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WO2011063500A1 - Procede pour preparer du furfural a partir de xylose - Google Patents

Procede pour preparer du furfural a partir de xylose Download PDF

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Publication number
WO2011063500A1
WO2011063500A1 PCT/CA2010/001817 CA2010001817W WO2011063500A1 WO 2011063500 A1 WO2011063500 A1 WO 2011063500A1 CA 2010001817 W CA2010001817 W CA 2010001817W WO 2011063500 A1 WO2011063500 A1 WO 2011063500A1
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WIPO (PCT)
Prior art keywords
nafion
process according
xylose
furfural
catalyst
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PCT/CA2010/001817
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English (en)
Inventor
Edmond Lam
Chi Woon Leung
John H.T. Luong
Khaled Mahmoud
Ehsan Majid
Jonathan Chong
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National Research Council Of Canada
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Publication of WO2011063500A1 publication Critical patent/WO2011063500A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C07D307/48—Furfural
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C07D307/48—Furfural
    • C07D307/50—Preparation from natural products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to the synthesis of furfural from xylose, in particular to the dehydration of xylose to furfural using a heterogeneous catalyst.
  • NafionTM a sulfonated tetrafluoroethylene-based fluoropolymer-copolymer
  • NafionTM As a superacid, NafionTM has been used as a catalyst for organic transformations including acylation, alkylation and isomerization reactions.
  • NafionTM has been used in the dehydration of fructose (a hexose sugar) to produce 5-hydroxymethylfurfural (HMF) at 50% yield.
  • NafionTM NR50 has been used for the depolymerization of cellulose (microcrystalline cellulose) to various sugars (Rinaldi 2008). Rinaldi et al. also noted that the catalytic performance of NafionTM NR50 for cellulose depolymerization was limited compared to AmberlystTM 15DRY, and that only trace amounts of furfural were produced. There has been no report that NafionTM can be used in the dehydration of xylose to produce furfural in high yield.
  • the sulfonated tetrafluoroethylene-based fluoropolymer-copolymer may be used in different forms, for example, as membranes, as the polymer on amorphous silica, as pellets or as solutions. Membranes and the polymer on amorphous silica are preferred as these forms have been found to be more recyclable providing a more stable and reproducible catalyst system than pellets. This may be due to a resistance to deactivation by impurity accumulation and/or to stable physical properties of the catalyst associated with less swelling under reaction conditions for furfural production.
  • Membranes are very particularly preferred as membranes additionally provide higher activities, leading to shorter reaction times, and higher furfural yields than other forms of the sulfonated tetrafluoroethylene-based fluoropolymer-copolymer and other heterogeneous catalysts used in dehydration of xylose to furfural.
  • NafionTM polymers include NafionTM membranes (e.g. NafionTM 117, NafionTM 1110, NafionTM 115, NafionTM 1035), NafionTM on amorphous silica (e.g. NafionTM SAC-13), NafionTM pellets (e.g. NafionTM NR50, NafionTM NR40) and NafionTM solutions in water/alcohol mixtures (e.g. NafionTM D520, NafionTM D521 ).
  • NafionTM membranes e.g. NafionTM 117, NafionTM 1110, NafionTM 115, NafionTM 1035
  • NafionTM on amorphous silica e.g. NafionTM SAC-13
  • NafionTM pellets e.g. NafionTM NR50, NafionTM NR40
  • NafionTM 117 is the most preferred as it surprisingly provides a better combination of stability, reproducibility, activity, catalysfcsubstrate ratio and furfural yield than other NafionTM forms and other dehydration catalysts (e.g. H 2 S0 4 , HCI, zeolites heteropolyacids and sulfonic acid functionalized-MCM).
  • dehydration catalysts e.g. H 2 S0 4 , HCI, zeolites heteropolyacids and sulfonic acid functionalized-MCM.
  • Another useful copolymer in accordance with Scheme 2 has the same basic structure as NafionTM polymers but have higher sulfonated side chain densities than NafionTM polymers.
  • the value of x in Scheme 2 is greater than 0.92.
  • sulfonated tetrafluoroethylene-based fluoropolymer-copolymers having a value of x less than 0.92 are also useful.
  • Such copolymers have higher ion exchange capacities (IEC) than NafionTM polymers, for example, an EC in a range of from 0.9-1.25 meq H + per gram of material. Examples of such copolymers are known in the art (Su 2009; Li 2010).
