CN103159707A - Method for preparing furan derivatives through biomass catalytic conversion - Google Patents
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Abstract
The invention relates to a method for preparing furan derivatives through biomass catalytic conversion. The method is characterized in that glucose, sucrose, cellobiose, cellulose, hemicellulose, lignocellulose, and the like are adopted as raw materials; under the effect of a catalyst, the raw materials are subjected to hydrolysis, isomerization, and dehydration reactions in a polar organic solvent, such that furan derivatives such as 5-hydroxymethylfurfural, 5-alkoxymethylfurfural, and furan acetals are obtained. The method has high raw material utilization rate. The system has the advantages of easy separation and easy purification.
Description
Technical field
The present invention relates to Wood Adhesives from Biomass and prepare fine chemicals and energy field of chemicals, particularly, the method that relates to the standby furan derivatives of hydrolysis, isomerization and the Dehydrations such as solid acid and catalyzed by solid base glucose, sucrose, cellobiose, Mierocrystalline cellulose, hemicellulose, lignocellulose in polar organic solvent.
Background technology
At present, energy chemical, fuel mainly depend on the fossil resources such as oil.Along with the minimizing day by day of the fossil resource reserves such as oil, seek their substitute and received domestic and international investigator's extensive concern to obtain Chemicals and the energy.Biomass resource is the organic carbon resource of the unique recyclable regenerative of nature, and carbohydrate accounts for the largest percentage in biomass resource, and especially Mierocrystalline cellulose, hemicellulose, lignocellulose belong to non-grain crop, and the source is abundant.
The furan derivatives such as furfural, 5 hydroxymethyl furfural (HMF) are one of important biomass-based hardware and software platform compounds, it is also the important intermediate of synthetic multiple fine chemicals and furyl polymkeric substance, mainly get by catalysis wood sugar, fructose Dehydration, make great progress (Energy Environ.Sci., 2011,4,2193-2205; Science, 2006,312,1933-1937).Furfural or HMF and alcohol etherificate, acetalation under acid catalysis can obtain 5-alkoxymethylfurfural and furans acetal (J.Catal., 2010,275,236-242).5-alkoxymethylfurfural and furans acetal are important fuel or fuel dopes.5-alkoxymethylfurfural and furans acetal also can obtain furfural or HMF under base catalysis.
Compare with fructose, glucose, Mierocrystalline cellulose have more the source advantage such as wide, cheap and easy to get, but realize that glucose, Mierocrystalline cellulose dehydration also have more challenge.Occurring in nature glucose major part exists with the pyrans form, and this form is unfavorable for the generation of dehydration reaction.Studies show that in a large number, glucose can be realized isomerization with fructose, the further standby HMF of Dehydration under the acid catalysis condition as alkali, glucose isomerase etc. under certain condition.
Produce HMF from biomass resource, the reaction medium of having reported comprise aprotic, polar high boiling solvent (DMSO and DMF), ionic liquid or some mixed systems (Green Chem., 2011,13,754-793).The aprotic, polar high boiling solvent as DMSO and DMF, is not easy and product separation; Use this kind solvent not only can energy expenditure larger, and it be also very large to improve the quality difficulty of product.From this viewpoint, the employing ionic liquid is reaction medium, and then may be an effective way through extraction process.Extraction solvent comprises methyl iso-butyl ketone (MIBK), methylene dichloride, ethyl acetate, tetrahydrofuran (THF), ether and acetone isopolarity solvent.Yet the HMF molecule has high polarity, and the solvability in ionic liquid is larger, and the extraction efficiency of HMF is low, needs repeated multiple times.In addition, ionic liquid is expensive, and easily by organic solvent pollution, recycling is also a great problem.At present, prepare HMF from carbohydrate and only rest on laboratory stage, large-scale application still is faced with formidable challenges, impact that environment is caused as cost, efficient, raw material supplying and commercial run etc.Separating, purifying of the poor efficiency of building-up process and HMF is topmost technical barrier.The method of producing HMF from biomass resource of having reported seldom provides the separation yield data, and the HMF yield of report is based on stratographic analysis mostly, is difficult to obtain the actual product yield.Therefore, exploitation is efficient, green method is efficiently produced the HMF product from biomass resource, has great importance and application prospect.
