WO2012038967A1 - Method for converting sucrose to 5 - hmf using a lanthanum containing porous silica catalyst - Google Patents
Method for converting sucrose to 5 - hmf using a lanthanum containing porous silica catalyst Download PDFInfo
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- WO2012038967A1 WO2012038967A1 PCT/IN2010/000834 IN2010000834W WO2012038967A1 WO 2012038967 A1 WO2012038967 A1 WO 2012038967A1 IN 2010000834 W IN2010000834 W IN 2010000834W WO 2012038967 A1 WO2012038967 A1 WO 2012038967A1
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- sucrose
- hydroxymethylfurfural
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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
- C07D307/42—Singly bound oxygen atoms
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- 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 for producing 5-hydroxymethyl furfural consisting of reacting sucrose solution with the heterogeneous solid acid ICaT-2 catalyst. All the operations are carried out in batch reactor. In this method mixture of solvents are used to produce 5-hydroxymethyl furfural. The kinetic parameter study revealed that sucrose conversion and 5-hydroxymethyl furfural yield are increased with increasing temperature and amount of catalyst. Catalyst is recycled many times without ' loss of its activity. Isolation procedure for 5-hydroxymethyl furfural is also discussed. BACKGROUND OF THE INVENTION
- HMF 5-hydroxymethyl furfural
- renewable resources act as key intermediate compound that bridge the gap between industrial chemistry 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 require 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 more expensive.
- US 4590283A disclose the process for manufacturing 5 -hydroxymethy furfural 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 poduct isolation tedious and costly.
- US 142599A1 disclose the process for preparation and purification of 5- hydroxymethy furfural.
- high fructose corn syrup is used as convenient fructose source and 5 -hydroxymethylfurfural is prepared by using ion exchange resin in presence of l-methyl-2-pyrrolidinone, dimethylacetamide, dimethylformamide and combinations.
- 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 033188 A 1 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 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.
- HMF ester is isolated from the product mixture by the process selected from the group consisting of filtration, evaporation, extraction and distillation.
- US 313889A1 disclose the process for making hydroxymethylfurfural from saccharide.
- a metal complex of an N-heterocyclic carbene and ionic liquid is used.
- Reaction mixture contains solvent immiscible with ionic liquid to extract 5 -hydroxymethylfurfural from ionic liquid.
- 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.
- HMF 5- hydroxymethylfurfural
- 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 .
- mineral acid catalyst such as HC1, H 2 S0 4 , H 3 P0 4 .
- the dehydration of sucrose to HMF was carried out by using mineral acids (such as HC1, H 3 P0 4 , H 2 S0 4 ), ion exchange resins, zeolites, transition metal ions and solid metal phosphates.
- Mineral acid catalysts are give high sucrose conversion with low selectivity to HMF yield and major disadvantage is corrosion of reactor, separation of the product and large amount of acid waste.
- Solid acid catalysts such as H-zeolite and metal phosphates (niobium phosphate) give low conversion and low selectivity.
- niobium phosphate metal phosphates
- This invention deals with to replace the mineral acid catalysts by stable, recyclable, nontoxic solid acid catalyst.
- This invention discloses a method for producing 5- hydroxymethylfurfural from sucrose by using reusable ICaT-2 catalyst. Reactions are carried out in batch reactor by using mixture of solvents.
- This invention is directed to a method for the production of 5-hydroxymethylfurfural from sucrose in the highest possible concentration and with minimum production cost.
- Another objective of the present invention is to develop method for production of 5- hydroxymethylfurfural which utilizes batch mode reactor.
- Another objective of the present invention is dehydrating the feedstock solution comprising of sucrose in the presence ICaT-2 catalyst by using mixed solvent system to yield 5-hydroxymethylfurfural in good yield.
- Another objective of the present invention is to utilize minimum quantity of heterogeneous reusable solid acid catalyst to produce 5-hydroxymethylfurfural from sucrose.
- Yet another objective of the present invention is to develop method for production of 5- hydroxymethylfurfural which utilizes mixture of various solvents to increase the product selectivity and reduces production cost.
- Another objective of the present invention is to develop method for preparation of 5- hydroxymethylfurfural from sucrose, which utilizes minimum energy and gives minimum waste.