  • LSC 0.97 resin having an ion exchange capacity (IEC) of 0.94 ⁇ 0.04 meq H + g "1 at 95% confidence, with a mass uptake of water of 9% at 25°C and 23% at 100°C, and with a volume change in liquid water from dry of 38% at 25°C and 78% at 100°C; and, LSC 1.13 resin having an IEC of .08 ⁇ 0.06 meq H + g A at 95% confidence, with a mass uptake of water of 24% at 25°C and 63% at 100°C, and with a volume change in liquid water from dry of 48% at 25°C and 226% at 100°C.
  • IEC ion exchange capacity
  • the process is performed at elevated temperature, for example at a temperature in a range of from about 110°C to 220°C, preferably at a temperature in a range of from about 110°C to 190°C, more preferably about 130°C to 180°C, yet more preferably about 145°C to 175°C. It is an advantage of the present process that the temperature at which the process can be conducted is lower than the temperature required for other acid catalysts like H 2 S0 4 and HCI. Heat treating the catalyst can reduce catalyst loading requirements by up to five times.
  • the process is generally performed for sufficient time to maximize furfural yield. It is an advantage of the present process that less time is required to maximize furfural yield than processes using other heterogeneous catalysts.
  • the process may be complete within about 4 h, and advantageously may even require up to only about 2 h to complete.
  • the process may be conducted batchwise or continuously, preferably batchwise.
  • the process is preferably performed in a reaction solvent.
  • the reaction solvent in which the process is performed preferably comprises a polar solvent, for example, dimethylsulfoxide (DMSO), dimethylformamide (DMF), water or mixtures thereof.
  • the reaction solvent more preferably comprises a polar, aprotic solvent having a boiling point higher than the desired reaction temperature, for example, DMSO, DMF or mixtures thereof.
  • DMSO is preferred as its hygroscopic nature enables it to suppress condensation side products and the rehydration of sugars, leading to improved selectivities and dehydration rates.
  • Water may be used when the reaction temperature is increased to about 170°C or greater. Water may be used especially in conjunction with one or more polar aprotic solvents.
  • water in the solvent mixture can also result in a decreased furfural yield.
  • Water content of up to about 10% v/v may be well tolerated, particularly when DMSO is used in the solvent system, but water content of 15% v/v or more reduces furfural yield significantly.
  • reaction solvent in which the process is performed may be used in conjunction with one or more extraction solvents to form a biphasic solvent system in which the furfural produced in an "aqueous phase" is extracted in situ into an "organic phase".
  • extraction solvents preferably comprise one or more organic solvents in which furfural is soluble. When two organic solvents are used in the extraction solvent, the ratio of the two is preferably in a range of from 25:75 to 75:25 v/v, for example 50:50 v/v.
  • the extraction solvent may comprise any number of organic solvents. Preferred examples of suitable organic solvents are methyl isobutyl ketone, 2-butanol, tetrahydrofuran (THF) or any mixture thereof.
  • the ratio of aqueous phase:organic phase is in a range of from about 25:75 to 75:25 v/v, for example about 50:50 v/v.
  • a particularly preferred biphasic solvent system comprises DMSO and water in the "aqueous phase” and methyl isobutyl ketone and 2-butanol in the "organic phase”.
  • Extracting furfural from the aqueous phase to the organic phase reduces side reactions of furfural (e.g. formation of furfural oligomers). Since side reactions reduce yield and selectivity, reducing side reactions helps maintain yield and selectivity of furfural.
  • Using biphasic solvent systems also permits the use of higher initial xylose concentrations, thereby reducing the amount of solvents required and aiding in product isolation and purification.
  • Xylose may be obtained from any suitable source.
  • the xylose is obtained from the degradation of vegetative biomass to higher saccharides or saccharide- containing molecules (e.g. sucrose, starch, cellulose, hemicellulose, inulin), and then the degradation of such higher saccharides or saccharide-containing molecules to xylose.
  • degradation of the vegetative biomass results from hydrolysis of the biomass, and vegetative biomass includes, for example, material from agricultural plant sources, material from wood sources, and the like. Examples of processes to obtain xylose are well known in the art. Degraded vegetative biomass at any suitable stage of purification may be used in the process of the present invention provided that it contains xylose.