Research Thinking of the present invention is, develop a kind of cheapness, efficiently, easily recycle, eco-friendly reaction medium, take biomass such as glucose, sucrose, cellobiose, Mierocrystalline cellulose, hemicellulose, lignocelluloses as raw material, catalysis process is produced furan derivatives, replenish and the alternative non-renewable fossil resource of part, have important scientific meaning and using value.
Summary of the invention
The objective of the invention is to develop a kind of efficient, green reaction medium system, take biomass resource as the waste Chemicals with technology and the method for energy chemical, the shortage of alleviating, substituting, replenish the fossil resources such as oil, for synthesizing of Chemicals and energy chemical, provide the new technology and method of Sustainable development.
Specifically, exactly take polar organic solvent as reaction medium, glucose, sucrose, cellobiose, Mierocrystalline cellulose, hemicellulose, lignocellulose etc. are raw material, under katalysis, purification and sepn process by hydrolysis, isomerization and dehydration reaction and product, prepare high-quality furan derivatives, and structure and the purity of product are tested, for application provides reference and foundation.
According to route provided by the invention, reaction raw materials is glucose and the disaccharides take glucose as structural unit or polysaccharide, as sucrose, cellobiose, Mierocrystalline cellulose, hemicellulose, lignocellulose.Cellobiose, Mierocrystalline cellulose, hemicellulose, lignocellulose are non-grain crop, and the source is wide, cheap and easy to get.Glucose in natural existence form take β-pyrans form as main, this existence form is unfavorable for that Direct Dehydration generates HMF under acid catalysis, need to be under glucose isomerase or base catalysis mutarotation and isomerization to fructose, realize under acid catalysis that further dehydration generates HMF.
According to route provided by the invention, glucose, sucrose, cellobiose, Mierocrystalline cellulose, hemicellulose, lignocellulose, and hydrolysis, isomerization and the dehydration reaction of the biomass materials such as Mierocrystalline cellulose, hemicellulose, lignocellulose are carried out in same reactor simultaneously, for avoiding the neutralization of protonic acid, alkali, the acid of using is solid acid, and the alkali that uses is solid alkali.Solid acid easily separates with product with solid alkali, realizes recycling of catalyzer, and little to the corrosion of equipment.
According to method provided by the invention, reaction substrate is the biomass such as glucose, sucrose, cellobiose, Mierocrystalline cellulose, hemicellulose, lignocellulose, and the catalyzer that the hydrolysis of reaction substrate and dehydration reaction are used comprises: SO
4 2-/ ZrO
2, SO
4 2-/ ZrO
2-Al
2O
3, SO
4 2-/ ZrO
2-SiO
2, Amberlyst-15, Nafion NR50, H-ZSM5, H-Beta, Nb
2O
5-nH
2One or more in the solid acids such as O, solid acid catalyst consumption are the 1-40wt% of biomass material amount; The catalyzer that reaction substrate or reaction intermediate isomerization reaction are used comprises: hydrotalcite (HT), MgO, Mg (OH)
2, MgAlO
2, CaO, Ca (OH)
2, Ba (OH)
2, Cu (OH)
2Deng one or more in solid alkali, the solid base catalyst consumption is the 1-40wt% of biomass material.Temperature of reaction is 80-180 ℃, and the reaction times is 1-48h.Optimal reaction temperature is 100-160 ℃, and optimum reacting time is 10-30h.
According to method provided by the invention, the selection of reaction solvent is to realize one of key of hydrolysis and dehydration.Polar organic solvent has apparent benefit as reaction medium, and except acetone, tetrahydrofuran (THF), acetonitrile isopolarity solvent, alcoholic solvent also has great advantage.One, alcohols hydroxyl are the key characters of the biomass such as carbohydrate, can be directed to biomass, and cheap.Its two, low-carbon alcohol series products boiling point is low, easily realizes recycling as solvent, energy consumption is low, and environmental friendliness.