- ICaT-2 catalyst is heterogeneous solid acid catalyst. It comprises of rare earth metals in the form of trifluromethane sulfonate anchored with organic-inorganic porous silica as base metal through organic linkage. This method has been developed for batch mode ⁇ reactor system. 5-hydroxymethylfurfural is isolated from reaction mass by extraction followed by distillation.
- the method for production of 5-hydroxymethylfurfural from sucrose are performed in batch mode operation.
- heterogeneous solid acid catalyst ICaT-2 is comprises of metal sulfonate anchored with hexagonal organic-inorganic mesoporous silica through organic linkage are used.
- the method for production of 5-hydroxymethylfurfural from sucrose has 0.1% to 50% wt/wt percentage of ICaT-2 catalyst based on reaction mass.
- 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.
- solvent used are more preferably the mixture of water: methanol, water: ethanol, water: propanol, water: acetone and water :acetonitrile and/or mixture thereof.
- the method for production of 5-hydroxymethylfurfural from sucrose has been carried out in the temperature range 10 °C to 300 °C, more preferably in the range of 100 °C to 250
- the method for production of 5-hydroxymethylfurfural from sucrose wherein autogeneous pressure or external pressure of the reaction are in the range of 2 bar to 30 bar.
- the method for production of 5-hydroxymethylfurfural from sucrose, wherein separation of the pure 5-hydroxymethylfurfural from final reaction mixture is carried out by extraction with organic solvent such ethyl acetate, ethers, dichloromethane or methyl- tertiary-butyl ether and/or mixture thereof followed by vacuum distillation.
- organic solvent such ethyl acetate, ethers, dichloromethane or methyl- tertiary-butyl ether and/or mixture thereof followed by vacuum distillation.
- ICaT-2 Institute of Chemical Technology
- ICaT-2 catalyst is comprises of rare earth metals in the form of trifluromethane sulfonate anchored with organic- inorganic porous silica as base metal through organic linkage.
- the present invention utilizes ICaT-2 which is easily 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.
- sucrose is dehydrated under mild conditions by using ICaT-2 as catalyst and mixture of solvents.
- 5 -Hydroxymethy furfural is the bio- based renewable chemical and act as key intermediate compound that bridge the gap between industrial chemistry because of the wide range of the chemical intermediates and end products that can be produced from these compounds for use in the polymer industry, fuel and pharmaceutical industries.
- the reaction mechanism is as follows:
- sucrose dehydration is carried out in the presence of solvent selected from the group of solvent such as water, methanol, ethandl, propanol, butanol, acetone, acetonitrile, dimethyl formamide, dimethyl sulfoxide and/or mixture thereof.
- solvent selected from the group of solvent such as water, methanol, ethandl, propanol, 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, propanol, acetonitrile, dimethyl formamide, dimethyl sulfoxide and acetone in the range of 10 to 99 %.
- the amount of catalyst employed is typically about 0.1 to 50% based on weight of the sucrose in the reaction mixture.
- the used catalyst is recycled several times to check process feasibility for industrial utilization.
- One of the embodiments of the present invention for 5-hydroxymethylfurfural production wherein sucrose is charged in the range of 0.1%) to 50 % wt/wt of the reaction mass.
- One of the embodiments of the present invention for method of 5-hydroxymethylfurfural production wherein reaction is carried out in the temperature range of 50 °C to 300 °C, preferably in the range of 100 to 250 °C.
- Another aspect of the present invention for method of manufacturing 5- hydroxymethylfurfural is that dehydration of sucrose to 5-hydroxymethylfurfural is carried out for the time 1 min to 10 hours, preferably for 30 min to 5 hours depending upon the type of solvent and amount of catalyst used.
- reaction is monitor on HPLC by using RI detector and ultraviolet (UV) detector both.
- Another aspect of the present invention is the product 5-hydroxymethylfurfural 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. Resulting material is oxidized. Further it is treated with lanthanum chloride (400 mg) in acetonitrile 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.
- Autoclave reactor is purged with nitrogen and loaded with sucrose (0.0125 mol), 100 ml mixture of solvents (acetone : water 7:3) and reaction temperature is 160 °C.
- sucrose 0.0125 mol
- 100 ml mixture of solvents acetone : water 7:3
- reaction temperature 160 °C.