  • initial xylose concentration in the solvent may be higher than in other processes. Higher initial xylose concentration leads to the use of less solvent and to a greater xylose:catalyst ratio, which is especially important on an industrial scale. In other processes, initial xylose concentration is generally restricted to less than about 3.3% wt. In the present process, initial xylose concentration in the solvent may be advantageously 4% wt. or higher, even more advantageously 6% wt. or higher, yet even more advantageously 8% wt. or higher. When a biphasic solvent system is not used, initial xylose concentration may be up to about 10% wt. When a biphasic solvent system is used, initial xylose concentration may be up to about 20% wt.
  • Furfural is produced in the process of the present invention in high yield. Yields may be about 35% or greater, even about 45% or greater, even about 50% or greater. Yields up to about 65% or more may be achievable, and yields up to about 60% can be achieved.
  • Furfural produced by the process of the present invention may be recovered by generally known methods, for example, by distillation, extraction (e.g. mixed solvent extraction), two-phase separation, supercritical carbon dioxide, polymeric adsorbents or a combination thereof. A combination of chemical and physical techniques may improve overall furfural selectivity and yield.
  • NafionTM especially NafionTM membranes (e.g. NafionTM 117), and similar sulfonated tetrafluoroethylene-based fluoropolymer-copolymers are efficient heterogeneous catalysts for the dehydration of xylose to yield furfural.
  • the catalysts exhibit one or more of the following advantages over catalysts currently reported in the literature: higher turnover frequencies (TOF); shorter reaction times; lower reaction temperatures; reduced undesirable by-products; reduced solvent requirements; lower substrate-to-catalyst requirements; reusability and regenerability of the catalyst; non- toxic; non-corrosive; easy to handle and easy to scale up.
  • TOF turnover frequencies
  • the reusable catalytic system of the present invention would be useful for the industrial production of furfural, an important chemical with diversified applications, from renewable xylose-containing biomass.
  • Commercial applications include production of furfural from various biomass sources.
  • the furfurals produced can be converted further to value-added products for industries involved with biofuels, fine chemicals, pharmaceuticals and furan-based polymers.
  • Fig. 1 A depicts a graph showing reaction profile for the dehydration of 0.67 M xylose with NafionTM 117 (20% wt. loading) at different temperatures in DMSO;
  • Fig. 1 B depicts a graph showing reaction profile for the dehydration of 0.67 M xylose with NafionTM SAC-13 (38% wt. loading) at different temperatures in DMSO;
  • Fig. 1 C depicts a graph showing reaction profile for the dehydration of 0.67 M xylose with NafionTM 117 (5% wt. loading) at different temperatures in DMSO
  • Fig. 1 D depicts a graph showing reaction profile for the dehydration of 0.67 M xylose with NafionTM SAC-13 (5% wt. loading) at different temperatures in DMSO
  • Fig. 1 E depicts a graph showing reaction profile for the dehydration of 0.67 M xylose with NafionTM 117 and NafionTM NR50 (50% wt. loading, 150 °C) at different times in DMSO;
  • Fig. 2 depicts Arrhenius plots of xylose conversion using NafionTM 117 and NafionTM SAC- 13 catalysts at different loadings
  • Fig. 3A depicts a graph showing the effects of water content on furfural yield, conversion and selectivity in the dehydration of xylose with NafionTM 117 (20% wt. loading, 150°C, 2 h) in DMSO;
  • Fig. 3B depicts a graph showing the effects of water content on furfural yield in the dehydration of xylose with NafionTM 117 (20% wt. loading, 150°C, 2 h) in DMSO;
  • Fig. 4 depicts infrared (IR) spectra of pristine NafionTM 117 and post-reaction NafionTM 117 (after three recycling runs);
  • Fig. 5 depicts atomic force microscopy (AFM) images of pristine NafionTM 117 (A) and post-reaction NafionTM 117 (after three recycling runs) (B);
  • Fig. 6A depicts a graph of furfural yield from recycling of NafionTM 117 (20% wt. loading, 150°C, 2 h) in 5 consecutive runs;
  • Fig. 6B depicts a graph of furfural yield from recycling of NafionTM 117 (20% wt. loading, 150°C, 2 h) in 5 consecutive runs without any treatment of the NafionTM 117 between runs;
  • Fig. 7 depicts a graph of furfural yield vs. time for the conversion of 3 wt% xylose in water to furfural using 2 wt% of LSC 0.97 resin catalyst at 205°C.