According to method provided by the invention, reaction medium is polar organic solvent, comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol, cyclopentanol, hexanol, hexalin, acetonitrile, acetone, tetrahydrofuran (THF), cheap, boiling point is low, easily and product separation, cycling and reutilization, for the scale operation furan derivatives provides may.In addition, alcohols easily further reacts with the HMF that generates, and obtains ether or acetal compound, can effectively stop degraded or the polyreaction of HMF, reduces the generation of other by products.Use alcoholic solvent, after sugar, Mierocrystalline cellulose, hemicellulose, cellulignin hydrolysis and dehydration, might directly obtain etherificate and the acetalation product of HMF, these products are high-quality fuel or fuel dope.
According to method provided by the invention, the method for purifying and separating of the thick product of gained is extraction, desalination, distillation, and separation efficiency is high.Wherein extraction process organic solvent used is methyl iso-butyl ketone (MIBK), methylene dichloride, ethyl acetate, ether, obtains high-quality furan derivatives through extracting and separating.
Hydrolysis and dehydration reaction system can highly selectivies, and high conversion catalysis glucose, sucrose, cellobiose, Mierocrystalline cellulose, hemicellulose, lignocellulose etc. prepare high-quality furan derivatives, and the product separation yield is high.Utilize
1H NMR can obtain the ratio of different sorts furan derivatives.
Embodiment
The below describes the present invention in detail with specific embodiments, but the invention process is not limited to these embodiment:
Embodiment 1: with 1.8g glucose, and 0.020g SO
4 2-/ ZrO
2, 0.020g HT, 20ml methyl alcohol join in 50mL band teflon-lined stainless steel cauldron, are heated to 100 ℃, react 4h at this temperature.Suction filtration is removed unreacted glucose and other insoluble impurities, adds appropriate NaOH solution to transfer to neutrality in filtrate, and the rotary evaporation desolventizing adds 2ml H
2O, to organic phase, gained organic phase rotary evaporation gets highly purified furan derivatives, separation yield 85% with ethyl acetate extraction.Use gas chromatography-mass spectrum (GC-MS) tentatively to determine the composition of reaction product, and compare with the retention time of reference material (HMF, 5-alkoxymethylfurfural and furans acetal) in gas-chromatography (GC), qualitative primary product is HMF, 5-alkoxymethylfurfural and furans acetal.The ratio of different sorts furan derivatives by
1H NMR is definite, and measurement result is: HMF: the 5-alkoxymethylfurfural: furans acetal=80: 16: 4.
Embodiment 2: with 1.8g sucrose, and 0.120g SO
4 2-/ ZrO
2-Al
2O
3, 0.120g MgO, 20ml ethanol joins in 50mL band teflon-lined stainless steel cauldron, is heated to 120 ℃, reacts 8h at this temperature.Suction filtration is removed unreacted fructose and other insoluble impurity, adds appropriate NaOH solution to transfer to neutrality in filtrate, and the rotary evaporation desolventizing adds 2ml H
2O, to organic phase, gained organic phase rotary evaporation gets highly purified furan derivatives, separation yield 91% with ethyl acetate extraction.Use GC-MS tentatively to determine the composition of reaction product, and compare with the retention time of reference material (HMF, 5-alkoxymethylfurfural and furans acetal) in GC, qualitative primary product is HMF, 5-alkoxymethylfurfural and furans acetal.The ratio of different sorts furan derivatives by
1H NMR is definite, and measurement result is: HMF: the 5-alkoxymethylfurfural: furans acetal=76: 16: 8.
Embodiment 3: with the 1.8g cellobiose, and 0.210g SO
4 2-/ ZrO
2-SiO
2, 0.210gMg (OH)
2, the 20ml n-propyl alcohol joins in 50mL band teflon-lined stainless steel cauldron, is heated to 180 ℃, reacts 40h at this temperature.Suction filtration is removed unreacted wood sugar and other insoluble impurity, adds appropriate NaOH solution to transfer to neutrality in filtrate, and the rotary evaporation desolventizing adds 2ml H
2O is extracted into organic phase with methyl iso-butyl ketone (MIBK), and gained organic phase rotary evaporation gets highly purified furfural, separation yield 89%.Use GC-MS tentatively to determine the composition of reaction product, and compare with the retention time of reference material (HMF, 5-alkoxymethylfurfural and furans acetal) in GC, qualitative primary product is HMF, 5-alkoxymethylfurfural and furans acetal.The ratio of different sorts furan derivatives by
1H NMR is definite, and measurement result is: HMF: the 5-alkoxymethylfurfural: furans acetal=40: 46: 14.
