WO2012038969A1 - Procédé de conversion de fructose en 5-hydroxyméthylfurfural à l'aide d'un catalyseur de silice mésoporeuse imprégné avec des métaux de terres rares - Google Patents

Procédé de conversion de fructose en 5-hydroxyméthylfurfural à l'aide d'un catalyseur de silice mésoporeuse imprégné avec des métaux de terres rares Download PDF

Info

Publication number
WO2012038969A1
WO2012038969A1 PCT/IN2011/000048 IN2011000048W WO2012038969A1 WO 2012038969 A1 WO2012038969 A1 WO 2012038969A1 IN 2011000048 W IN2011000048 W IN 2011000048W WO 2012038969 A1 WO2012038969 A1 WO 2012038969A1
Authority
WO
WIPO (PCT)
Prior art keywords
fructose
hydroxymethylfurfural
catalyst
production
mixture
Prior art date
Application number
PCT/IN2011/000048
Other languages
English (en)
Inventor
Ganapati Dadasaheb Yadav
Rajesh Vishnudev Sharma
Original Assignee
Ganapati Dadasaheb Yadav
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ganapati Dadasaheb Yadav filed Critical Ganapati Dadasaheb Yadav
Priority claimed from IN2442MU2010 external-priority patent/IN268182B/en
Publication of WO2012038969A1 publication Critical patent/WO2012038969A1/fr

Links

Classifications

    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2252—Sulfonate ligands
    • B01J31/2256—Sulfonate ligands being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional ligands
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/226—Sulfur, e.g. thiocarbamates
    • 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
    • C07D307/42—Singly bound oxygen atoms
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/37—Lanthanum
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/38—Lanthanides other than lanthanum
    • 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
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
    • 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