  • D-(+)-Xylose (BDH), NafionTM SAC-13, furfural, dimethyl sulfoxide, phloroglucinol (Sigma-Aldrich), acetonitrile (J.T.Baker), hydrochloric acid (Fisher), and glacial acetic acid (EMD) were used as received without further purification.
  • NafionTM 117 (Sigma-Aldrich) was purified by treatment with hot, 3% hydrogen peroxide to remove organic impurities and hot, 1 M sulfuric acid to remove metallic/ionic impurities prior to use (Yang 2004).
  • Catalytic acid sites of the NafionTM species were determined by a known titration technique (Lopez 2007). Analytical Methods for Xylose and Furfural
  • Furfural determination was performed by HPLC at 25°C using a spectrophotometer (Waters Lambda-Max Model 487) set at 250 nm, equipped with a pump (Waters Model 590), and a Beckman UltrasphereTM (#235330) 5 pm column. An acetonitrile/water (10:90 v/v) mixture was used as the mobile phase at 2.0 mL/min. The furfural concentration was calculated from a calibration curve.
  • Unreacted xylose content was determined by a colorimetric assay (Eberts 1979) using a Beckman DU 640 spectrophotometer. In brief, xylose samples were reacted with phloroglucinol in acidic media at 100°C for 4 min. Absorbances were measured at 554 nm with the xylose concentration calculated from a calibration curve.
  • Turnover frequency (TOF) by weight was calculated as:
  • SEM-EDX Scanning electron microscope energy dispersive X-ray
  • EDX spectra were collected at 30° angle, 20 kV accelerating voltage and 20 nm working distance. EDX results were analyzed using incorporated Inca, Point and Analyze software. SEM micrographs acquired in backscattered electron mode images were obtained at low vacuum of 15 Pa, 25 kV of accelerating voltage and 12 mm working distance. Attenuated total reflectance FTIR (ATR-FTIR) spectra were collected (Bruker
  • Tensor 27 FTIR spectrophotometer from 4000 to 600 cm “1 for 64 scans and 4 cm “1 resolution using a zinc selenide (ZnSe) crystal.
  • AFM Anamic Force Microscopy
  • tapping mode at scan rates of 0.5 Hz with 512x512 pixels on a Dimension 3100 with a NanoScope IV controller (Vecco Digital Instruments, Santa Barbara, CA). All measurements were made using a silicon cantilever (MPP-11000, spring constant about 40 N/m, resonance frequency about 300 kHz, NanoDevices, Inc., CA).
  • Example 1 General procedure for converting xylose to furfural
  • NafionTM is available in several forms including pellets, membranes, and solutions (in water/alcohol mixtures).
  • NafionTM 117 polymeric transparent membrane, 0.91 meq H + g "1
  • NafionTM SAC-13 NafionTM polymer on amorphous silica, 0.12 meq H + g "
  • NafionTM NR50 NafionTM polymer pellets
  • the NafionTM catalysts were used in the dehydration of 0.67 M xylose solution in DMSO (9.1 % initial wt. concentration).
  • the hygroscopic DMSO was able to suppress condensation side products and the rehydration of sugars, resulting in improved selectivities and dehydration rates (Chheda 2007).
  • a control experiment in DMSO was performed in the absence of a catalyst and gave only a 1 % furfural yield.
  • Figs. 1A-1 D show the reaction profiles for NafionTM 117 and NafionTM SAC-13, respectively at different temperatures.
  • NafionTM membranes e.g. NafionTM 117
  • NafionTM on amorphous silica e.g. NafionTM SAC-13
  • Xylose conversion increased with reaction temperature for both catalysts.
  • the furfural production rate also increased with temperature, but furfural yields began to decrease at the elevated temperatures, particularly at 175°C.
  • NafionTM 117 and NafionTM SAC-13 were compared at different reaction conditions with results summarized in Table 1A.
  • NafionTM 117 achieved the highest furfural yield at 60% with a selectivity of 66% (Table 1 , Entry 3). In comparing equivalent weight loadings of 5% wt, NafionTM 117 (Entries 1 and 2) exhibited higher yields than NafionTM SAC-13 (Entries 5 and 6).
