CN101613331B - Method for preparing 5-acetoxymethyl furfural with carbohydrate - Google Patents
Method for preparing 5-acetoxymethyl furfural with carbohydrate Download PDFInfo
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- CN101613331B CN101613331B CN200910060096XA CN200910060096A CN101613331B CN 101613331 B CN101613331 B CN 101613331B CN 200910060096X A CN200910060096X A CN 200910060096XA CN 200910060096 A CN200910060096 A CN 200910060096A CN 101613331 B CN101613331 B CN 101613331B
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- QAVITTVTXPZTSE-UHFFFAOYSA-N CC(OCc1ccc(C=O)[o]1)=O Chemical compound CC(OCc1ccc(C=O)[o]1)=O QAVITTVTXPZTSE-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N OCc1ccc(C=O)[o]1 Chemical compound OCc1ccc(C=O)[o]1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
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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
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- Y02P20/584—Recycling of catalysts
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Abstract
A method for preparing 5-acetoxymethyl furfural with carbohydrate at normal pressure comprises the following steps: adopting fructose or glucose as raw material and dimethylsulphoxide as reaction medium to produce 5-methylol furfural through dehydration in the present of solid acid catalyst, cooling the obtained products, removing the solid acid, removing the water generated in the dehydration reaction with 4A molecular sieve, separating the molecular sieve through filtration and then adding anion-exchange resin of which anions are displaced by acetate and acetic anhydride to perform acetylation reaction to generate 5-acetoxymethyl furfural. The method has high yield, mild reaction conditions, cheap and accessible raw materials and catalyst, the catalyst can be recycled and the whole process is non-corrosive to devices and environmentally friendly.
Description
Technical field:
The present invention relates to a kind of method for preparing 5-acetyl-o-methyl furfural by carbohydrate.
Background technology:
5-acetyl-o-methyl furfural (AMF) is a kind of novel liquid fuel, has the calorific value suitable with gasoline (8.7kWh/L).In addition, AMF can be used as and produces novel plastic monomer 2, and 5-furyl dimethyl carbinol and 2, the presoma of 5-furans dioctyl phthalate, AMF can also be used for producing agricultural chemicals, spices, fine chemicals etc.
The carbohydrate dehydration generates 5 hydroxymethyl furfural (HMF), and repeated hydrogenation system dimethyl furan or long chain alkane are that biomass resource replaces the effective ways that fossil resource is produced liquid fuel.But hydrogenation reaction need consume extra hydrogen and harsh hydrogenation conditions.AMF is the acetylizad product of HMF, be acetylation reagent with acetate or diacetyl oxide usually, and acetate can be made equally by reproducible carbohydrate, so this route more meets the viewpoint of Sustainable development.
Employing sulfuric acid such as M.Bicker are catalyzer, and fructose is raw material, and acetate is reaction medium and acetylation reagent, are 180 ℃ in temperature, pressure be under the 20MPa condition reaction to obtain the fructose transformation efficiency in 2 minutes be 98%, the selectivity of AMF is 38%, yield is 37%.The condition harshness of this method, very high to equipment requirements, and with sulfuric acid as catalyzer to the conversion unit seriously corroded, contaminate environment, catalyzer is difficult to separate with product, and the AMF yield is low.
In patent WO2007104515, be reaction medium with the mixing solutions of water and acetate, 10% sulfuric acid is catalyzer, reacts under 195 ℃ high temperature.With glucose is raw material, and transformation efficiency is 10% o'clock, and the overall selectivity of HMF and AMF is greater than 90%, when being raw material with sucrose, transformation efficiency be the overall selectivity of 25% o'clock HMF and AMF still greater than 90%, but further improve when transformation efficiency, product selectivity descends.This method is carried out under High Temperature High Pressure equally, and the condition harshness is very high to equipment requirements, and the AMF yield is low.