  • This invention related to method of producing 5-ydroxymethylfurfural (HMF) from fructose by using heterogeneous solid acid catalyst ICaT-2 without giving any considerable byproduct.
  • This process is very economical as it involved high yield and simple separation process for the product.
  • the use of the green solvents and heterogeneous ICaT-2 catalyst makes this process clean and sustainable. All the operations are carried out in batch reactor. The process is tolerance towards high fructose loading.
  • the catalyst found to be very active without any substantial deactivation.
  • the simplification in work-up, separation of product and very good recyclability of the catalyst make the process cost-effective and efficient. Isolation procedure for 5- hydroxymethyl furfural is also discussed.
  • HMF 5-hydroxymethylfurfural
  • renewable resources act as platform chemical because of the wide range of the chemical intermediates and end products is produced from these compounds which used in the polymer industry, fuel and pharmaceutical industries.
  • HMF possesses a high potential industrial demand, and is reviewed as a sleeping giant to produce intermediate chemical from bio based renewable resources.
  • HMF is versatile chemical compound; however, no technical process has been constructed through sugar route till now. The reasons are low selectivity to HMF, requirement of strong acids, which requires neutralization and lead to large amount of acid waste.
  • the high boiling polar solvents like dimethylsulfoxide, dimethylformamide, acetonitrile, poly(glycol ether) etc. give good selectivity to HMF but makes separation process most expensive.
  • WO 012445A1 disclose a method of producing HMF by mixing or agitating an aqueous solution of fructose and inorganic acid catalyst with water immiscible organic solvent to form an emulsion. The mixture is heated to 240 °C to 270 °C in a flow reactor at high pressure and then separated into aqueous and organic phase to obtain HMF.
  • US 313889A1 disclose the process for making hydroxymethylfurfural from saccharide. A metal complex of an N-heterocyclic carbine and ionic liquid is used. Reaction mixture contains solvent immiscible with ionic liquid to extract 5-hydroxymethylfurfural from ionic liquid.
  • US 156841 Al disclose a method of producing substantially pure HMF, HMF esters and other derivatives from carbohydrate source.
  • Carbohydrate solution containing organic acid is heated and continuously flowed through a solid phase catalyst to form HMF or/and HMF ester.
  • US 033188A1 disclose the process for converting sugars to furan derivatives by using a biphasic reactor containing reactive aqueous phase and an organic extracting phase.
  • the aqueous reaction solution contains an acid catalyst.
  • Both aqueous solution and organic extraction solution contain at least one modifier such as dimethylsulfoxide, dimethylformamide, N-methylpyrrolidinone, acetonitrile, butyrolactone, dioxane and pyrrolidinone.
  • US 033187A1 disclose the process for converting carbohydrate to 5- hydroxymethylfurfural in the presence of metal halide and acid catalyst. In this process ionic liquids are used as solvent to dissolve carbohydrates.
  • US 142599A1 disclose the process for preparation and purification of 5- hydroxymethyfurfural. In this process high fructose corn syrup is used as convenient fructose source and 5-hydroxymethylfurfural is prepared by using ion exchange resin in presence of 1 -methyl-2-pyrrolidinone, dimethylacetamide, dimethylformamide and combinations.
  • US 4590283A disclose the process for manufacturing 5-hydroxymethyfurfural from hexose by heterogeneous catalyst comprising of strong acid cation exchange resin. This process is carried out continuously, particularly by the countercurrent principle. Strongly polar aprotic solvent such as dimethylsulfoxide, dimethylformamide, N- methylpyrrolidone, are used, this makes product isolation tedious and costly.
  • 5-hydroxymethylfurfural is produce by dehydration of fructose and glucose using a biphasic reactor system, comprised of reactive aqueous phase modified with DMSO, combined with an organic extracting phase consisting of a 7:3 (w/w) MIBK-2-butanol mixture or dichloromethane by using mineral acid catalyst such as HC1, H 2 S0 4 , H 3 P0 4 .
  • Solid acid catalysts such as H-zeolite and metal phosphates (vanadyl phosphate) give low conversion and low selectivity.
  • metal phosphates vanadyl phosphate
  • This invention deals with to replace the mineral acid catalysts by stable, reusable, non- toxic solid acid catalyst.
  • This invention discloses a method for producing 5- hydroxymethylfurfural from fructose by using reusable ICaT-2 catalyst. Reactions are carried out in batch reactor by using mixture of solvents. OBJECTIVE OF THE INVENTION
  • the objective of the present invention is to develop a process for production of 5- hydroxymethylfurfural from fructose with simplest reaction workup and with minimum production cost.
  • Another objective of the present invention is reacting feedstock solution comprising of fructose with the heterogeneous ICaT-2 catalyst by using mixed solvent system to yield 5 -hydroxymethylfurfural in good yield.
  • Yet another objective of the present invention is to use of cheaper and readily available biomass resources such as fructose to develop industrially feasible 5- hydroxymethylfurfural process.
