Title of Invention

PROCESS FOR PRODUCTION OF FURFURAL FROM XYLOSE BY USING HETEROGENEOUS CATALYST

Abstract

The invention relates to a process for producing furfural from xylose by using heterogeneous catalyst. Reactions are carried out in batch reactor by using mixture of solvents. Effect of temperature, amount of catalyst loading and xylose concentration are studied in detail. Xylose conversion and furfural yield are increased with increasing temperature and amount of catalyst. Xylose conversion is 92% with furfural yield 67% achieved after 3 h at 170 °C. Catalyst is recycled several times without loss of its activity.

Full Text

F0RM 2 THE PATENTS ACT, 1970 (39 of 1970) COMPLETE SPECIFICATION (See section 10 and rule 13) 1. TITLE OF THE INVENTION "PROCESS FOR PRODUCTION OF FURFURAL FROM XYLOSE BY USING HETEROGENEOUS CATALYST" 2. APPLICANT NAME : YADAV GANAPATI DADASAHEB (Last Name/Surname) (First Name) (Father's Name/Middle Name) NATIONALITY: INDIAN ADDRESS : CHEMICAL ENGINEERING DEPARTMENT, INSTITUTE OF CHEMICAL TECHNOLOGY (DEEMED UNIVERSITY), NATHALAL PARIKH MARG, MATUNGA (EAST) MUMBAI 400 019 INDIA The following specification particularly describes the invention and the manner in which is to be performed. FIELD OF INVENTION The invention relates to a process for producing furfural 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 furfury] 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 nernatocide. 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 m 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. According to the process in Catalysis Communication 9 (2008) 2144-2148, Zeolites (faujasites and mordenites) have been used for dehydration of xylose to furfural but these process suffers with diffusion limitation leading to poor yield of furfural and poor recyclability of catalyst. According to the process in Journal of Catalysis 244 (2006) 230-237, exfoliated titanate, niobate and titanoniobate nanosheets as solid acid catalyst are used for liquid-phase dehydration of D-xylose into furfural. According to the process in Bioresource Technology 98 (2007) 3053-3056, 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. According to the process in Catalysis Letters 108 (2006) 179-186, 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. OBJECTIVE OF THE INVENTION The principal objective of the present invention is to provide a process for the production of furfural in the highest possible concentrations with minimum production cost of the process. Another objective of the present invention is to develop efficient process for production of furfural by utilizing the cheap renewable resources. Yet another objective of the present invention is to provide a safe and simple process for production of furfural at low cost to validate the possibility of its extrapolation to industry. 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. Yet another objective of the present invention is to develop process for production of furfural which utilizes mixture of solvents to increase the furfural selectivity. Yet another objective of the present invention is to develop a process for production of furfural with minimum reaction time. Another objective of the present invention is to develop process for production of furfural which utilizes batch mode reactor. Another objective of the present invention is to provide an improved process for furfural production whereby drawbacks of prior art approaches aer avoided. ' SUMMARY OF INVENTION In the group of invention, convenient process for manufacture of furfural for xylose has been developed wherein 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 trifiuromethane 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. BRIEF DISCRIPTION OF DRAWINGS Drawing 1: Effect of catalyst loading Drawing 2: Effect of xylose concentration Drawing 3: Effect of temperature STATEMENT OF INVENTION Batch mode process of producing furfural from xylose hy using heterogeneous solid acid ICaT-2 catalyst in the presence of mixture of the solvents has been developed. Heterogeneous solid acid catalyst ICaT-2 is comprises of metal triflate anchored with hexagonal organic-inorganic mesoporous silica through Organic linkage. Process for producing furfural from xylose comprises of following steps. - (a) Mixing xylose with mixture of solvents to make homogeneous solution. (b) Reacting the said homogeneous solution with heterogeneous ICaT-2 catalyst at higher temperature and pressure to produced furfural. (c) Recovery of the ICaT-2 catalyst from reaction mass by filtration. (d) Isolation of furfural from mother liquor by extraction with organic solvent and distillation. Process for producing furfural from xylose wherein amount of xylose used is in the range of 0.5 to 50% wt/wt of the reaction mass. More preferably in the range of 1 to 25 % wt/wt of reaction mass. Process for producing furfural from xylose wherein amount of catalyst used are in the range of 0.1 to 50% based on xylose weight percentage. Process for producing furfural from xylose 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. Process for producing furfural from xylose wherein content of water to organic solvent are in the range of 0.1 to 99.9 %. More preferably in the range of 10 to 50 %. Process for producing furfural from xylose wherein reaction is carried out in the temperature range 10 to 400 °C more preferably in the range of 100 to 250 °C. Process for producing furfural from xylose wherein reaction is carried out at least 10 hrs, more preferably 15 min to 5 hrs. Process for producing furfural from xylose wherein separation of the pure furfural from final reaction mixture is carried out by extraction with organic solvent such ethyl acetate, ethers, dichloromethane or methyl tertiary butyl ether and followed by vacuum distillation. DETAIL DESCRIPTION OF INVENTION In accordance with the principle of the present invention, a process for preparation of furfural from xylose 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 hexagonal organic-inorganic mesoporous silica as base metal through organic linkage. The said 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. The present invention, utilizes ICaT-2 which shows excellent reusability for furfural production. In the present invention, 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 +1°C of the desired value by PID controller. One of the embodiments of the present invention wherein xylose is dehydrated into furfural in the presence of solvent selected from the group of solvent such as water, methanol, ethanol, propanol, butanol, acetone, acetonitrile, dimethyl formamide, dimethyl sulfoxide and/or mixture thereof. One of the embodiments of present invention for process of furfural production, wherein 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 99 %. In the present invention for furfural production, wherein the amount of catalyst employed is typically about 0.01 to 50% based on weight of the xylose in the reaction mixture. One of the embodiments of the present invention for process of furfural production, wherein xylose is used in the range of 0.1 % to 50 % 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 400 °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. 