Adopting ionic liquid [EMIM] Cl and [HMIM] Cl in patent WO2009030512 is reaction medium, CrCl
2Be catalyzer, acetate is acetylation reagent, 100 ℃; 1.25Mpa down reaction 3 hours of nitrogen atmosphere; with fructose is that raw material can obtain 74.8% AMF yield, and, source more cheap with price can only obtain 9.2% yield when glucose is raw material more widely.This method need be carried out under condition of high voltage, and ionic liquid costs an arm and a leg, and its application as reaction medium only limits to laboratory study.In addition, catalyzer is difficult to from ionic liquid to separate and continues to recycle, and therefore also can't be applied in the fairly large production.
In patent US2008200698, fructose is dehydration generation HMF in high boiling solvent earlier, under the catalysis of 4-Dimethylamino pyridine, adds the diacetyl oxide acetylize and prepares AMF, the highest about 80% the AMF yield that obtains again.The 4-Dimethylamino pyridine costs an arm and a leg in this method, as a kind of homogeneous catalyst, is difficult to partitioning cycle and uses, and this catalyzer still is a kind of deleterious chemical simultaneously, and is harmful to people's health.
Summary of the invention:
The object of the present invention is to provide a kind of easy method that can prepare 5-acetyl-o-methyl furfural by carbohydrate, with overcome cost height in the prior art, yield is low and catalyzer can not reclaim shortcomings such as repeated use.
The invention main points: normal pressure is reaction down; with fructose or glucose is raw material; methyl-sulphoxide is made reaction medium; dehydration generates 5 hydroxymethyl furfural under solid acid catalysis; remove solid acid after the cooling; add diacetyl oxide again and carry out acetylization reaction generation 5-acetyl-o-methyl furfural; adopt the 4A molecular sieve to remove the water that dehydration reaction generates before the acetylization reaction; anionite-exchange resin with the acetate moiety exchange is the catalyzer of acetylization reaction; wherein temperature of reaction is 30-90 ℃; reaction times is 0.1-4 hour, 5 hydroxymethyl furfural and diacetyl oxide mol ratio be 1: 1-1: 10.Optimal reaction temperature is 50-80 ℃, and optimum reacting time is 0.5-2 hour, 5 hydroxymethyl furfural and diacetyl oxide optimum mole ratio be 1: 2-1: 5.The anionite-exchange resin of acetate moiety exchange refers to the weak basic anion exchange resin of acetate moiety exchange or the strong anion-exchange resin of acetate moiety exchange, and wherein the weak basic anion exchange resin with the acetate moiety exchange is good.
The preparation of the anion-exchange resin catalyst of acetate moiety exchange: with the anionite-exchange resin massfraction is 10% NaCl solution soaking 8h, then with the distilled water cleaning to using AgNO
3Solution detects till the no white precipitate, is 7% ammonium acetate solution exchange again with massfraction, cleans to using AgNO with distilled water again
3Solution detects till the no white precipitate, and suction filtration is dried again, makes the anionite-exchange resin of acetate moiety exchange.
The present invention compares with existing technology has following characteristics: 1. be reflected under the gentle condition and carry out normal pressure, low temperature, less energy-consumption; 2. catalyzer is a heterogeneous catalyst, and is nontoxic, is easy to preparation, is easy to separate renewable recycling; 3. process does not have equipment corrosion; 4. the target product yield height reaches as high as more than 90%, has the favorable industrial application prospect.
Embodiment:
Embodiment 1:
With 301 type weak basic anion exchange resin massfractions is 10% NaCl solution soaking 8h, cleans to using AgNO with distilled water then
3Solution detects till the no white precipitate, is 7% ammonium acetate solution exchange again with massfraction, cleans to using AgNO with distilled water again
3Solution detects till the no white precipitate, and suction filtration is dried again, makes the weak basic anion exchange resin of acetate moiety exchange.
