CN102206198A - Method for synthesizing 5-(alcoxylmethyl) furfural by using microwaves - Google Patents
Method for synthesizing 5-(alcoxylmethyl) furfural by using microwaves Download PDFInfo
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Abstract
The invention discloses a method for synthesizing 5-(alcoxylmethyl) furfural by using microwaves. In the invention, the 5-(alcoxylmethyl) furfural is formed by microwave catalysis process of sugar in alcohol in the presence of an acidic catalyst, and by adding a small amount of inorganic salt into reaction solution, the yield of the 5-(alcoxylmethyl) furfural can be improved. In the invention, microwave catalysis is adopted, the reaction time is short, the reaction energy consumption is low, the process is simple, the conversion is quick and the yield is high. Compared with the conventional method, discharge of harmful waste liquid is avoided.
Description
Technical field
The invention belongs to the organic synthesis energy technology field, relate to the method for synthetic 5-(alkoxyl-methyl) furfural of a kind of use microwave method particularly.
Background technology
5-(alkoxyl-methyl) furfural has an alkoxyl-methyl and an aldehyde radical in the molecule, generally is to react in ethanol by carbohydrate to obtain or in alcohol, become ether by 5 hydroxymethyl furfural, and be a kind of fuel or fuel dope that application prospect is arranged.People such as Gruter report that the energy density of 5-(ethoxymethyl) furfural reaches 8.7kwh/L, a little less than gasoline (8..8kwh/L) and diesel oil (9.7kwh/L), than alcoholic acid energy density (6.1kwh/L) height.In hydrogen environment, it can continue reaction with ethanol and generate 2 under an acidic catalyst existence condition, and 5-two (ethoxymethyl) furfural can directly use as biofuel.5-(ethoxymethyl) furfural and 2,5-two (ethoxymethyl) furfural all from biomass obtain, 100% renewable energy source compound, and can not generate low value or valueless by product, such as in the process of production biofuel, not producing glycerol.
The Another application of 5-(alkoxyl-methyl) furfural is aspect aviation fuel, and aviation fuel requires to have high energy density, burning-point and lower zero pour.Aviation fuel in the ideal should be obtained as raw material by biomass or biological product, and in other words, these aviation fuel should be feasible economically, can accept on energy requirement.
Making the people interested is some characteristics and the potential that some furfuran compounds have had becomes aviation fuel.Different with the compound that from fossil oil, obtains, these compounds that obtain from biomass have very high degree of unsaturation, hydrogen and the furan compound of storing hydrogen can be used as the media of cheap storage hydrogen and do not need hydrogen is discharged, because can act as a fuel together.More valuable is, these biomass fuels flash-point when higher energy density is provided is higher than 38 ℃, and zero pour is lower than-47 ℃, and in other words, these fuel are highly stable as the aviation fuel use properties.
Microwave is the hertzian wave of frequency between 300MHz-300GHz, between the ir radiation and radiowave of electromagnetic spectrum.The microwave frequency that is usually used in heating generally is fixed on 2450MHz or 915MHz.The ultimate principle of microwave heating is the conduction and the dielectric substance polarization of charged particle.The material molecule dipole polarization speed of response and microwave frequency are suitable in the microwave field, yet the dielectric medium dipole polarization that causes under microwave action often lags behind microwave frequency again, make the microwave field energy waste and are converted into heat energy.Microwave just more and more is subjected to people's attention to the promoter action of chemical reaction, utilizes the heat effect of microwave and speed that magnetoresistive effect can improve chemical reaction significantly and changes reaction mechanism, has obtained widespread use in organic synthesis.
Summary of the invention
The method that the object of the present invention is to provide a kind of microwave to synthesize 5-(alkoxyl-methyl) furfural uses microwave heating to replace traditional heating means, can guarantee better conversion rate and productive rate when shortening the reaction times.
For achieving the above object, microwave provided by the invention synthesizes the method for 5-(alkoxyl-methyl) furfural, and with sugar and pure in the presence of an acidic catalyst, microwave heating is reacted the back and added ethyl acetate extraction, collects organic phase, obtains 5-(alkoxyl-methyl) furfural; Described sugar is a kind of or mixture of monose, disaccharides, polysaccharide, glycan; Described catalyzer is solid acid, mineral acid or organic acid.Catalyzer add-on of the present invention and alcoholic solvent are not strict with on consumption.
In the described method, microwave heating reaction back adding inorganic salt and ethyl acetate extraction can improve the output capacity of product.