- the experiments are carried out in a 300 cm 3 stainless steel Parr autoclave. A four bladed pitch turbine impeller was used for agitation. The temperature + 1 °C of the desired value is maintained at by PID controller.
- UV and RI detector are utilized for quantitative analysis of the samples after specific time intervals. Calibration curve method is adopted for calculation of percentage conversion and percentage yield. The reusability of the catalyst is tested by conducting four runs. After completion of the reaction, the catalyst is filtered and washed with acetone.
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- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Saccharide Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
This invention related to method for production of 5-hydroxymethylfurfural from sucrose by using heterogeneous solid acid ICaT-2 catalyst in presence of mixture of solvents. The kinetic parameter study revealed that sucrose conversion and 5 -hydroxy methyl furfural yield are increased with increasing temperature and amount of catalyst. Sucrose conversion of 73 % with 5-hydoxymethyl furfural yield 58 % is achieved after 60 min at 180 °C. Reactions are carried, out in batch mode operation. Catalyst is recycled many times without loss of its activity. Isolation procedure for 5-hydroxymethyl furfural is also discussed. 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.
Description
TITLE OF THE INVENTION
METHOD FOR CONVERTING SUCROSE TO 5 - HMF USING A
LANTHANUM CONTAINING POROUS SILICA CATALYST
FIELD OF INVENTION
This invention related to method for producing 5-hydroxymethyl furfural consisting of reacting sucrose solution with the heterogeneous solid acid ICaT-2 catalyst. All the operations are carried out in batch reactor. In this method mixture of solvents are used to produce 5-hydroxymethyl furfural. The kinetic parameter study revealed that sucrose conversion and 5-hydroxymethyl furfural yield are increased with increasing temperature and amount of catalyst. Catalyst is recycled many times without' loss of its activity. Isolation procedure for 5-hydroxymethyl furfural is also discussed. BACKGROUND OF THE INVENTION
5-hydroxymethyl furfural (HMF) obtained from renewable resources act as key intermediate compound that bridge the gap between industrial chemistry 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 require 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 more expensive.
US 4590283A disclose the process for manufacturing 5 -hydroxymethy furfural 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 poduct isolation tedious and costly.
US 142599A1 disclose the process for preparation and purification of 5- hydroxymethy furfural. 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 l-methyl-2-pyrrolidinone, dimethylacetamide, dimethylformamide and combinations. 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 033188 A 1 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 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. HMF ester is isolated from the product mixture by the process selected from the group consisting of filtration, evaporation, extraction and distillation.
US 313889A1 disclose the process for making hydroxymethylfurfural from saccharide. A metal complex of an N-heterocyclic carbene and ionic liquid is used. Reaction mixture contains solvent immiscible with ionic liquid to extract 5 -hydroxymethylfurfural from ionic liquid.
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.
According to the process in Speciality Petrochemicals 25, (2008), 19-22. 5- hydroxymethylfurfural (HMF) was produced from sucrose under micro-wave irradiation by using sulfuric acid as catalyst. Under optimal conditions, HMF yield and selectivity were 32.4 % and 36.2 % respectively.
According to the process in Journal of Molecular Catalysis A: Chemical 253, (2006), 165-169; acid catalyzed dehydration of fructose and sucrose into 5- hydroxymethylfurfural is achieved in the presence of l-H-3 -methyl imidazolium chloride acting as both solvent and catalyst.
According to the process in Applied Catalysis A: General 183 (1999) 295-302; selective dehydration of different substrates such as fructose, sucrose and inulin to 5- hydroxymethylfurfural has been studied in aqueous medium by using niobium phosphate catalyst in batch experiments.
According to the process in Journal of Chemical Society (Resumed) 1960, 787-791 ; sucrose was dissolved in dimethylformamide containing small amount of iodine is heated at 400 °C to get 5-hydroxymethylfurfural. In absence of iodine, formation of aldehyde was found negligible.
According to the process in Green Chemistry 9 (2007) 342-350; 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, H2S04, H3P04.
