBK as solvent and found that the catalyst can be regenerated in situ. The complete transformation of 5-HMF and a yield of 2,5- DFF as high as 90% are achieved with a monolayered V2 O5 /TiO2 at 90 ◦ C under 1.6 MPa within 4 h. It was found also that, when a Pt/C catalyst was used in the reaction, the product distribution showed dependence on the type of the solvent, pH value, partial pressure of oxygen, temperature, and the nature of the catalyst. As a result, the oxidation of 5-HMF prevails to give 2,5-DFF as the major product under a high temperature and neutral pH, where 19% yield of DFF is obtained. Besides, a homogeneous metal/bromide cata- lyst was also used in the air oxidation of 5-HMF , in which the yield of 2,5-DFF was 57%. However, a prominent disadvantage is the corrosion problem of this reaction system. Recently, Amarasekara et al. found that 5-HMF was efﬁciently oxidized to 2,5-DFF in 6. Catalytic oxidation and hydrogenation route of 5-HMF. X. Tong et al. / Applied Catalysis A: General 385 (2010) 1–13 9 7. Pathways from renewable resources to chemical products. natives for their petroleum-based counterparts in the chemical industry (as shown in Fig. 7). The noble metal catalysts, e.g. carbon or alumina-supported platinum have been found to be efﬁcient for the oxidation of 5-HMF to 2,5-FDCA [168,169]. In these reaction systems, the oxidation of 5-HMF favorably proceeds to the deep oxidation to diacid when the reaction was performed under oxygen pressure and a controlled pH value. The oxidation of 5-HMF in aqueous phase to 2,5-FDCA was demonstrated with a near-quantitative yield on a Pt/Al2 O3 cata- lyst in basic reaction conditions at 60 ◦ C. In addition, it was found that a high yield of 2,5-FDCA was also obtained when a Pt/Pb bimetallic catalyst is used. However, when Pt-based catalysts were used for the HMF to 2,5-FDCA reaction with oxygen as oxidant in water, a high catalyst-to-substrate weight ratio could be required on the. Furthermore, a Co/Mn/Br catalyst was applied in the air oxi- dation of 5-HMF to 2,5-FDCA, and a 60% yield was obtained when the reaction was performed at 125 ◦ C under 7.0 MPa air pressure for 3 h. This catalyst system has been used in commercial oxidation reactions. Kröger et al. studied the production of 2,5-FDCA from fructose via acid-catalyzed formation and subsequent oxidation of 5-HMF. As shown in Fig. 8, an effective separation of the oxida- tion catalyst and the formed 5-HMF and its derivatives into the MIBK phase with the automatic extraction facilitates the efﬁcient formation of 2,5-FDCA via the consequent oxidation in the MIBK phase. The maximum selectivity of 50% with a yield of 25% for 2,5-FDCA were achieved. Ribeiro and Schuchardt investi- gated the one-pot dehydration and oxidation of d-fructose over a bifunctional redox catalyst, i.e. cobalt acetylacetonate encap- sulated in sol–gel silica. The synergic effect of the two catalyst functions was impressive, and a 99% selectivity of 2,5-FDCA with 72% conversion of d-fructose was obtained at 160 ◦ C under 2.0 MPa air. in membrane reactor and batch reactor ((a) Membrane reactor, (1) 5-HMF formation in water phase; (2) diffusion of 5-HMF. (b) Batch reactor, (1) dehydration of fructose in batch reactor; (2) diffusion and oxidation of of Plenum Publishing Corporation. 2000 Copyright Springerlink publishing). et al. / Applied Catalysis A: General 385 (2010) 1–13 pathway for aqueous 5-HMF aerobic oxidation with gold catalysts. therefore extremely demanding (as shown in Scheme 2). Herein, the catalytic hydrogenation of aldehyde group (–CHO) and furan ring take place and a careful control of the conditions allows to improve the selectivity of 2,5-BHF. Nearly quantitative yields in 2,5-BHF or 2,5-bis(hydroxymethyl)-tetrahydrofuran were obtained over conventional hydrogenation catalysts, such as Raney nickel and different supported metal catalysts (copper, platinum, palladium, cobalt, chromium, molybdenum) with H2 O as solvent at high temperature and under high hydrogen pressure [182–185]. 2,5-DMF, produced from the selective removal of ﬁve oxygen atoms from hexoses molecules, has a boiling point suitable for a liquid transportation fuel, and has the lowest water solubility and the highest research octane number (RON) among all the mono- oxygenated C6 compounds. Moreover, compared to bioethanol, it has also a energy density, ca. 30 kJ cm−3 higher, by 40% and a boil- ing point higher by 20 ◦ C [46,78]. Recently, Roman-Leshkov et al. developed a catalytic route for the production of 2,5-DMF from d-fructose, via a two-step process. The ﬁrst step is the acid- catalyzed dehydration of d-fructose to produce 5-HMF in a biphasic reactor. Then, 5-HMF is extracted in the organic phase of the reac- tor and is subsequently converted to 2,5-DMF by hydrogenolysis of C–O bonds over a copper–ruthenium (CuRu) catalyst (Fig. 10). Binder and Raines also reported the preparation of 2,5-DMF from d-fructose with a two-step method. Firstly, based on produc- tion of 5-HMF from d-fructose with H2 SO4 as catalyst, they studied the separation of 5-HMF with a ﬂow-chromatograph method with loading the mixture into a column of ion-exchange resin and elut- ing with deionized water. In the following step, the 5-HMF was taken up in 1-butanol and hydrogenated with a Cu–Ru/C cata- lyst. As a result, a 32.5% yield of 2,5-DMF based on d-fructose was obtained. Very recently, Luijkx et al. reported the production of 2,5-DMF by the hydrogenation of 5-HMF over a palladium cat- alyst in 1-propanol. During the reaction the main intermediate is synthesis route of 2,5-BHF and 2,5-DMF from hexoses. X. Tong et al. / Applied Catalysis A: General 385 (2010) 1–13 11 biphasic reactor (Diagram includes selective dehydration of fructose to form 5-HMF in the reactor (R1); evaporation of leading to precipitation of NaCl (E1); hydrogenolysis of 5-HMF to 2,5-DMF over a CuRu catalyst (R2); and separation (S1). Reprinted from Ref. with permission of Macmillan Publishers Limited. 2007 Copyright Nature The near term challenges can be listed as: (a) Mechanism of the transformation reactions, and the structure–property relationships of catalysts. (b) Catalyst development and optimization. (c) Multi-functional catalyst and the suitable solvent systems. (d) Process composition and large-scale production. is a vital of real sig- Acknowledgements we focus on 2,5-DFF, Tong is thankful to the ﬁnancial support from China Postdoctoral In sum- Science Foundation (20080440676 and 200902273). Li is thankful from the to the support from the Natural Science Foundation of China under acids, solid contract number 20425619. The work has been also supported by 2,5-FDCA, the Program of Introducing Talents to the University Disciplines under ﬁle number B06006, and the Program for Changjiang Scholars and Innovative Research Teams in Universities under ﬁle number and 2,5-DMF IRT 0641. biphasic References A.J. Ragauskas, C.K. Williams, B.H. Davison, G. Britovsek, J. Cairney, C.A. Eckert, W.J. Frederick Jr., J.P. Hallett, D.J. Leak, C.L. Liotta, J.R. Mielenz, R. Murphy, R. Templer, T. Tschaplinski, Science 311 (2006) 484–489. G.W. Huber, S. Iborra, A. Corma, Chem. Rev. 106 (2006) 4044–4098. C. Luo, S. Wang, H. Liu, Angew. Chem., Int. 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