In the described method, inorganic salt are a kind of or mixtures of sodium-chlor, Repone K, magnesium chloride.
In the described method, sugar is glucose, sucrose, inulin, cellulosic a kind of or mixture.
In the described method, catalyzer is CT-700, Amberlyst-15, hydrochloric acid, sulfuric acid, zeolite or Lewis acid.
In the described method, alcohol is methyl alcohol, ethanol, Virahol or the trimethyl carbinol; The product that adding methyl alcohol obtains is 5-(methoxyl methyl) furfural; The product that adding ethanol obtains is 5-(ethoxymethyl) furfural; The product that the adding Virahol obtains is 5-(the different third an oxygen methyl) furfural; The product that the adding trimethyl carbinol obtains is 5-(uncle's fourth oxygen methyl) furfural.
In the described method, the temperature of reacting by heating is 60 ℃-180 ℃.
In the described method, the reaction times was at 30 minutes to 2 hours.
The invention has the advantages that:
1) use be simple and easy to acid catalyst replace complicated catalyst system, as solvent, greatly reduce production cost with cheap free of contamination alcohol;
2) reaction conditions is gentle, and energy consumption is low;
3) do not pollute the environment in reaction process, solvent is environmentally friendly.
Embodiment
The characteristics that microwave catalysis of the present invention synthesizes 5-(alkoxyl-methyl) furfural are with alcohol as solvent, green non-pollution, realized in the whole process environment-friendly green being synthesized theory, and at utmost reduced production cost, for later suitability for industrialized production provides possibility.
Below implementation method be to the further specifying of the inventive method, but the present invention is not limited to following implementation method.
Embodiment 1
Take by weighing fructose 4.5g (25mmol) and CT-700 solid acid catalyst 900mg (10wt%), join in the reactor of tetrafluoroethylene, add the 40mL dehydrated alcohol then and stir magneton in reactor, the sealing back is 120 ℃ of reaction 10min in microwave reactor.After reaction stops, with Rotary Evaporators ethanol is spun off, add ethyl acetate extraction again (because ethyl acetate and salt solution do not dissolve each other, the productive rate that therefore can add a small amount of saturated aqueous common salt extraction can raising product), collected organic layer, on Rotary Evaporators, be spin-dried for,, mix the back and use to wherein adding quantitative sym-trimethylbenzene as interior mark
1The productive rate that H NMR calculates 5-(ethoxymethyl) furfural is 28.2%
Embodiment 2
(wherein fructose is as reaction substrate to take by weighing fructose 4.5g (25mmol), CT-700 solid acid catalyst 900mg (10wt%) and sodium-chlor 146mg (2.5mmol), CT-700 and sodium-chlor are as catalyzer, down together), join in the reactor of tetrafluoroethylene, add the 40mL dehydrated alcohol then and stir magneton in reactor, the sealing back is 120 ℃ of reaction 10min in microwave reactor.After reaction stops, with Rotary Evaporators ethanol being spun off, add ethyl acetate again, after the saturated aqueous common salt extraction of newly joining on a small quantity, collected organic layer is spin-dried on Rotary Evaporators, to wherein adding quantitative sym-trimethylbenzene, mixes the back and uses
1The productive rate that H NMR calculates 5-(ethoxymethyl) furfural is 49.5%
Embodiment 3
Take by weighing fructose 4.5g (25mmol), CT-700 solid acid catalyst 900mg (10wt%) and sodium-chlor 146mg (2.5mmol), join in the reactor of tetrafluoroethylene, add the 40mL dehydrated alcohol then and stir magneton in reactor, the sealing back is 120 ℃ of reaction 30min in microwave reactor.After reaction stops, with Rotary Evaporators ethanol being spun off, add ethyl acetate again, after a small amount of saturated aqueous common salt extraction, collected organic layer is spin-dried on Rotary Evaporators, to wherein adding quantitative sym-trimethylbenzene, mixes the back and uses
1The productive rate that H NMR calculates 5-(ethoxymethyl) furfural is 52.4%.
Embodiment 4
Take by weighing fructose 4.5g (25mmol), 98% the vitriol oil 135 μ L (2.5mmol) and Repone K 190mg (2.5mmol), join in the reactor of tetrafluoroethylene, add the 40mL dehydrated alcohol then and stir magneton in reactor, the sealing back is 120 ℃ of reaction 10min in microwave reactor.After reaction stops, with Rotary Evaporators ethanol being spun off, add ethyl acetate again, after a small amount of saturated aqueous common salt extraction, collected organic layer is spin-dried on Rotary Evaporators, to wherein adding quantitative sym-trimethylbenzene, mixes the back and uses
1The productive rate that H NMR calculates 5-(ethoxymethyl) furfural is 39.6%.