  • NafionTM SAC-13 The reduced activity of NafionTM SAC-13 compared to NafionTM 117 may be due to the interaction of the NafionTM polymer with the silanol groups, which would decrease the availability of the sulfonic acid groups. Overall, NafionTM 117 is a more efficient catalyst than NafionTM SAC- 13 for furfural production due to the higher furfural yields obtained. Table 1 B
  • Fig. 1 E shows a comparison of the reaction profiles of NafionTM 117 and NafionTM NR50 with 50% wt. loading at 150°C for different reaction times. From Fig. 1 E, it is evident that maximum yields for both NafionTM 117 (53%) and NafionTM NR50 (48%) were achieved in 1 h. The formation of oligomeric furfural by-products is accelerated by the higher weight loadings of the catalyst: 6 h for 20% weight loading compared with 1 h for 50% weight loading for NafionTM 117. By-products were also detected for NafionTM NR50 after 1 h of reaction.
  • Example 2 The general procedure described in Example 1 for dehydrating xylose to furfural, as modified by the parameters in Table 2, was used to compare the activities of other heterogeneous catalysts to NafionTM 117. The results are presented in Table 2.
  • HY Faujasite and delaminated H-Nu6(2) are zeolites; Amberlyst-15 is a macroreticular-type cation exchange resin; MCM-41-S0 3 Hc is a sulfonic acid functionalized silica; and, H 3 PW 12 04o is a heteropoly acid.
  • Table 2 The general procedure described in Example 1 for dehydrating xylose to furfural, as modified by the parameters in Table 2, was used to compare the activities of other heterogeneous catalysts to NafionTM 117. The results are presented in Table 2.
  • HY Faujasite and delaminated H-Nu6(2) are zeolites; Amberlyst-15 is a macroreticular-type cation exchange resin; MCM-41
  • Example 4 Analysis of selectivity considerations Acid-catalyzed dehydration of xylose is postulated to involve successive protonation of the xylose hydroxyl groups, leading to the release of three water molecules and the formation of furfural (Zeitsch 2000).
  • the cluster-channel model for NafionTM shows hydrophillic clusters of sulfonic acid groups (4 nm in diameter) (Jeske 2008; Gierke 1981 ) that are dispersed through the hydrophobic semicrystailine perfluorocarbon matrix (Mauritz 2004; Deng 1997). Most likely, xylose migrates to these hydrophillic clusters where sulfonic acid groups catalyze the xylose dehydration.
  • the highest yield of furfural was achieved in 2 h at 150°C with 91 % xylose conversion for NafionTM 117 (20% wt. loading). As the reaction continued with time, yield began to decrease, ultimately leading to the formation of an insoluble oligomeric side product, which was detected after 6 h, resulting in a decrease of furfural yield by 10-15%.
  • the pore size of the NafionTM catalysts may play a significant role in the formation of by-products that reduce furfural selectivity and yield. The size of a furfural molecule along its longest axis is 0.57 nm (Sjoman 2007).
  • Activation energies for NafionTM catalysts are lower than other aqueous catalysts such as H 2 S0 4 (134 kJ/mol; Bhandari 1984) and HCI (142 kJ/mol; Smuk 1966) used in xylose conversion.
  • Figs. 3A and 3B shows the effect of water on xylose dehydration for NafionTM 117.
  • Fig. 3A when water content in DMSO was less than 10%, an average furfural yield of 56% was obtained with 89% xylose conversion. At 20% water content, furfural yield decreased significantly to 33% with 43% xylose conversion.
  • Fig. 3B a more intensive comparison confirms that NafionTM 117 can tolerate a water content of up to 10% v/v in DMSO without significant loss of activity, as an average furfural yield of 56% was obtained.
  • Example 7 Catalyst recyclability
  • NafionTM 117 is capable of dehydrating xylose to furfural within 2 h at 150°C at a 60% yield with high xylose concentration (9.1 % initial weight concentration) in dimethyl sulfoxide (DMSO) resulting in activities significantly higher than previously reported for other heterogeneous catalysts.
  • DMSO dimethyl sulfoxide
  • the hygroscopic nature of DMSO enables it to suppress condensation side products and the rehydration of sugars, leading to improved selectivities and dehydration rates.