  • Another objective of the present invention is to develop method for preparation of 5- hydroxymethylfurfural from fructose, which utilizes minimum energy and gives minimum waste.
  • the group of invention directed to a convenient method for production of 5- hydroxymethylfurfural (HMF) form renewable feedstock more precisely from fructose has been developed wherein fructose is dehydrated to 5-hydroxymethylfurfural 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, butanol, acetone, acetonitrile, dimethyl formamide, dimethyl sulfoxide and/or mixture thereof.
  • ICaT-2 catalyst is heterogeneous solid acid catalyst. It comprises of rare earth metal complex anchored with organic-inorganic porous silica as base metal through organic linkage. This process has been developed for batch mode operation. 5- hydroxymethylfurfural is isolated from reaction mass by extraction followed by distillation.
  • a present invention deals with the process for production of 5-hydroxymethylfurfural at substantial yield and purity from fructose in presence of heterogeneous mesoporous solid acid (ICaT-2) catalyst and mixed solvents system.
  • IaT-2 heterogeneous mesoporous solid acid
  • Process of invention comprises steps of
  • step D) Isolating 5-hydroxymethylfurfural from product mixture of step A) to C) by a process selected from the group comprising of filtration, evaporation, extraction and distillation alone or in combination.
  • heterogeneous solid acid catalyst comprises of rare earth metal complex anchored with hexagonal organic-inorganic mesoporous silica through organic linkage.
  • Reaction of invention is performed in batch reactor or a batch reactor system in series for production of 5-hydroxymethylfurfural from fructose.
  • Fructose solution are used in the range of 0.1% to 70% wt/wt, more preferably in the range of 1.0% to 50 % wt/wt of fructose solution and contacting of homogeneous solution of fructose with heterogeneous mesoporous ICaT-2 catalyst is done percentage in the range of 0.1 % to 50% wt wt percentage.
  • Solvent used in the process of invention is selected from the group of solvents such as water, methanol, ethanol, butanol, acetone, acetonitrile, dimethyl formamide, dimethyl sulfoxide, N-methyl pyrrolidone and/or mixture thereof and solvent can be preferably the mixture of water: methanol, water: ethanol, water: acetone and water: acetonitrile and/or mixture thereof.
  • Water content in organic solvent is in the range of 1 to 90 %, more preferably in the range of 5 to 50 %.
  • reaction temperature is in the range. 50 °C to 300 °C, more preferably in the range of 80 °C to 250 °C and reaction time for contacting step is at least 10 hrs, more preferably in the range 1.0 min to 3 hrs.
  • ICaT-2 Institute of Chemical Technology
  • HMF 5-hydroxymethylfurfural
  • ICaT-2 catalyst is comprises of rare earth metal complex anchored with organic-inorganic hexagonal porous silica as base metal through organic linkage.
  • the present invention utilizes heterogeneous ICaT-2 which is easily re-generable and shows excellent reusability for 5-hyroxymethylfurfural process.
  • the ICaT-2 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.
  • fructose dehydration reaction is carried out under moderate conditions by using ICaT-2 as catalyst and mixture of solvents.
  • 5 -hydroxymethylfurfural (HMF) produced from renewable resources act as platform chemical because of the wide range of the chemical intermediates and end products is produced from these compounds which used in the polymer industry, fuel and pharmaceutical industries. The reaction is shown as below:
  • fructose dehydration is carried out in batch mode operation by using an autoclave reactor. Reaction is agitated with four bladed pitch turbine impeller and temperature is maintained at +1°C of the desired value by PID controller.
  • One of the embodiments of the present invention for 5-hydroxymethylfurfural production method wherein reactions are carried'out using heterogeneous ICaT-2 solid acid catalyst. It gives high efficiency for fructose conversion and excellent selectivity for 5- hydroxymethylfurfural.
  • ICaT-2 catalyst is easily separable, regenerable, reusable and cost effective catalyst.
  • 1.0 % to 50 % wt/wt fructose is present to the reaction mixture.
  • fructose dehydration is carried out by using the solvent selected from the group of solvent such as water, methanol, ethanol, butanol, acetone, acetonitrile, dimethyl formamide, dimethyl sulfoxide and/or mixture thereof.
  • solvent used for reaction is the mixture of aqueous and organic solvent.
  • Organic solvents used are such as methanol, ethanol, acetonitrile and acetone and/or mixture of thereof in the range of 1 to 90 %, more preferably in the range of 5 to 50 %.
  • reaction temperature is in the range of 50 °C to 300 °C, more preferably in the range of 50 °C to 250 °C are selected.
  • reaction is online monitor on HPLC by using RI detector and ultraviolet (UV) detector both.
  • ICaT-2 is 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.
  • the reaction is performed by loading autoclave reactor with fructose (0.025 mol), 100 ml mixture of solvents (acetone and water 7:3) and specific amount of the ICaT-2 catalyst.
  • the reactor is purged with nitrogen and temperature is raised to 160 °C.