The dehydration of sucrose to HMF was carried out by using mineral acids (such as HC1, H3P04, H2S04), ion exchange resins, zeolites, transition metal ions and solid metal phosphates. Mineral acid catalysts are give high sucrose conversion with low selectivity to HMF yield and major disadvantage is corrosion of reactor, separation of the product and large amount of acid waste. Solid acid catalysts, such as H-zeolite and metal phosphates (niobium phosphate) give low conversion and low selectivity. Several heterogeneous catalysts have been reported but these are also suffered with poor HMF 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 method for producing 5- hydroxymethylfurfural from sucrose by using reusable ICaT-2 catalyst. Reactions are carried out in batch reactor by using mixture of solvents. OBJECTIVE OF THE INVENTION
This invention is directed to a method for the production of 5-hydroxymethylfurfural from sucrose in the highest possible concentration and with minimum production cost.
Another objective of the present invention is to develop method for production of 5- hydroxymethylfurfural which utilizes batch mode reactor.
Yet , another objective of the present invention is dehydrating the feedstock solution comprising of sucrose in the presence ICaT-2 catalyst by using mixed solvent system to yield 5-hydroxymethylfurfural in good yield.
Another objective of the present invention is to develop an improved method for 5- hydroxymethylfurfural production from sucrose whereby drawbacks of prior art approaches are avoided.
Yet another objective of the present invention is to provide a safe and simple method for production of 5-hydroxymethylfurfural at low cost to validate the possibility of its extrapolation to industry. Yet another objective of the present invention is to use of cheaper biomass resources such as sucrose to develop industrially viable 5-hydroxymethylfurfural process.
Another objective of the present invention is to utilize minimum quantity of heterogeneous reusable solid acid catalyst to produce 5-hydroxymethylfurfural from sucrose.
Yet another objective of the present invention is to develop method for production of 5- hydroxymethylfurfural which utilizes mixture of various solvents to increase the product selectivity and reduces production cost.
Another objective of the present invention is to develop method for preparation of 5- hydroxymethylfurfural from sucrose, which utilizes minimum energy and gives minimum waste. SUMMARY OF INVENTION
In the group of invention, a convenient method for production of 5- hydroxymethylfurfural (HMF) for renewable feedstock more precisely from sucrose has been developed wherein sucrose 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, propanol, butanol, acetone, acetonitrile, dimethyl formamide, dimethyl sulfoxide and/or mixture thereof.
ICaT-2 catalyst is heterogeneous solid acid catalyst. It comprises of rare earth metals in the form of trifluromethane sulfonate anchored with organic-inorganic porous silica as base metal through organic linkage. This method has been developed for batch mode \
reactor system. 5-hydroxymethylfurfural is isolated from reaction mass by extraction followed by distillation.
BRIEF DISCRIPTION OF DRAWINGS
Drawing 1 : Effect of catalyst loading
Drawing 2: Effect of sucrose concentration
Drawing 3: Effect of temperature
STATEMENT OF INVENTION
The method for selective conversion of sucrose to produce 5-hydroxymethylfurfural at substantial yield by using heterogeneous porous solid acid ICaT-2 catalyst in the presence of mixture solvents system has been developed. This method comprising of following steps:
, A) Mixing sucrose with the mixture of solvents, up to limit of its solubility to make homogeneous solution.
B) Heating the said homogeneous solution of sucrose with heterogeneous porous ICaT-2 catalyst to produce 5-hydroxymethylfurfural at reaction temperature and autogeneous pressure.
C) Catalyst recovery from reaction mass after completion of reaction, has done by filtration and washing with solvent.
C) Isolation of 5-hydroxymethylfurfural from mother liquor has been done by extraction with organic solvent and followed by distillation.
The method for production of 5-hydroxymethylfurfural from sucrose are performed in batch mode operation.
The method for production of 5-hydroxymethylfurfural from sucrose, wherein heterogeneous solid acid catalyst ICaT-2 is comprises of metal sulfonate anchored with hexagonal organic-inorganic mesoporous silica through organic linkage are used.
The method for production of 5-hydroxymethylfurfural from sucrose has 0.1% to 50% wt/wt percentage of ICaT-2 catalyst based on reaction mass.
The method for production of 5-hydroxymethylfurfural from sucrose, wherein 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.
The method for production of 5-hydroxymethylfurfural from sucrose, wherein solvent used are more preferably the mixture of water: methanol, water: ethanol, water: propanol, water: acetone and water :acetonitrile and/or mixture thereof.