  • the high activity of NafionTM 117 promotes shorter reaction times ( ⁇ 2 h) which limits the formation of undesirable side-products that could lead to catalyst deactivation.
  • Example 8 Use of non-NafionTM sulfonated tetrafluoroethylene-based fluoropolymer- copolymer
  • LSC 0.97 resin (Su 2009; Li 2010) is a non-NafionTM sulfonated tetrafluoroethylene-based fluoropolymer-copolymer having higher sulfonated side chain density than NafionTM and having an ion exchange capacity of 0.94 + 0.04 meq H + g "1 of material. Reactions were carried out using a starting solution of 2.25 g xylose in 75 mL of water with 45 mg (2% wt. relative to xylose) of LSC 0.97 resin as the catalyst. Zero time is defined to be the moment when the temperature of the solution reached the target temperature of 205°C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Furan Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé pour produire du furfural, consistant à : déshydrater le xylose à température élevée au moyen d'un catalyseur hétérogène comprenant un copolymère de fluoropolymère à base de tétrafluoroéthylène sulfoné. Ledit copolymère de fluoropolymère à base de tétrafluoroéthylène sulfoné est de préférence un polymère Nafion™, en particulier des membranes Nafion™, tel que le Nafion™ 117.
PCT/CA2010/001817 2009-11-24 2010-11-09 Procede pour preparer du furfural a partir de xylose WO2011063500A1 (fr)

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CN102391217A (zh) * 2011-12-06 2012-03-28 中国科学院过程工程研究所 一种添加阻聚剂的固体酸催化汽爆秸秆水洗液制糠醛方法
EP2574609A1 (fr) * 2011-09-30 2013-04-03 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Procédé de fabrication de liaisons de furane à partir de matières premières renouvelables
CN103130755A (zh) * 2013-01-23 2013-06-05 华南理工大学 酸性光催化剂在紫外光下催化转化木糖制备糠醛的方法
WO2013102015A1 (fr) * 2011-12-28 2013-07-04 E. I. Du Pont De Nemours And Company Procédé de production de furfural
WO2013102007A1 (fr) * 2011-12-28 2013-07-04 E. I. Du Pont De Nemours And Company Procédé de production de furfural
WO2014008364A2 (fr) 2012-07-03 2014-01-09 Xyleco, Inc. Conversion de biomasse
FR3006687A1 (fr) * 2013-06-05 2014-12-12 Agro Ind Rech S Et Dev Ard Procede de production de furfural a partir de biomasse lignocellulosique
US9024047B2 (en) 2010-12-21 2015-05-05 E I Du Pont De Nemours And Company Methods for furfural production from branched non-fermentable sugars in stillage or syrup
US9073847B2 (en) 2011-11-04 2015-07-07 Taminco Finland Method and an arrangement for separating at least one carboxylic acid and furfural from a dilute aqueous mixture thereof
US9181210B2 (en) 2011-12-28 2015-11-10 E I Du Pont De Nemours And Company Processes for making furfurals
US9181209B2 (en) 2011-12-28 2015-11-10 E I Du Pont De Nemours And Company Process for the production of furfural
US9181211B2 (en) 2011-12-28 2015-11-10 E I Du Pont De Nemours And Company Process for the production of furfural
EP3071556A1 (fr) * 2013-11-21 2016-09-28 Lali, Arvind Mallinath Procédé de synthèse d'un dérivé de furane faisant appel à un catalyseur acide et préparation dudit dérivé de furane
WO2016166421A1 (fr) * 2015-04-17 2016-10-20 Teknologian Tutkimuskeskus Vtt Oy Procédé de production de carboxylates de furane à partir d'acides aldariques faisant appel à des catalyseurs hétérogènes solides
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US9045449B2 (en) 2011-09-30 2015-06-02 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Method for the manufacture of furan compounds for renewable primary products
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FR3006687A1 (fr) * 2013-06-05 2014-12-12 Agro Ind Rech S Et Dev Ard Procede de production de furfural a partir de biomasse lignocellulosique
EP3071556A1 (fr) * 2013-11-21 2016-09-28 Lali, Arvind Mallinath Procédé de synthèse d'un dérivé de furane faisant appel à un catalyseur acide et préparation dudit dérivé de furane
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