In a single necked round bottom flask, add 0.09g fructose (0.5mmol) and 1mL methyl-sulphoxide, add the 0.09g acidic cation-exchange resin then, connect prolong and be placed in the oil bath pan, oil bath pan is warming up to 100 ℃, constant temperature stirs, and reacts stopped reaction after 6 hours.To room temperature, centrifugation goes out catalyzer with the reaction system water-cooled.High performance liquid chromatography detects and shows that the yield of HMF is 93%.The weak basic anion exchange resin that adds the exchange of 0.05g acetate moiety, and be to add diacetyl oxide at 1: 3 according to HMF and diacetyl oxide mol ratio, 70 ℃ react 1 hour down after stopped reaction.The reaction system water-cooled to room temperature, is filtered to isolate catalyzer.High performance liquid chromatography detects and shows that the yield of AMF is 60%, in fructose.
Embodiment 2:
In a single necked round bottom flask, add 0.09g fructose (0.5mmol) and 1mL methyl-sulphoxide, add the 0.09g acidic cation-exchange resin then, connect prolong and be placed in the oil bath pan, oil bath pan is warming up to 100 ℃, constant temperature stirs, and reacts stopped reaction after 6 hours.To room temperature, centrifugation goes out catalyzer with the reaction system water-cooled.High performance liquid chromatography detects and shows that the yield of HMF is 93%.Adopt the 4A molecular sieve to remove the water that dehydration reaction generates, filter to isolate the 4A molecular sieve.According to HMF and diacetyl oxide mol ratio is 1: 3 adding diacetyl oxide, stopped reaction after reacting 1 hour under 70 ℃.With the reaction system water-cooled to room temperature.High performance liquid chromatography detects and shows that the yield of AMF is 71%, in fructose.
Embodiment 3:
In a single necked round bottom flask, add 0.09g fructose (0.5mmol) and 1mL methyl-sulphoxide, add the 0.09g acidic cation-exchange resin then, connect prolong and be placed in the oil bath pan, oil bath pan is warming up to 100 ℃, constant temperature stirs, and reacts stopped reaction after 6 hours.To room temperature, centrifugation goes out catalyzer with the reaction system water-cooled.High performance liquid chromatography detects and shows that the yield of HMF is 93%.Adopt the 4A molecular sieve to remove the water that dehydration reaction generates, filter to isolate the 4A molecular sieve.Add the weak basic anion exchange resin of 0.05g, and be to add diacetyl oxide at 1: 3 according to HMF and diacetyl oxide mol ratio according to the acetate moiety exchange of embodiment 1 preparation, 70 ℃ react 1 hour down after stopped reaction.The reaction system water-cooled to room temperature, is filtered to isolate catalyzer.High performance liquid chromatography detects and shows that the yield of AMF is 91%, in fructose.
Embodiment 4:
In a single necked round bottom flask, add 0.09g glucose (0.5mmol) and 1mL methyl-sulphoxide, add 0.018gSO then
4 2-/ ZrO
2-Al
2O
3Catalyzer connects prolong and is placed in the oil bath pan, and oil bath pan is warming up to 130 ℃, and constant temperature stirs, and reacts stopped reaction after 6 hours.To room temperature, centrifugation goes out catalyzer with the reaction system water-cooled.High performance liquid chromatography detects and shows that the yield of HMF is 50%.Adopt the 4A molecular sieve to remove the water that dehydration reaction generates, filter to isolate the 4A molecular sieve.Add the weak basic anion exchange resin of 0.05g, and be to add diacetyl oxide at 1: 3 according to HMF and diacetyl oxide mol ratio according to the acetate moiety exchange of embodiment 1 preparation, 70 ℃ react 1 hour down after stopped reaction.The reaction system water-cooled to room temperature, is filtered to isolate catalyzer.High performance liquid chromatography detects and shows that the yield of AMF is 46%, with glucose meter.
Embodiment 5:
With 717 type strong anion-exchange resin massfractions is 10% NaCl solution soaking 8h, cleans to using AgNO with distilled water then
3Solution detects till the no white precipitate, is 7% ammonium acetate solution exchange again with massfraction, cleans to using AgNO with distilled water again
3Solution detects till the no white precipitate, and suction filtration is dried again, makes the strong anion-exchange resin of acetate moiety exchange.