The method for production of 5-hydroxymethylfurfural from sucrose, wherein water content to organic solvent are in the range of 1 to 90 %, more preferably in the range of 10 to 50 %.
The method for production of 5-hydroxymethylfurfural from sucrose has been carried out in the temperature range 10 °C to 300 °C, more preferably in the range of 100 °C to 250
°C. · .
The method for production of 5-hydroxymethylfurfural from sucrose, wherein autogeneous pressure or external pressure of the reaction are in the range of 2 bar to 30 bar. The method for production of 5-hydroxymethylfurfural from sucrose, wherein separation of the pure 5-hydroxymethylfurfural from final reaction mixture is carried out by extraction with organic solvent such ethyl acetate, ethers, dichloromethane or methyl- tertiary-butyl ether and/or mixture thereof followed by vacuum distillation.
DETAIL DESCRIPTION OF INVENTION
In accordance with the principle of a present invention, a method for preparation of 5- hydroxymethyfurfural from renewable feedstock more precisely from sucrose has been developed, wherein sucrose is dehydrated to 5-hydroxymethylfurfural by using ICaT-2 (Institute of Chemical Technology) catalyst is described. ICaT-2 catalyst is comprises of rare earth metals in the form of trifluromethane sulfonate anchored with organic- inorganic porous silica as base metal through organic linkage.
The present invention, utilizes ICaT-2 which is easily generable and shows excellent reusability for 5-hyroxymethylfurfural process. The ICaT-2 catalyst composition has specific surface area in the range of 50 m2/g to 1000 m2/g and pore diameter in the range of 20-100 A. In the present invention, sucrose is dehydrated under mild conditions by using ICaT-2 as catalyst and mixture of solvents. 5 -Hydroxymethy furfural is the bio- based renewable chemical and act as key intermediate compound that bridge the gap between industrial chemistry because of the wide range of the chemical intermediates and end products that can be produced from these compounds for use in the polymer industry, fuel and pharmaceutical industries. The reaction mechanism is as follows:
Sucrose to 5-hydroxymethylfurfural reaction mechanism 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. I^gives high efficiency and excellent selectivity for 5-hydroxymethylfurfural with good conversion of sucrose. ICaT-2 catalyst is easily separable, regenerable, reusable and cost effective catalyst.
One of embodiments of the present invention for production of 5-hydroxymethylfurfural from sucrose is carried out in batch mode operation by using an autoclave. A four bladed pitch turbine impeller is used for agitation and temperature is maintained at +1°C of the desired value by PID controller.
One of the embodiments of the present invention wherein sucrose dehydration is carried out in the presence of solvent selected from the group of solvent such as water, methanol, ethandl, propanol, butanol, acetone, acetonitrile, dimethyl formamide, dimethyl sulfoxide and/or mixture thereof.
One of the embodiments of present invention for method of 5-hydroxymethylfurfural production, wherein solvent used for reaction is the mixture of aqueous and organic solvent. Organic solvents used are such as methanol, ethanol, propanol, acetonitrile, dimethyl formamide, dimethyl sulfoxide and acetone in the range of 10 to 99 %.
In the present invention for 5-hydroxymethylfurfural production, wherein the amount of catalyst employed is typically about 0.1 to 50% based on weight of the sucrose in the reaction mixture. The used catalyst is recycled several times to check process feasibility for industrial utilization.
One of the embodiments of the present invention for 5-hydroxymethylfurfural production, wherein sucrose is charged in the range of 0.1%) to 50 % wt/wt of the reaction mass. One of the embodiments of the present invention for method of 5-hydroxymethylfurfural production, wherein reaction is carried out in the temperature range of 50 °C to 300 °C, preferably in the range of 100 to 250 °C.
Another aspect of the present invention for method of manufacturing 5- hydroxymethylfurfural is that dehydration of sucrose to 5-hydroxymethylfurfural is
carried out for the time 1 min to 10 hours, preferably for 30 min to 5 hours depending upon the type of solvent and amount of catalyst used.
One of the embodiments of the present is that reaction is monitor on HPLC by using RI detector and ultraviolet (UV) detector both.
Another aspect of the present invention is the product 5-hydroxymethylfurfural 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.