  • the experiments are carried out in a 300 cm stainless steel Parr autoclave. Reaction mixture is agitated with a four bladed pitch turbine impeller. The reaction temperature is maintained at 160 °C with an accuracy of + 1 °C by PID controller.
  • Specific amount of ICaT-2 catalyst is added to reaction mixture (mentioned in Table 1). The effect of catalyst loading is studied with respect to variation in the quantity of catalyst (Drawing 1).
  • the reaction is performed by loading autoclave reactor with fructose (0.025 mol), 100 ml mixture of solvents (7:3) and specific amount of the ICaT-2 catalyst (0.01 gm/cc). The reactor is purged with nitrogen and temperature is raised to 160 C.
  • the experiments are carried out in a 300 cm stainless steel Parr autoclave. Reaction mixture is agitated with a four bladed pitch turbine impeller. The reaction temperature is maintained at 160 °C with an accuracy of + 1 °C by PID controller.
  • the different mixture of solvents is used in these examples to evaluate the effect of solvent (mentioned in Table-2).
  • the progress of the reaction is monitor on HPLC by using UV and RI detector. Calibration curve method is adopted for calculating percentage conversion and percentage yield quantitatively.
  • catalyst is filtered and washed with acetone. Extraction and distillation procedures are employed for isolation of 5-hydroxymethylfurfural from the reaction mixture.
  • the reactions are carried out in batch mode operation.
  • the reaction is performed by loading autoclave reactor with fructose, 100 ml mixture of solvents (acetone :water 7:3) and specific amount of the ICaT-2 catalyst (0.01 gm/cc).
  • the reactor is purged with nitrogen and temperature is raised to 160 °C.
  • the experiments are carried out in a 300 cm stainless steel Parr autoclave. Reaction mixture is agitated with a four bladed pitch turbine impeller. The reaction temperature is maintained at 160 °C with an accuracy of + 1 °C by PID controller. Specific amount of fructose is added to reaction mixture (mentioned in Table-3). The progress of the reaction is monitor on HPLC by using UV and RI detector.
  • Calibration curve method is adopted for calculating percentage conversion and percentage yield quantitatively.
  • the different amount of fructose is used in these examples to evaluate its effect on conversion and yield (Drawing 2).
  • catalyst is filtered and washed with acetone. Extraction and distillation procedures are employed for isolation of 5-hydroxymethylfurfural from the reaction mixture.
  • the reaction is carried out in batch mode operation.
  • the reaction is performed by loading autoclave reactor with fructose (0.025 mol), 100 ml mixture of solvents (acetone :water 7:3) and specific amount of the ICaT-2 catalyst (0.01 gm/cc).
  • the reactor is purged with nitrogen and temperature is raised to desire value.
  • the experiments are carried out in a 300 cm 3 stainless steel Parr autoclave.
  • Reaction mixture is agitated with a four bladed pitch turbine impeller.
  • the reaction temperature is maintained at desire value with an accuracy of + 1 °C by PID controller.
  • the temperature of the reaction is varied in these examples (mentioned in Table-4).
  • the progress of the reaction is monitor on HPLC by using UV and RI detector.
  • Calibration curve method is adopted for calculating percentage conversion and percentage yield quantitatively. The effect of temperature in conversion and yield are shown in drawing 3. After completion of the reaction, catalyst is filtered and washed with acetone. Extraction and distillation procedures are employed for isolation of 5-hydroxymethylfurfural from the reaction mixture.
  • the reaction is performed by loading autoclave reactor with fructose (0.025 mol), 100 ml mixture of solvents (acetone rwater 7:3) and specific amount of the ICaT-2 catalyst (0.01 gm/cc). The reactor is purged with nitrogen and temperature is raised to 160 °C. The experiments are carried out in a 300 cm stainless steel Parr autoclave. Reaction mixture is agitated with a four bladed pitch turbine impeller. The reaction temperature is maintained at 160 °C with an accuracy of + 1 °C by PID controller. The progress of the reaction is monitor on HPLC by using UV and RI detector. Calibration curve method is adopted for calculating percentage conversion and percentage yield quantitatively.
  • 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 3 of acetone for 30 min and dried at 120 °C for 2 h. The reusability of the catalyst is mentioned in these examples (Table 5). Extraction and distillation procedures are employed for isolation of 5- hydroxymethylfurfural from the reaction mixture.
  • the isolation and purification of 5-hydroxymethylfurfural is carried out by a process selected from the group consisting of filtration, evaporation, extraction and distillation.
  • Reaction mass is filtered through filter paper to remove solid heterogeneous ICaT-2 catalyst. Catalyst was washed with 50 cm of acetone.
  • Reaction mass is distilled under reduced pressure to remove acetone and then aqueous mother liquor is extracted with 100 X 3 times organic solvent such as ethyl acetate, diethylether, methyl isobutyl ketone, dichloromethane, methyl -tertiary-butyl ether, butyl acetate.
  • Organic layer is dried by using sodium sulfate and distilled under reduced pressure to get pure 98 % HMF.