In a single necked round bottom flask, add 0.09g fructose (0.5mmol) and 1mL methyl-sulphoxide, add the 0.09g acidic cation-exchange resin then, connect prolong and be placed in the oil bath pan, oil bath pan is warming up to 100 ℃, constant temperature stirs, and reacts stopped reaction after 6 hours.To room temperature, centrifugation goes out catalyzer with the reaction system water-cooled.High performance liquid chromatography detects and shows that the yield of HMF is 93%.Adopt the 4A molecular sieve to remove the water that dehydration reaction generates, filter to isolate the 4A molecular sieve.The strong anion-exchange resin that adds the exchange of 0.05g acetate moiety, and be to add diacetyl oxide at 1: 3 according to HMF and diacetyl oxide mol ratio, 70 ℃ react 1 hour down after stopped reaction.The reaction system water-cooled to room temperature, is filtered to isolate catalyzer.High performance liquid chromatography detects and shows that the yield of AMF is 87%, in fructose.
Embodiment 6-11:
In six single necked round bottom flask, add 0.09g fructose (0.5mmol) and 1mL methyl-sulphoxide, add the 0.09g acidic cation-exchange resin then, connect prolong and be placed in the oil bath pan, oil bath pan is warming up to 100 ℃, constant temperature stirs, and reacts stopped reaction after 6 hours.To room temperature, centrifugation goes out catalyzer with the reaction system water-cooled.High performance liquid chromatography detects and shows that the yield of HMF is 93%.Adopt the 4A molecular sieve to remove the water that dehydration reaction generates, filter to isolate the 4A molecular sieve.Add the weak basic anion exchange resin of 0.05g according to the acetate moiety exchange of embodiment 1 preparation, and be to add diacetyl oxide at 1: 3 according to HMF and diacetyl oxide mol ratio, respectively 30,40,50,60,80,90 ℃ are reacted stopped reaction after 1 hour down.The reaction system water-cooled to room temperature, is filtered to isolate catalyzer.Reaction solution detects with high performance liquid chromatography, and the result that reaction obtains under the differing temps is set forth in the table 1.
Table 1
| The embodiment sequence number | Temperature of reaction (℃) | The yield of AMF is, in fructose % |
| 6 | 30 | 72 |
| 7 | 40 | 77 |
| 8 | 50 | 84 |
| 9 | 60 | 88 |
| 10 | 80 | 85 |
| 11 | 90 | 80 |
Embodiment 12-16:
In five single necked round bottom flask, add 0.09g fructose (0.5mmol) and 1mL methyl-sulphoxide, add the 0.09g acidic cation-exchange resin then, connect prolong and be placed in the oil bath pan, oil bath pan is warming up to 100 ℃, constant temperature stirs, and reacts stopped reaction after 6 hours.To room temperature, centrifugation goes out catalyzer with the reaction system water-cooled.High performance liquid chromatography detects and shows that the yield of HMF is 93%.Adopt the 4A molecular sieve to remove the water that dehydration reaction generates, filter to isolate the 4A molecular sieve.Add the weak basic anion exchange resin of 0.05g, and be 1: 3 adding diacetyl oxide, under 70 ℃, react 0.1,0.25,0.5,2 respectively, stopped reaction after 4 hours according to HMF and diacetyl oxide mol ratio according to the acetate moiety exchange of embodiment 1 preparation.The reaction system water-cooled to room temperature, is filtered to isolate catalyzer.Reaction solution detects with high performance liquid chromatography, and the result that reaction obtains under the differential responses time is set forth in the table 2.