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 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. 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 (TEOS+MPTS=0.1 mol) were added to the above solution. Precipitate was dried and template was removed by soxhlet extraction. Resulting material is oxidized by 30% H2O2. Further it was treated with lanthanum chloride (400 mg) in acetonitrile for 2 h. The slurry was filtered and dried under vacuum. Finally, it was 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). After specific time intervals 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. After 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. Table-1 Example Catalyst loading (gm/cc) Time (min) %Conversion (xylose) %Yield (furfural) 2 0 150 18 7- 3 0.0025 150 56 36 4 0.005 150 67 45 5 0.01 150 89 57 6 0.02 150 98 69 EXAMPLE 7-11: The reactions are carried out in 300 ml autoclave has four bladed pitch turbine for agitation and temperature is maintained at +_l°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). 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 percentage conversion and percentage yield are calculated through calibration curve method. Furfural is isolated by extraction and distillation. Table-2 Example Solvent Time (minutes) Temperature %Conversion of xylose %Yield of furfural 7 Water 180 170°C 79 32 8 Methanol: Water 180 170°C 98 . 51 9 Isopropyl alcohol: Water 180 170°C 87 57 10 Ethanol: Water 180 170°C 89 62 11 Acetone: Water 180 170 °C 92 67 EXAMPLE 12-15: 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 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. Table-3 Example Xylose (mol/lit) Time (min) Temperature %Conversion of xylose %Yield of furfural 12 0.125 180 170 °C 95 70 13 0.250 180 170°C 92 67 14 0.500 180 170°C 86 64 15 0.750 180 170°C 77 59 EXAMPLE 16-19: The reactions are carried out in 300 ml autoclave has four bladed pitch turbine for agitation and temperature is maintained at +_10C 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. Table-4 Example Temperature Time (min) Xylose (mol) %(.Conversion of xylose %Yield of furfural 16 160 °C 90 0.025 49 32 17 170 °C 90 0.025 63 40 18 175 °C 90 0.025 78 53 19 180 °C 90 0.025 94 66 EXAMPLE 20-23: 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 .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 cm3 of acetone for 30 min and dried at 120 °C for 2 h. The reusability of the catalyst is mentioned in these examples (Table5). Table-5 Example Reusability Time (min) Xylose (mol) %Conversion of xylose %yield of furfural 20 Fresh 180 0.025 92 67 21 First reuse 180 0.025 90 66 22 Second reuse 180 0.025 92 65 23 Third reuse 180 0.025 89 67 CLAIMS We Claim: 1. Batch mode process of producing furfural from xylose by using heterogeneous solid acid ICaT-2 catalyst in the presence of mixture of the solvents has been developed. 2. Process for producing furfural from xylose as claimed in claim 1 comprises of following steps. (e) Mixing xylose with a mixture of solvents to make homogeneous solution. (f) Reacting the said homogeneous solution with heterogeneous ICaT-2 catalyst at higher temperature and autogeneous pressure to produced furfural, (g) Recovery of the ICaT-2 catalyst from reaction mass by filtration. (h) Isolation of furfural from mother liquor by extraction with organic solvent and distillation. 3. Process for producing furfural from xylose as claimed in claim 1 wherein amount of xylose used are in the range of 0.25% to 100% wt/wt of xylose, more preferably in the range of 1.0% to 50 % wt/wt of xylose. 4. Process for producing furfural from xylose as claimed in claim 1 wherein heterogeneous solid acid catalyst ICaT-2 is comprises of metal sulfonate anchored with hexagonal organic-inorganic mesoporous silica through organic linkage are used. 5. Process for producing furfural from xylose as claimed in claim 1 wherein amount of catalyst used are in the range of 0.1% to 20% wt/wt percentage based on reaction mass. 6. Process for producing furfural from xylose as claimed in claim 1 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. 7. Process for producing furfural from xylose as claimed in claim 1 and 6 wherein solvent used are more preferably the mixture of water: methanol, water : ethanol, water: propanol, water: acetone and water :acetonitrile. 8. Process for producing furfural from xylose as claimed in claim 1, 6 and 7 wherein content of water to organic solvent are in the range of 0.1 to 99.9 %, more preferably in the range of 10 to 50 %. 9. Process for producing furfural from xylose as claimed in claim 1 wherein reaction is carried out in the temperature range 10 °C to 400 °C, more preferably in the range of 100 °C to 250 °C. 10. Process for producing furfural from xylose as claimed in claim 1 wherein reaction is carried out at least 10 hrs, more preferably 1 min to 5 hrs. 11. Process for producing furfural from xylose as claimed in claim 1 and 2 wherein autogeneous pressure or external pressure of the reaction are in the range of 1bar to 30 bar. 12. Process for producing furfural from xylose as claimed in claim 1 and 2 wherein separation of the pure furfural from final reaction mixture is carried out by extraction with organic solvent such ethyl acetate, ethers, dichloromethane or methyl-tertiary-butyl ether and followed by vacuum distillation.

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