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WO2012038968A1 - Procédé de production de furfural à partir de xylose à l'aide d'un catalyseur hétérogène de silice mésoporeuse contenant des métaux de terres rares - Google Patents

Procédé de production de furfural à partir de xylose à l'aide d'un catalyseur hétérogène de silice mésoporeuse contenant des métaux de terres rares Download PDF

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Publication number
WO2012038968A1
WO2012038968A1 PCT/IN2010/000835 IN2010000835W WO2012038968A1 WO 2012038968 A1 WO2012038968 A1 WO 2012038968A1 IN 2010000835 W IN2010000835 W IN 2010000835W WO 2012038968 A1 WO2012038968 A1 WO 2012038968A1
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WIPO (PCT)
Prior art keywords
xylose
furfural
catalyst
water
mixture
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Ceased
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PCT/IN2010/000835
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English (en)
Inventor
Ganapati Dadasaheb Yadav
Rajesh Vishnudev Sharma
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Priority claimed from IN2442MU2010 external-priority patent/IN268182B/en
Publication of WO2012038968A1 publication Critical patent/WO2012038968A1/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
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to a process for furfural production from xylose by using heterogeneous solid acid ICaT-2 catalyst. Reactions are carried out in the batch reactor by using mixture of solvents. Xylose conversion and furfural yield are increased with increasing temperature and amount of catalyst. Xylose conversion of 92% with furfural yield 67% is achieved after 3 h at 170 °C. Catalyst is recycled several times without loss of its performance. BACKGROUND OF THE INVENTION
  • Furfural is extensively produced by dehydration of xylose. It is act as raw material for the production of furan based chemicals. Furfural on hydrogenation gives furfuryl alcohol and tetrahydrofuran, which- is used extensively in the chemical industry. Furfural and its derivatives are act as multipurpose intermediates and can replace petroleum based building blocks that are used to make resins, pharmaceuticals, and fine chemicals. Furfural is also widely used in the refining of lubricating oil, removing aromatics from diesel, and as fungicide and nematocide. Furfural after condensation with formaldehyde, phenol, acetone or urea to produces resin with high corrosion resistance, low fire hazard and good physical strength
  • US 4912237 disclose the process for furfural production wherein suspension of pentosan in dilute sulfuric acid passing continuously through a flow reactor with a pressure steam under high temperature.
  • US 4366322 disclose process and apparatus for producing furfural from plant materials. Pentosans are hydrolyzed in presence of concentrated hydrochloric acid at 20-70 °C in the first reactor. The dehydration of pentoses into furfural is carried out in the second reactor by vapor phase reaction in strong acid concentration medium.
  • US 4533743 discloses process for production of furfural from pentosans by feeding aqueous solution of pantoses into plug flow reactor along with mineral acid in temperature range 220 to 300 °C and the residence time is in between 0.5 to 100 second.
  • US 20100048924 discloses process for producing furfural by mixing xylose solution with sub-critical or near critical water then rapidly cooling the mixture to produce furfural.
  • exfoliated titanate, niobate and titanoniobate nanosheets as solid acid catalyst are used for liquid-phase dehydration of D-xylose into furfural.
  • furfural is produced by hydrolysis of sorghum straw with phosphoric acid at 134 °C. Several concentration of phosphoric acid in the range of 2-6% was evaluated.
  • microporous AM- 11 crystalline niobium silicates were studied as solid acid catalyst for the dehydration of xylose in a water-toluene solvent mixture.
  • Mineral acids like sulfuric, hydrochloric, hydrofluoric, and phosphoric acid, as well as acetic acid are usually used for furfural production.
  • the homogenous mineral acid need to be neutralized and result into a large amount acid waste, corrosion and safety related problems. These processes also have extensive side reactions and hence selectivity to furfural is poor and its recovery from the reaction medium is also hampered.
  • Several heterogeneous catalysts have been reported but these are also suffered with poor furfural yield and poor catalyst recyclability.
  • This invention deals with to replace the mineral acid catalysts by stable, recyclable, nontoxic solid acid catalyst.