Embodiment 4: with the 1.8g Mierocrystalline cellulose, and 0.352g Amberlyst-15,0.352g MgAlO
2, the 20ml Virahol joins in 50mL band teflon-lined stainless steel cauldron, is heated to 130 ℃, reacts 48h at this temperature.Suction filtration is removed unreacted Mierocrystalline cellulose and other insoluble impurity, adds appropriate NaOH solution to transfer to neutrality in filtrate, and the rotary evaporation desolventizing adds 2ml H
2O, to organic phase, gained organic phase rotary evaporation gets highly purified HMF, separation yield 95% with dichloromethane extraction.Use GC-MS tentatively to determine the composition of reaction product, and compare with the retention time of reference material (HMF, 5-alkoxymethylfurfural and furans acetal) in GC, qualitative primary product is HMF, 5-alkoxymethylfurfural and furans acetal.The ratio of different sorts furan derivatives by
1H NMR is definite, and measurement result is: HMF: the 5-alkoxymethylfurfural: furans acetal=90: 8: 2.
Embodiment 5: with the 1.8g hemicellulose, 0.468g Nafion NR50,0.468g CaO, the 20ml trimethyl carbinol join in 50mL band teflon-lined stainless steel cauldron, are heated to 80 ℃, react 24h at this temperature.Suction filtration is removed unreacted hemicellulose and other insoluble impurity, adds appropriate NaOH solution to transfer to neutrality in filtrate, and the rotary evaporation desolventizing adds 2ml H
2O, to organic phase, gained organic phase rotary evaporation gets highly purified HMF, separation yield 80% with ethyl acetate extraction.Use GC-MS tentatively to determine the composition of reaction product, and compare with the retention time of reference material (furfural, HMF, 5-alkoxymethylfurfural and furans acetal) in GC, qualitative primary product is furfural, HMF, 5-alkoxymethylfurfural and furans acetal.The ratio of different sorts furan derivatives by
1H NMR is definite, and measurement result is: furfural: HMF: the 5-alkoxymethylfurfural: furans acetal=21: 72: 5: 2.
Embodiment 6: with the 1.8g cellulignin, and 0.549g H-ZSM5,0.549g Ca (OH)
2, the 20ml propyl carbinol joins in 50mL band teflon-lined stainless steel cauldron, is heated to 150 ℃, reacts 16h at this temperature.Suction filtration is removed unreacted cellulignin and other insoluble impurity, adds appropriate NaOH solution to transfer to neutrality in filtrate, and the rotary evaporation desolventizing adds 2ml H
2O, to organic phase, gained organic phase rotary evaporation gets highly purified HMF, separation yield 92% with extracted with diethyl ether.Use GC-MS tentatively to determine the composition of reaction product, and compare with the retention time of reference material (furfural, HMF, 5-alkoxymethylfurfural and furans acetal) in GC, qualitative primary product is furfural, HMF, 5-alkoxymethylfurfural and furans acetal.The ratio of different sorts furan derivatives by
1H NMR is definite, and measurement result is: furfural: HMF: the 5-alkoxymethylfurfural: furans acetal=12: 83: 3: 2.
Embodiment 7: with the 1.8g Mierocrystalline cellulose, and 0.643g H-Beta, 0.643g Ba (OH)
2, the 20ml amylalcohol joins in 50mL band teflon-lined stainless steel cauldron, is heated to 140 ℃, reacts 30h at this temperature.Suction filtration is removed unreacted Mierocrystalline cellulose and other insoluble impurity, adds appropriate NaOH solution to transfer to neutrality in filtrate, and the rotary evaporation desolventizing adds 2ml H
2O, to organic phase, gained organic phase rotary evaporation gets highly purified HMF, separation yield 88% with ethyl acetate extraction.Use GC-MS tentatively to determine the composition of reaction product, and compare with the retention time of reference material (HMF, 5-alkoxymethylfurfural and furans acetal) in GC, qualitative primary product is HMF, 5-alkoxymethylfurfural and furans acetal.The ratio of different sorts furan derivatives by
1H NMR is definite, and measurement result is: HMF: the 5-alkoxymethylfurfural: furans acetal=83: 12: 5.