Table 2
| The embodiment sequence number | Reaction times (hour) | The yield of AMF is, in fructose % |
| 12 | 0.1 | 67 |
| 13 | 0.25 | 81 |
| 14 | 0.5 | 86 |
| 15 | 2 | 91 |
| 16 | 4 | 90 |
Embodiment 17-20:
In four single necked round bottom flask, add 0.09g fructose (0.5mmol) and 1mL methyl-sulphoxide, add the 0.09g acidic cation-exchange resin then, connect prolong and be placed in the oil bath pan, oil bath pan is warming up to 100 ℃, constant temperature stirs, and reacts stopped reaction after 6 hours.To room temperature, centrifugation goes out catalyzer with the reaction system water-cooled.High performance liquid chromatography detects and shows that the yield of HMF is 93%.Adopt the 4A molecular sieve to remove the water that dehydration reaction generates, filter to isolate the 4A molecular sieve.The weak basic anion exchange resin that the acetate moiety that adding 0.05g prepares according to embodiment 1 exchanges, and be 1: 1 according to HMF and diacetyl oxide mol ratio respectively, 1: 2,1: 5,1: 10 adding diacetyl oxide, stopped reaction after reacting 1 hour under 70 ℃.The reaction system water-cooled to room temperature, is filtered to isolate catalyzer.Reaction solution detects with high performance liquid chromatography, and the result that reaction obtains under different HMF and the diacetyl oxide mol ratio is set forth in the table 3.
Table 3
| The embodiment sequence number | HMF and diacetyl oxide mol ratio | The yield of AMF is, in fructose % |
| 17 | 1∶1 | 62 |
| 18 | 1∶2 | 86 |
| 19 | 1∶5 | 91 |
| 20 | 1∶10 | 92 |
Claims (5)
1. method for preparing 5-acetyl-o-methyl furfural by carbohydrate; normal pressure is reaction down; with fructose or glucose is raw material; methyl-sulphoxide is made reaction medium; dehydration generates 5 hydroxymethyl furfural under solid acid catalysis; remove solid acid after the cooling; add diacetyl oxide again and carry out acetylization reaction generation 5-acetyl-o-methyl furfural; it is characterized in that adopting the 4A molecular sieve to remove the water that dehydration reaction generates before the acetylization reaction; anionite-exchange resin with the acetate moiety exchange is the catalyzer of acetylization reaction; wherein temperature of reaction is 30-90 ℃, and the reaction times is 0.1-4 hour, and the mol ratio of 5 hydroxymethyl furfural and diacetyl oxide is 1: 1-1: 10.
2. method according to claim 1 is characterized in that temperature of reaction is 50-80 ℃.
3. method according to claim 1 is characterized in that the reaction times is 0.5-2 hour.
4. method according to claim 1, the mol ratio that it is characterized in that 5 hydroxymethyl furfural and diacetyl oxide is 1: 2-1: 5.
5. method according to claim 1 is characterized in that the anionite-exchange resin of the acetate moiety exchange of indication is the weak base type anionite-exchange resin of acetate moiety exchange.
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| CN102453007A (en) * | 2010-10-22 | 2012-05-16 | 王天任 | Method for preparing 5-hydroxymethylfurfural |
| CN102477020A (en) * | 2010-11-29 | 2012-05-30 | 中国科学院大连化学物理研究所 | Method for preparing 5-hydroxymethyl furfural by catalysis of carbohydrate |
| KR101374219B1 (en) * | 2012-03-18 | 2014-03-13 | 서울대학교산학협력단 | Novel method for preparing 5-acetoxymethylfurfural using alkylammonium acetate salts |
| CN102993140B (en) * | 2012-12-13 | 2014-12-17 | 浙江大学 | Method for preparing 5-hydroxymethyl furfural by catalyzing biomass conversion |
| CA2977391A1 (en) | 2015-03-05 | 2016-09-09 | Bp Corporation North America Inc. | Synthesis of furans from sugars via keto intermediates |
| CN108913271A (en) * | 2018-07-05 | 2018-11-30 | 吴亚琴 | A kind of preparation method of biomass fuel feed additives |
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| CN101367782A (en) * | 2008-10-09 | 2009-02-18 | 四川大学 | Method for preparing 5-hydroxymethyl furfural by catalyzing glucose with solid ultra-strong acid |
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