Embodiment 5
Take by weighing inulin 4.5g, Amberlist-15 solid acid catalyst 900mg (10wt%) and Repone K 190mg (2.5mmol), join in the reactor of tetrafluoroethylene, add the 40mL dehydrated alcohol then and stir magneton in reactor, the sealing back is 120 ℃ of reaction 10min in microwave reactor.After reaction stops, with Rotary Evaporators ethanol being spun off, add ethyl acetate again, after a small amount of saturated aqueous common salt extraction, collected organic layer is spin-dried on Rotary Evaporators, to wherein adding quantitative sym-trimethylbenzene, mixes the back and uses
1The productive rate that H NMR calculates 5-(ethoxymethyl) furfural is 19.9%.
Embodiment 6
Take by weighing glucose 4.5g (25mmol), 38% concentrated hydrochloric acid 207 μ L (2.5mmol) and five water tin chloride 875mg (2.5mmol), join in the reactor of tetrafluoroethylene, add the 40mL dehydrated alcohol then and stir magneton in reactor, the sealing back is 140 ℃ of reaction 30min in microwave reactor.After reaction stops, with Rotary Evaporators ethanol being spun off, add ethyl acetate again, after a small amount of saturated aqueous common salt extraction, collected organic layer is spin-dried on Rotary Evaporators, to wherein adding quantitative sym-trimethylbenzene, mixes the back and uses
1The productive rate that H NMR calculates 5-(ethoxymethyl) furfural is 11.1%.
Claims (10)
1. the method for synthetic 5-(alkoxyl-methyl) furfural of microwave with sugar and pure in the presence of an acidic catalyst, adds ethyl acetate extraction after microwave heating is reacted, and collects organic phase, obtains 5-(alkoxyl-methyl) furfural.
2. method according to claim 1, wherein, described sugar is a kind of or mixture of monose, disaccharides, polysaccharide, glycan.
3. method according to claim 1 and 2, wherein, described sugar is glucose, sucrose, inulin, cellulosic a kind of or mixture.
4. method according to claim 1, wherein, described catalyzer is solid acid, mineral acid or organic acid.
5. according to claim 1 or 4 described methods, wherein, described catalyzer is CT-700, Amberlyst-15, hydrochloric acid, sulfuric acid, zeolite or Lewis acid.
6. method according to claim 1, wherein, microwave heating reaction back adds inorganic salt and ethyl acetate extraction.
7. method according to claim 6, wherein, described inorganic salt are a kind of or mixtures in sodium-chlor, Repone K, the magnesium chloride.
8. method according to claim 1, wherein, described alcohol is methyl alcohol, ethanol, Virahol or the trimethyl carbinol; The product that adding methyl alcohol obtains is 5-(methoxyl methyl) furfural; The product that adding ethanol obtains is 5-(ethoxymethyl) furfural; The product that the adding Virahol obtains is 5-(the different third an oxygen methyl) furfural; The product that the adding trimethyl carbinol obtains is 5-(uncle's fourth oxygen methyl) furfural.
9. method according to claim 1, wherein, the temperature of reacting by heating is 60 ℃-180 ℃.
10. method according to claim 1, wherein, the reaction times was at 30 minutes to 2 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977058A (en) * | 2012-12-07 | 2013-03-20 | 中国科学院过程工程研究所 | Method for producing furfural |
| CN105330622A (en) * | 2015-11-12 | 2016-02-17 | 中国石油化工股份有限公司 | 5-ethoxy methyl furfural microwave catalytic synthesis method |
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2011
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| EP2233476A1 (en) * | 2004-12-10 | 2010-09-29 | Archer-Daniels-Midland Company | Preparation of an ether of 2,5-(hydroxymethyl)furfural (HMF) from a fructose source, an alcohol solvent and an acid catalyst |
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| US20100218416A1 (en) * | 2007-09-07 | 2010-09-02 | Furanix Technologies B.V. | Hydroxymethylfurfural ethers from sugars or hmf and branched alcohols |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102977058A (en) * | 2012-12-07 | 2013-03-20 | 中国科学院过程工程研究所 | Method for producing furfural |
| CN105330622A (en) * | 2015-11-12 | 2016-02-17 | 中国石油化工股份有限公司 | 5-ethoxy methyl furfural microwave catalytic synthesis method |
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Application publication date: 20111005 |