Landscapes

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

Abstract

Cette invention concerne un procédé de production de 5-hydroxyméthylfurfural à partir de fructose à l'aide d'un catalyseur acide solide hétérogène, ICaT-2, sans génération considérable de sous-produit. Le procédé est très économique dans la mesure où il implique un rendement élevé et un procédé de séparation simple du produit. Les réactions sont mises en œuvre par mélange du système de solvants dans le réacteur discontinu. Le procédé est tolérant vis-à-vis des charges à teneur élevée de fructose. La simplification de sa mise en œuvre, de la séparation du produit et la bonne recyclabilité du catalyseur en fait un procédé rentable, durable et efficace pour une utilisation industrielle. Un procédé d'isolation du 5-hydroxyméthylfurfural est également décrit. 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 triflurométhanesulfonique (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/IN2011/000048 2010-09-03 2011-01-24 Procédé de conversion de fructose en 5-hydroxyméthylfurfural à l'aide d'un catalyseur de silice mésoporeuse imprégné avec des métaux de terres rares WO2012038969A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
IN2442/MUM/2010 2010-09-03
IN3052/MUM/2010 2010-11-03
IN3052MU2010 2010-11-03
IN2442MU2010 IN268182B (fr) 2010-09-03 2011-02-18

Publications (1)

Publication Number Publication Date
WO2012038969A1 true WO2012038969A1 (fr) 2012-03-29

Family

ID=44627037

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/IN2011/000048 WO2012038969A1 (fr) 2010-09-03 2011-01-24 Procédé de conversion de fructose en 5-hydroxyméthylfurfural à l'aide d'un catalyseur de silice mésoporeuse imprégné avec des métaux de terres rares
PCT/IN2011/000102 WO2012029071A2 (fr) 2010-09-03 2011-02-18 Composition de catalyseur (icat-2) comprenant du métal de terre rare

Family Applications After (1)

Application Number Title Priority Date Filing Date
PCT/IN2011/000102 WO2012029071A2 (fr) 2010-09-03 2011-02-18 Composition de catalyseur (icat-2) comprenant du métal de terre rare

Country Status (1)

Country Link
WO (2) WO2012038969A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103028424A (zh) * 2013-01-10 2013-04-10 厦门大学 用于5-羟甲基糠醛合成的固体酸催化剂及其制备方法
CN115806535A (zh) * 2021-09-14 2023-03-17 中国科学院大连化学物理研究所 一种5-羟甲基糠醛的制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US33188A (en) 1861-09-03 Improvement in mounting glaziers diamonds
US33187A (en) 1861-09-03 Diamond-protector for dressing millstones
US142599A (en) 1873-09-09 Improvement in seed drills and planters
US156841A (en) 1874-11-17 Improvesvient in gum shoes
US313889A (en) 1885-03-17 Dash-board for vehicles
US4590283A (en) 1983-09-14 1986-05-20 Roquette Freres Process for manufacturing 5-hydroxymethylfurfural
WO2001002445A1 (fr) 1999-07-03 2001-01-11 Northwestern University Catalyseurs de polymerisation d'olefines de metaux de transition precoces a basse valence contenant du cyclopentadienyle
IN2010MU02442A (fr) * 2010-09-03 2010-10-22 Ganapati Dadasaheb Yadav