Embodiment 8: with 1.8g glucose, and 0.719g Nb
2O
5-nH
2O, 0.719g Cu (OH)
2, the 20ml acetonitrile joins in 50mL band teflon-lined stainless steel cauldron, is heated to 125 ℃, reacts 1.5h at this temperature.Suction filtration is removed unreacted glucose and other insoluble impurity, adds appropriate NaOH solution to transfer to neutrality in filtrate, and the rotary evaporation desolventizing adds 2ml H
2O is extracted into organic phase with methyl iso-butyl ketone (MIBK), and gained organic phase rotary evaporation gets highly purified HMF, separation yield 82%.Use GC-MS tentatively to determine the composition of reaction product, and compare with the retention time of reference material (HMF, 5-alkoxymethylfurfural and furans acetal) in GC, qualitative primary product is HMF, 5-alkoxymethylfurfural and furans acetal.The ratio of different sorts furan derivatives by
1H NMR is definite, and measurement result is: HMF: the 5-alkoxymethylfurfural: furans acetal=88: 2: 10.
Embodiment 9: with the 1.8g cellobiose, and 0.687g SO
4 2-/ ZrO
2-SiO
2, 0.687gMg (OH)
2, 20ml acetone joins in 50mL band teflon-lined stainless steel cauldron, is heated to 110 ℃, reacts 36h at this temperature.Suction filtration is removed unreacted Mierocrystalline cellulose and other insoluble impurity, adds appropriate NaOH solution to transfer to neutrality in filtrate, and the rotary evaporation desolventizing adds 2ml H
2O, to organic phase, gained organic phase rotary evaporation gets highly purified HMF, separation yield 96% with dichloromethane extraction.Use GC-MS tentatively to determine the composition of reaction product, and compare with the retention time of reference material (HMF, 5-alkoxymethylfurfural and furans acetal) in GC, qualitative primary product is HMF, 5-alkoxymethylfurfural and furans acetal.The ratio of different sorts furan derivatives by
1H NMR is definite, and measurement result is: HMF: the 5-alkoxymethylfurfural: furans acetal=95: 2: 3.
Embodiment 10: with 1.8g sucrose, and 0.198g Aberlyst-15,0.198gSO
4 2-/ ZrO
2-Al
2O
3, 0.396g Cu (OH)
2, the 20ml tetrahydrofuran (THF) joins in 50mL band teflon-lined stainless steel cauldron, is heated to 90 ℃, reacts 28h at this temperature.Suction filtration is removed unreacted wood sugar and other insoluble impurity, adds appropriate NaOH solution to transfer to neutrality in filtrate, and the rotary evaporation desolventizing adds 2ml H
2O, to organic phase, gained organic phase rotary evaporation gets highly purified HMF, separation yield 90% with ethyl acetate extraction.Use GC-MS tentatively to determine the composition of reaction product, and compare with the retention time of reference material (HMF, 5-alkoxymethylfurfural and furans acetal) in GC, qualitative primary product is HMF, 5-alkoxymethylfurfural and furans acetal.The ratio of different sorts furan derivatives by
1H NMR is definite, and measurement result is: HMF: the 5-alkoxymethylfurfural: furans acetal=90: 6: 4.
Embodiment 11: with the 1.8g hemicellulose, and 0.518g H-ZSM5,0.259g HT, 0.259g MgAlO
2, the 20ml hexalin joins in 50mL band teflon-lined stainless steel cauldron, is heated to 160 ℃, reacts 12h at this temperature.Suction filtration is removed unreacted hemicellulose and other insoluble impurity, adds appropriate NaOH solution to transfer to neutrality in filtrate, and the rotary evaporation desolventizing adds 2ml H
2O, to organic phase, gained organic phase rotary evaporation gets highly purified HMF, separation yield 86% with ethyl acetate extraction.Use GC-MS tentatively to determine the composition of reaction product, and compare with the retention time of reference material (furfural, HMF, 5-alkoxymethylfurfural and furans acetal) in GC, qualitative primary product is furfural, HMF, 5-alkoxymethylfurfural and furans acetal.The ratio of different sorts furan derivatives by
1H NMR is definite, and measurement result is: furfural: HMF: the 5-alkoxymethylfurfural: furans acetal=19: 76: 3: 2.