  • This invention discloses a process for producing furfural from xylose by using reusable ICaT-2 catalyst. Reactions are carried out in batch reactor by using mixture of solvent.
  • the principal objective of the present invention is to provide a process for furfural production in the highest possible concentrations with minimum production cost of the process.
  • Yet another objective of the present invention is to use of heterogeneous reusable solid acid catalyst to produce furfural from xylose in the minimum catalyst loading.
  • Another objective of the present invention is to develop process which utilizes minimum energy and gives minimum waste for production of furfural.
  • Another objective of the present invention is to provide an improved process for furfural production whereby drawbacks of prior art approaches are avoided.
  • xylose is dehydrated to furfural by using ICaT-2 (Institute of Chemical Technology) catalyst in the presence of mixture of the solvents.
  • Solvent selected from the group of water, methanol, ethanol, propanol, butanol, acetone, acetonitrile, dimethyl formamide, dimethyl sulfoxide and/or mixture thereof.
  • ICaT-2 catalyst is comprises of rare earth metals in the form of trifluromethane sulfonate anchored with hexagonal organic-inorganic mesoporous silica as base metal through organic linkage. Furfural is isolated from reaction mass by extraction followed by distillation.
  • Heterogeneous solid acid catalyst ICaT-2 is comprises of metal sulfonate anchored with hexagonal organic-inorganic mesoporous silica through organic linkage.
  • Process for furfural production from xylose comprises of following steps.
  • solvent used is selected from the group of solvents such as water, methanol, ethanol, propanol, butanol, acetone, acetonitrile, dimethyl formamide, dimethyl sulfoxide, N-methyl pyrrolidone and/or mixture thereof.
  • Process for furfural production from xylose wherein content of water to organic solvent are in the range of 1 to 90 %. More preferably in the range of 5 to 50 %.
  • reaction is carried out in the temperature range 50 to 300 °C more preferably in the range of 100 to 250 °C.
  • ICaT-2 Institute of Chemical Technology
  • ICaT-2 catalyst is comprises of rare earth metals in the form of trifluromethane sulfonate anchored with hexagonal organic-inorganic mesoporous silica as base metal through organic linkage.
  • the said catalyst composition has specific surface area in the range of 50 m 2 /g to 1000 m 2 /g and pore diameter in the range of 20-100 A.
  • the present invention utilizes ICaT-2 which shows excellent reusability for furfural production.
  • furfural synthesis is carried out under mild condition by using mixture of solvents.
  • Furfural is the bio-based renewable chemical and has wide application in chemical industry.
  • the reaction scheme is as follows:
  • One of the embodiments of the present invention for furfural production process wherein reactions are carried out using heterogeneous ICaT-2 solid acid catalyst to give excellent conversion of xylose to furfural with high efficiency and selectivity.
  • ICaT-2 catalyst is easily seperable, regenerable and reusable in furfural production process.
  • One of embodiments of the present invention for manufacturing furfural from xylose is carried out in an autoclave.
  • a four bladed pitch turbine impeller is used for agitation and temperature is maintained at ; °C of the desired value by PID controller.
  • solvent used for reaction is the mixture of water and organic solvent.
  • Organic solvents used are such as methanol, ethanol, propanol, acetonitrile and acetone in the range of 1 to 90 %.
  • the amount of catalyst employed is typically about 0.01 to 20% based on weight of the xylose in the reaction mixture.
  • One of the embodiments of the present invention for furfural production wherein xylose is used in the range of 0.5% to 60 % wt/wt of the reaction mass.
  • One of the embodiments of the present invention for process of furfural production wherein reaction is carried out in the temperature range of 30 °C to 300 °C, preferably in the range of 100 to 250 °C.
  • Another aspect of the present invention for process of manufacturing furfural is that dehydration of xylose to furfural is carried out for the time 1 min to 5 hours, preferably for 30 min to 5 hours depending upon the type of solvent used.
  • reaction is monitor on HPLC by using RI detector and ultraviolet (UV) detector both.
  • Another aspect of the present invention is the product furfural is separated from reaction mixture by extraction and simple distillation technique. Therefore, the foregoing examples are considered as illustrative in terms of principles of the invention.