EXAMPLE 1: Preparation of ICaT-2 catalyst
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. Resulting material is oxidized. Further it is treated with lanthanum chloride (400 mg) in acetonitrile 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:
Autoclave reactor is purged with nitrogen and loaded with sucrose (0.0125 mol), 100 ml mixture of solvents (acetone and water 7:3) and reaction temperature is 160 °C. The experiments are carried out in a 300 cm stainless steel Parr autoclave. A four bladed pitch turbine impeller is used for agitation. The temperature + 1 °C of the desired value is maintained at by PID controller. Specific amount of ICaT-2 catalyst is added to reaction mixture (mentioned in Table 1). The catalyst loading is studied with respect to variation in the quantity of catalyst (Drawing 1). UV and RI detector are utilized for quantitative analysis of the samples after specific time intervals. Calibration curve method is adopted for calculation of percentage conversion and percentage yield. Increase in catalyst
loading results in higher conversion of sucrose and HMF yield, due to a proportional increase in the number of active sites of the catalyst. Acetone is used for catalyst washing. Extraction and distillation procedures are employed for isolation of 5- hydroxymethylfurfural .
EXAMPLE 7-11:
Autoclave reactor is purged with nitrogen and loaded with sucrose (0.0125 mol), 100 ml mixture of solvents and reaction temperature is 160 °C. The experiments are carried out in a 300 cm stainless steel Parr autoclave. A four bladed pitch turbine impeller was used for agitation. The temperature + 1 °C of the desired value is maintained at by PID controller. Specific amount of ICaT-2 catalyst (0.01 gm/cc) is added to reaction mixture. The different mixture of solvents is used in these examples to evaluate the effect of solvent (mentioned in Table-2). UV and RI detector are utilized for quantitative analysis of the samples after specific time intervals. Calibration curve method is adopted for calculation of percentage conversion and percentage yield. Acetone is used for catalyst washing. Extraction and distillation procedures are employed for isolation of 5- hydroxymethylfurfural.
Table-2
Time Temperature %Conversion %Yield of
Example Solvent (minutes) of sucrose HMF
7 Water 180 160 °C 59 19
8 Methanol: Water 180 160 °C 65 27
9 Isopropyl alcohol: Water 180 160 °C 61 52
10 Ethanol: Water 180 160 °C 60 43
11 Acetone: Water 180 160 °C 63 54
EXAMPLE 12-15:
Autoclave reactor is purged with nitrogen and loaded with sucrose, 100 ml mixture of solvent (acetone : water 7:3) and reaction temperature is 160 °C. The experiments are carried out in a 300 cm stainless steel Parr autoclave. A four bladed pitch turbine impeller was used for agitation. The temperature + 1 °C of the desired value is maintained at by PID controller. Specific amount of sucrose is added to reaction mixture (mentioned in Table-3). The different amount of sucrose used in these examples to evaluate its effect on conversion and yield (Drawing 2). UV and RI detector are utilized for quantitative analysis of the samples after specific time intervals. Calibration curve method is adopted for calculation of percentage conversion and percentage yield. Acetone is used for catalyst washing. Extraction and distillation procedures are employed for isolation of 5- hydroxymethylfurfural .
EXAMPLE 16-19:
Autoclave reactor is purged with nitrogen and loaded with sucrose (0.0125 mol) and 100 ml mixture of solvents (acetone :water 7:3). The experiments are carried out in a 300 cm3 stainless steel Parr autoclave. A four bladed pitch turbine impeller was used for agitation.
The temperature + 1 C of the desired value is maintained at by PID controller. The temperature of the reaction is varied in these examples (mentioned in Table-4). The effect of temperature in conversion and yield are shown in drawing 3. UV and RI detector are utilized for quantitative analysis of the samples after specific time intervals. Calibration curve method is adopted for calculation of percentage conversion and percentage yield. Acetone is used for catalyst washing. Extraction and distillation procedures are employed for isolation of 5-hydroxymethylfurfural.