Embodiment 12: with 1.8g glucose, and 0.194g Na
2O
5-nH
2O, 0.194g MgO, 20ml cyclopentanol join in 50mL band teflon-lined stainless steel cauldron, are heated to 140 ℃, react 12h at this temperature.Suction filtration is removed unreacted glucose and other insoluble impurity, adds appropriate NaOH solution to transfer to neutrality in filtrate, and the rotary evaporation desolventizing adds 2ml H
2O, to organic phase, gained organic phase rotary evaporation gets highly purified HMF, separation yield 80% with extracted with diethyl ether.Use GC-MS tentatively to determine the composition of reaction product, and compare with the retention time of reference material (HMF, 5-alkoxymethylfurfural and furans acetal) in GC, qualitative primary product is HMF, 5-alkoxymethylfurfural and furans acetal.The ratio of different sorts furan derivatives by
1H NMR is definite, and measurement result is: HMF: the 5-alkoxymethylfurfural: furans acetal=96: 1: 3.
Embodiment 13: with the 9.0g Mierocrystalline cellulose, and 1.826g Amberlyst-15,1.826g MgAlO
2, the 100ml hexanol joins in 250mL band teflon-lined stainless steel cauldron, is heated to 150 ℃, reacts 48h at this temperature.Suction filtration is removed unreacted Mierocrystalline cellulose and other insoluble impurity, adds appropriate NaOH solution to transfer to neutrality in filtrate, and the rotary evaporation desolventizing adds 10ml H
2O, to organic phase, gained organic phase rotary evaporation gets highly purified HMF, separation yield 94% with ethyl acetate extraction.Use GC-MS tentatively to determine the composition of reaction product, and compare with the retention time of reference material (HMF, 5-alkoxymethylfurfural and furans acetal) in GC, qualitative primary product is HMF, 5-alkoxymethylfurfural and furans acetal.The ratio of different sorts furan derivatives by
1H NMR is definite, and measurement result is: HMF: the 5-alkoxymethylfurfural: furans acetal=30: 45: 25.
Embodiment 14: with the 18.0g Mierocrystalline cellulose, and 1.837g SO
4 2-/ ZrO
2-SiO
2, 1.837g Ba (OH)
2, the 200ml isopropylcarbinol joins in 500mL band teflon-lined stainless steel cauldron, is heated to 100 ℃, reacts 36h at this temperature.Suction filtration is removed unreacted Mierocrystalline cellulose and other insoluble impurity, adds appropriate NaOH solution to transfer to neutrality in filtrate, and the rotary evaporation desolventizing adds 20ml H
2O, to organic phase, gained organic phase rotary evaporation gets highly purified HMF, separation yield 90% with ethyl acetate extraction.Use GC-MS tentatively to determine the composition of reaction product, and compare with the retention time of reference material (HMF, 5-alkoxymethylfurfural and furans acetal) in GC, qualitative primary product is HMF, 5-alkoxymethylfurfural and furans acetal.The ratio of different sorts furan derivatives by
1H NMR is definite, and measurement result is: HMF: the 5-alkoxymethylfurfural: furans acetal=22: 46: 34.
The present invention has developed a kind of polar organic solvent system of efficient, cleaning, take biomass such as glucose, sucrose, cellobiose, Mierocrystalline cellulose, hemicellulose, lignocelluloses as raw material, has produced high-quality furan derivatives under katalysis.This catalyzer, solvent system are cheap and easy to get, easily and product separation, can realize the recycle of catalyzer, solvent.Excellent product performance, purity are very high.This technological line reduces Chemicals and energy chemical to the dependence of the fossil resources such as oil for the shortage of alleviating petroleum resources, has great importance.
Claims (8)
1. a biomass catalyzing transforms the method for preparing furan derivatives, it is characterized in that: the method is in the polar organic solvent medium, one or two or more kinds in glucose, sucrose, cellobiose, Mierocrystalline cellulose, hemicellulose, the lignocellulose is as raw material, under catalyst action, be hydrolyzed, isomerization and dehydration reaction, obtain the furan derivatives crude product; After separation and purification, obtain furan derivatives.