  • ICaT-2 was prepared by a co-condensation sol-gel route. Hexadecyl amine was dissolved in ethanol and water mixture. Mixture of tetraethyl orthosilicate and 3- (mercaptopropyl)trimethoxysilane were added to the above solution. It is treated with lanthanum chloride (400 mg) for 2 h. The slurry was filtered and treated with trifluromethanesulfonic acid (5.4 mmol) at 30 °C for 2 h. The slurry was filtered and washed with water and dried under vacuum to get the active ICaT-2 catalyst. EXAMPLE 2-6:
  • the reactions are carried out in 300 ml autoclave has four bladed pitch turbine for agitation and temperature is maintained at +_1°C of the desired value by PID controller.
  • Autoclave reactor is purged with nitrogen and loaded with xylose (0.025 mol), 100 ml mixture of solvents (acetone and water 7:3) and reaction temperature is 170 °C.
  • Specific amount of ICaT-2 catalyst is added to reaction mixture (mentioned in Table 1).
  • the quantity of catalyst is varied in these examples to show the effect of catalyst loading (Drawing 1).
  • samples are withdrawn and analyzed by HPLC with the help of UV and RI detector. The conversion increases with increasing catalyst loading due to a proportional increase in the number of active sites of the catalyst.
  • reaction autoclave is cooled and catalyst is filtered.
  • the percentage conversion and percentage yield is calculated through calibration curve method. Furfural is isolated by extraction and distillation.
  • the reactions are carried out in 300 ml autoclave has four bladed pitch turbine for agitation and temperature is maintained at +_1°C of the desired value by PID controller.
  • Autoclave reactor is purged with nitrogen and loaded with xylose (0.025 mol), 100 ml mixture of solvents (7:3) and reaction temperature is 170 °C.
  • ICaT-2 catalyst (0.01 gm/cc) was added to reaction mixture.
  • the different mixture of solvents is used in these examples to show the effect of solvent (mentioned in Table-2).
  • samples are withdrawn and analyzed by HPLC with the help of UV and RI detector.
  • reaction autoclave is cooled and catalyst is filtered. The percentage conversion and percentage yield are calculated through calibration curve method. Furfural is isolated by extraction and distillation.
  • the reactions are carried out in 300 ml autoclave has four bladed pitch turbine for agitation and temperature is maintained at Ll°C of the desired value by PID controller.
  • Autoclave reactor is purged with nitrogen and loaded with about 100 ml mixture of solvents (acetone :water 7:3) and reaction temperature is 170 °C.
  • ICaT-2 catalyst (0.01 gm/cc) is added to reaction mixture.
  • the specific amount of xylose is used in these examples (mentioned in Table-3). After specific time intervals samples are withdrawn and analyzed by HPLC with the help of UV and RI detector. Effect of xylose concentration during the progress of reaction is mentioned in drawing-2. After reaction autoclave is cooled and catalyst is filtered. Furfural is isolated by extraction and distillation.
  • the reactions are carried out in 300 ml autoclave has four bladed pitch turbine for agitation and temperature is maintained at ⁇ _ ⁇ °C of the desired value by PID controller.
  • Autoclave reactor is purged with nitrogen and loaded with xylose (0.025 mol), 100 ml mixture of solvents (acetone :water 7:3).
  • ICaT-2 catalyst (0.01 ' gm/cc) is added to reaction mixture.
  • the temperature of the reaction is varied in these examples (mentioned in Table-4). After specific time intervals samples are withdrawn and analyzed by HPLC with the help of UV and RI detector. Effect of temperature during the progress of reaction is mentioned in the drawing-3. After reaction autoclave cooled and catalyst is filtered. Furfural is isolated by extraction and distillation.
  • the reactions are carried out in 300 ml autoclave has four bladed pitch turbine for agitation and temperature is maintained at ⁇ _ ⁇ °C of the desired value by PID controller.
  • Autoclave reactor is purged with nitrogen and loaded with xylose (0.025 mol), 100 ml mixture of solvents (acetone :water 7:3).
  • ICaT-2 catalyst (0.01 gm/cc) is added to reaction mixture and the reaction temperature is 170 °C. After specific time intervals samples are withdrawn and analyzed by HPLC with the help of UV and RI detector. After reaction autoclave is cooled and catalyst is filtered. The reusability of the catalyst is tested by conducting four runs. After completion of the reaction, the catalyst is filtered and washed with acetone. Then it is refluxed with 50 cm of acetone for 30 min and dried at 120 °C for 2 h. The reusability of the catalyst is mentioned in these examples (Table5).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Furan Compounds (AREA)