Autoclave reactor is purged with nitrogen and loaded with sucrose (0.0125 mol), 100 ml mixture of solvents (acetone : water 7:3) and reaction temperature is 160 °C. The experiments are carried out in a 300 cm3 stainless steel Parr autoclave. A four bladed pitch turbine impeller was used for agitation. The temperature + 1 °C of the desired value is maintained at by PID controller. UV and RI detector are utilized for quantitative analysis of the samples after specific time intervals. Calibration curve method is adopted for calculation of percentage conversion and percentage yield. 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 cm3 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 .
Claims
1. A method for selective conversion of sucrose to produce 5-hydroxymethylfurfural at substantial yield by using heterogeneous porous solid acid ICaT-2 catalyst in the presence of mixture of solvents system has been developed. This method comprising of following steps:
a) Making solution of sucrose with the mixture of solvents, up to limit of its solubility to make homogeneous solution.
b) Heating the said homogeneous solution of sucrose with heterogeneous porous ICaT-2 catalyst to produce 5-hydroxymethylfurfural at reaction temperature and autogeneous pressure.
c) Catalyst recovery from reaction mass after completion of reaction, has done by filtration and washing with solvent.
d) Isolation of 5-hydroxymethylfurfural from mother liquor has been done by extraction with organic solvent and followed by distillation.
2. The method of claim 1 for production of 5-hydroxymethylfurfural from sucrose, wherein reactions are performed in batch mode operation.
3. The method of claim 1 for production of 5-hydroxymethylfurfural from sucrose, wherein heterogeneous solid acid catalyst ICaT-2 is comprises of metal sulfonate anchored with hexagonal organic-inorganic mesoporous silica through organic linkage are used.
4. The method of claim 1 for production of 5-hydroxymethylfurfural from sucrose, wherein 0.1% to 50% wt/wt of sucrose solution are used for the reaction, more preferably in the range of 1.0 % to 30 % wt/wt of sucrose solution.
5. The method of claim 1 for production of 5-hydroxymethylfurfural from sucrose, wherein 0.1% to 50% wt/wt percentage of ICaT-2 catalyst used in the reaction.
6. The method of claim 1 for production of 5-hydroxymethylfurfural from sucrose, wherein solvent used are more preferably the mixture of water: methanol, water: ethanol, water: propanol, water: acetone, water: acetonitrile, water: dimethyl formamide, water: dimethyl sulfoxide, water: N-methyl pyrrolidone and/or mixture thereof.
7. The method of claim 1 and 6 for production of 5-hydroxymethylfurfural from sucrose, wherein water content to organic solvent are in the range of 1 to 90 %, more preferably in the range of 10 to 50 %.
8. The method of claim 1 for production of 5-hydroxymethylfurfural from sucrose, wherein reaction is carried out in the temperature range 50 °C to 300 °C, more preferably in the range of 100 °C to 250 °C.
9. The method of claim 1 for production of 5-hydroxymethylfurfural from sucrose, wherein reaction is carried out at least 10 hrs, more preferably 1 min to 5 hrs.
10. The method of claim 1 for production of 5-hydroxymethylfurfural from sucrose, wherein autogeneous pressure or external pressure of the reaction are in the range of 2 bar to 30 bar.
11. The method of claim 1 for production of 5-hydroxymethylfurfural from sucrose, wherein separation of the pure 5-hydroxymethylfurfural from final reaction mixture is carried out by filtration, extraction with organic solvent such ethyl acetate, ethers, dichloromethane or methyl-tertiary-butyl ether and/or mixture thereof followed by vacuum distillation.
Signature of Applicant:
YADAV GANAPATI DADASAHEB
(Last Name/Surname) (First Name) (Father 's Name/Middle Name)
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| IN2442MU2010 IN268182B (en) | 2010-09-03 | 2011-02-18 |
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| CN106632164A (en) * | 2016-12-29 | 2017-05-10 | 江南大学 | Preparation and application of magnetic metallic oxide coupled acid poly-ionic liquid |
| CN114957173A (en) * | 2022-05-12 | 2022-08-30 | 浙江恒逸石化研究院有限公司 | Method for continuously converting and separating 5-hydroxymethylfurfural from high-concentration biomass sugar under catalysis of solid acid |
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| CN114957173B (en) * | 2022-05-12 | 2024-04-05 | 浙江恒逸石化研究院有限公司 | Method for continuously converting and separating 5-hydroxymethylfurfural by catalyzing high-concentration biomass sugar through solid acid |
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