2. method according to claim 1, it is characterized in that: the reaction medium that catalyzed conversion prepares furan derivatives is polar organic solvent, comprises one or more in the cycloalcohol of tetrahydrofuran (THF), acetonitrile or acetone, C1-C6 low carbon fat alcohol, five-ring or six-ring.
3. method according to claim 2, it is characterized in that: described C1-C6 low carbon fat alcohol is one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, amylalcohol, hexanol; Cycloalcohol is cyclopentanol or hexalin.
4. method according to claim 1, it is characterized in that: hydrolysis, isomerization and dehydration reaction that catalyzed conversion prepares furan derivatives are to carry out in same reactor, the catalyst component of hydrolysis and dehydration reaction use comprises: SO
4 2-/ ZrO
2, SO
4 2-/ ZrO
2-Al
2O
3, SO
4 2-/ ZrO
2-SiO
2, Amberlyst-15, Nafion NR50, H-ZSM5, H-Beta, Nb
2O
5-nH
2One or more in the O solid acid, solid acid catalyst consumption are the 1-40wt% of biomass material amount;
The catalyst component that reaction substrate or reaction intermediate isomerization reaction are used comprises: hydrotalcite (HT), MgO, Mg (OH)
2, MgAlO
2, CaO, Ca (OH)
2, Ba (OH)
2, Cu (OH)
2One or more in solid alkali, solid base catalyst consumption are the 1-40wt% of biomass material.
5. according to claim 1,2 or 4 described methods, it is characterized in that: temperature of reaction is 80-180 ℃, the reaction times is 1-48h.
6. method according to claim 5, it is characterized in that: optimal reaction temperature is 100-160 ℃, optimum reacting time is 10-30h.
7. method according to claim 1, it is characterized in that: furan derivatives comprises one or more in 5 hydroxymethyl furfural, 5-alkoxymethylfurfural, furans acetal.
8. method according to claim 1 is characterized in that:
Biomass catalyzing transforms and prepares the thick product of furan derivatives, and the method for purifying and separating of taking is extraction, desalination, distillation;
Extraction process organic solvent used is one or more plural components in methyl iso-butyl ketone (MIBK), methylene dichloride, ethyl acetate, ether.
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| WO2017003294A1 (en) * | 2015-07-01 | 2017-01-05 | Furanix Technologies B.V. | Process for the preparation of a furfural derivative comprising neutralizing an acid reaction mixture |
| CN107382920A (en) * | 2017-07-11 | 2017-11-24 | 武汉轻工大学 | A kind of method by one pot of 5 hydroxymethylfurfural of preparation of cellulose |
| CN107912039A (en) * | 2015-07-01 | 2018-04-13 | 辛维纳有限合伙公司 | It is used to prepare the method for furfural derivatives |
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| WO2017003294A1 (en) * | 2015-07-01 | 2017-01-05 | Furanix Technologies B.V. | Process for the preparation of a furfural derivative comprising neutralizing an acid reaction mixture |
| CN107848996A (en) * | 2015-07-01 | 2018-03-27 | 辛维纳有限合伙公司 | The method for preparing alditol derivative including neutralizing acidic reaction mixture |
| CN107912039A (en) * | 2015-07-01 | 2018-04-13 | 辛维纳有限合伙公司 | It is used to prepare the method for furfural derivatives |
| US10266508B2 (en) | 2015-07-01 | 2019-04-23 | Synvina C.V. | Process for the preparation of a furfural derivative comprising neutralizing an acid reaction mixture |
| CN107848996B (en) * | 2015-07-01 | 2021-07-27 | 福兰尼克斯科技公司 | Process for the preparation of furfural derivatives comprising neutralization of the acidic reaction mixture |
| CN107912039B (en) * | 2015-07-01 | 2021-11-05 | 福兰尼克斯科技公司 | Process for producing furfural derivative |
| CN107382920A (en) * | 2017-07-11 | 2017-11-24 | 武汉轻工大学 | A kind of method by one pot of 5 hydroxymethylfurfural of preparation of cellulose |
| CN107382920B (en) * | 2017-07-11 | 2020-01-17 | 武汉轻工大学 | Method for preparing 5-hydroxymethylfurfural from cellulose in one pot |
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