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2750394A (en) 1952-05-22 1956-06-12 Food Chemical And Res Lab Inc Manufacture of 5-hydroxymethyl 2-furfural
US2929823A (en) 1956-11-26 1960-03-22 Merck & Co Inc Production of 5-hydroxymethylfurfural
US2917520A (en) 1957-09-11 1959-12-15 Arthur C Cope Production and recovery of furans
US3118912A (en) 1960-04-18 1964-01-21 Rayonier Inc Preparation of hydroxymethylfurfural
FR2464260A1 (fr) 1979-09-05 1981-03-06 Roquette Freres Procede de fabrication du 5-hydroxymethylfurfural
DE3601281A1 (de) 1986-01-17 1987-07-23 Sueddeutsche Zucker Ag Verfahren zur herstellung von 5-hydroxymethylfurfural einschliesslich eines kristallinen produktes unter ausschliesslicher verwendung von wasser als loesungsmittel
US5728901A (en) 1996-10-04 1998-03-17 Air Products And Chemicals, Inc. Nitration process which employs water tolerant Lewis acid catalysts
FR2760744B1 (fr) 1997-03-12 1999-04-23 Rhodia Chimie Sa Procede d'acylation d'un compose aromatique
US5948696A (en) 1997-06-16 1999-09-07 Pharmacopeia, Inc. Combinatorial biaryl amino acid amide libraries
US6111107A (en) 1997-11-20 2000-08-29 Enzon, Inc. High yield method for stereoselective acylation of tertiary alcohols
DE19857314A1 (de) * 1997-12-12 2000-02-03 Sec Dep Of Science And Technol Stark saurer mensoporöser synergistischer Festkörper-Katalysator und Verwendung desselben
US6352954B1 (en) 1998-02-13 2002-03-05 Japan Science And Technology Corporation Microencapsulated lewis acid
US7572925B2 (en) 2006-06-06 2009-08-11 Wisconsin Alumni Research Foundation Catalytic process for producing furan derivatives in a biphasic reactor

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US33188A (en) 1861-09-03 Improvement in mounting glaziers diamonds
US33187A (en) 1861-09-03 Diamond-protector for dressing millstones
US142599A (en) 1873-09-09 Improvement in seed drills and planters
US156841A (en) 1874-11-17 Improvesvient in gum shoes
US313889A (en) 1885-03-17 Dash-board for vehicles
US4590283A (en) 1983-09-14 1986-05-20 Roquette Freres Process for manufacturing 5-hydroxymethylfurfural
WO2001002445A1 (fr) 1999-07-03 2001-01-11 Northwestern University Catalyseurs de polymerisation d'olefines de metaux de transition precoces a basse valence contenant du cyclopentadienyle
IN2010MU02442A (fr) * 2010-09-03 2010-10-22 Ganapati Dadasaheb Yadav

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
APPLIED CATALYSIS A: GENERAL, vol. 275, 2004, pages 111 - 118
CATALYSIS COMMUNICATION, vol. 4, 2003, pages 517 - 520
CATALYSIS COMMUNICATION, vol. 9, 2008, pages 2244 - 2249
CHHEDA ET AL: "An overview of dehydration, aldol-condensation and hydrogenation processes for production of liquid alkanes from biomass-derived carbohydrates", CATALYSIS TODAY, vol. 123, no. 1-4, 19 May 2007 (2007-05-19), ELSEVIER, NL, pages 59 - 70, XP022085575, ISSN: 0920-5861, DOI: 10.1016/J.CATTOD.2006.12.006 *
GREEN CHEMISTRY, vol. 9, 2007, pages 342 - 350
JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, vol. 112, 1996, pages L163 - LI65
JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, vol. 253, 2006, pages 165 - 169
SERI, KEI-ICHI; INOUE, YOSHIHISA; ISHIDA, HITOSHI: "Highly efficient catalytic activity of lanthanide(III) ions for conversion of saccharides to 5-hydroxymethyl-2-furfural in organic solvents", CHEMISTRY LETTERS., no. 1, 2000, pages 22 - 23, XP008137077, ISSN: 0366-7022 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103028424A (zh) * 2013-01-10 2013-04-10 厦门大学 用于5-羟甲基糠醛合成的固体酸催化剂及其制备方法
CN115806535A (zh) * 2021-09-14 2023-03-17 中国科学院大连化学物理研究所 一种5-羟甲基糠醛的制备方法