Abstract

Cette invention concerne un procédé de production de furfural à partir de xylose à l'aide d'un catalyseur hétérogène. Les réactions sont mises en œuvre dans un réacteur en mode discontinu à l'aide d'un mélange de solvants. L'effet de la température, de la quantité de charge catalytique et de la concentration de xylose est étudié en détails. La conversion du xylose et le rendement du furfural sont augmentés avec une température et une quantité de catalyseur croissantes. La conversion de xylose est de 92 % avec un rendement de furfural de 67 % obtenu après 3 h à 170°C. Le catalyseur est recyclé plusieurs fois sans perte de son activité. (I) L'ICaT-2 est préparé par une voie de co-condensation sol-gel. Une hexadécylamine est dissoute dans un mélange d'éthanol et d'eau. Un mélange d'orthosilicate de tétraéthyle et de 3-(mercaptopropyl)triméthoxysilane est ajouté à la solution ci-dessus. Le mélange obtenu est traité avec du chlorure de lanthane (400 mg) pendant 2 h. La suspension épaisse est filtrée et traitée avec de l'acide trifluorométhanesulfonique (5,4 mmol) à 30°C pendant 2 h. Elle est ensuite filtrée et lavée à l'eau, puis séchée sous vide pour obtenir le catalyseur ICaT-2 actif.
PCT/IN2010/000835 2010-09-03 2010-12-21 Procédé de production de furfural à partir de xylose à l'aide d'un catalyseur hétérogène de silice mésoporeuse contenant des métaux de terres rares Ceased WO2012038968A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
IN2442/MUM/2010 2010-09-03
IN2768/MUM/2010 2010-10-05
IN2768MU2010 2010-10-05
IN2442MU2010 IN268182B (fr) 2010-09-03 2011-02-18

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WO2012038968A1 true WO2012038968A1 (fr) 2012-03-29

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130317239A1 (en) * 2011-01-28 2013-11-28 Mitsubishi Chemical Corporation Method for producing 2-furaldehyde
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
EP2797905A4 (fr) * 2011-12-28 2015-07-08 Du Pont Procédé de production de furfural

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4366322A (en) 1979-08-03 1982-12-28 Bertin & Cie Method for the production of furfural from vegetable matter
US4533743A (en) 1983-12-16 1985-08-06 Atlantic Richfield Company Furfural process
US4912237A (en) 1988-01-08 1990-03-27 Fried. Krupp Gesellschaft Mit Beschrankter Haftung Process for producing furfural
WO2008019219A1 (fr) * 2006-08-07 2008-02-14 Battelle Memorial Institute Procédé de conversion de glucides dans des liquides ioniques en hydroxyméthylfurfural
US20100048924A1 (en) 2008-07-16 2010-02-25 Srinivas Kilambi Solvo-thermal hydrolysis of xylose
IN2010MU02442A (fr) * 2010-09-03 2010-10-22 Ganapati Dadasaheb Yadav

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4366322A (en) 1979-08-03 1982-12-28 Bertin & Cie Method for the production of furfural from vegetable matter
US4533743A (en) 1983-12-16 1985-08-06 Atlantic Richfield Company Furfural process
US4912237A (en) 1988-01-08 1990-03-27 Fried. Krupp Gesellschaft Mit Beschrankter Haftung Process for producing furfural
WO2008019219A1 (fr) * 2006-08-07 2008-02-14 Battelle Memorial Institute Procédé de conversion de glucides dans des liquides ioniques en hydroxyméthylfurfural
US20100048924A1 (en) 2008-07-16 2010-02-25 Srinivas Kilambi Solvo-thermal hydrolysis of xylose
IN2010MU02442A (fr) * 2010-09-03 2010-10-22 Ganapati Dadasaheb Yadav

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BIORESOURCE TECHNOLOGY, vol. 98, 2007, pages 3053 - 3056
CATALYSIS COMMUNICATION, vol. 9, 2008, pages 2144 - 2148
CATALYSIS LETTERS, vol. 108, 2006, pages 179 - 186
JOURNAL OF CATALYSIS, vol. 244, 2006, pages 230 - 237

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130317239A1 (en) * 2011-01-28 2013-11-28 Mitsubishi Chemical Corporation Method for producing 2-furaldehyde
US9403787B2 (en) * 2011-01-28 2016-08-02 Mitsubishi Chemical Corporation Method for producing 2-furaldehyde
US9815807B2 (en) 2011-01-28 2017-11-14 Mitsubishi Chemical Corporation Method for producing 2-furaldehyde
EP2797905A4 (fr) * 2011-12-28 2015-07-08 Du Pont Procédé de production de furfural
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

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