Also Published As

Publication number Publication date
WO2012029071A2 (fr) 2012-03-08
WO2012029071A3 (fr) 2012-06-14

Similar Documents

Publication Publication Date Title
Slak et al. A review of bio-refining process intensification in catalytic conversion reactions, separations and purifications of hydroxymethylfurfural (HMF) and furfural
Zhao et al. Continuous flow alcoholysis of furfuryl alcohol to alkyl levulinates using zeolites
Agirrezabal-Telleria et al. Heterogeneous acid-catalysts for the production of furan-derived compounds (furfural and hydroxymethylfurfural) from renewable carbohydrates: A review
Takagaki et al. Catalytic transformations of biomass-derived materials into value-added chemicals
Matsagar et al. Effects of cations, anions and H+ concentration of acidic ionic liquids on the valorization of polysaccharides into furfural
Sun et al. One-pot depolymerization of cellulose into glucose and levulinic acid by heteropolyacid ionic liquid catalysis
CN103242270B (zh) 一种从生物质制备糠醛类化合物的方法
Liu et al. One-pot conversion of carbohydrates into 5-ethoxymethylfurfural and ethyl D-glucopyranoside in ethanol catalyzed by a silica supported sulfonic acid catalyst
Daengprasert et al. Application of sulfonated carbon-based catalyst for solvothermal conversion of cassava waste to hydroxymethylfurfural and furfural
Perez et al. Production of HMF in high yield using a low cost and recyclable carbonaceous catalyst
Hu et al. State-of-the-art advances and perspectives in the separation of biomass-derived 5-hydroxymethylfurfural
Zhang et al. Recent progress in direct production of furfural from lignocellulosic residues and hemicellulose
KR101217137B1 (ko) 프록토오스를 포함하는 옥수수시럽으로부터 5-히드록시메틸-2-푸르푸랄을 제조하는 방법
JPH06504272A (ja) 不均一系触媒による５−ヒドロキシメチルフルフラールの調製方法
KR20100092054A (ko) 탄수화물의 히드록시메틸퓨르퓨랄(ｈｍｆ) 및 그 유도체로의 전환
TWI421243B (zh) 製備５-羥甲基糠醛之方法及裝置
Xu et al. Recent advances on solid acid catalyic systems for production of 5-Hydroxymethylfurfural from biomass derivatives
Portilla-Zuñiga et al. Etherification of 5-hydroxymethylfurfural using a heteropolyacid supported on a silica matrix
Guo et al. Critical assessment of reaction pathways for next-generation biofuels from renewable resources: 5-ethoxymethylfurfural
WO2012038967A1 (fr) Procédé de conversion du saccharose en 5-hmf à l'aide d'un catalyseur de silice poreux contenant un lanthane
WO2012038969A1 (fr) Procédé de conversion de fructose en 5-hydroxyméthylfurfural à l'aide d'un catalyseur de silice mésoporeuse imprégné avec des métaux de terres rares
WO2012038968A1 (fr) 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
Wagh et al. An efficient heterogeneous acid catalyst DICAT-1 for one-pot conversion of sucrose into 5-(hydroxymethyl) furfural
RU2608609C2 (ru) Способ дегидратации углеводсодержащих композиций
CN114163319A (zh) 一种生物基丙烯醛的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11714850

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11714850

Country of ref document: EP

Kind code of ref document: A1