CN105330622A - 5-ethoxy methyl furfural microwave catalytic synthesis method - Google Patents
5-ethoxy methyl furfural microwave catalytic synthesis method Download PDFInfo
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- CN105330622A CN105330622A CN201510770684.8A CN201510770684A CN105330622A CN 105330622 A CN105330622 A CN 105330622A CN 201510770684 A CN201510770684 A CN 201510770684A CN 105330622 A CN105330622 A CN 105330622A
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- ethoxymethyl
- ethoxymethyl furfural
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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
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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Abstract
The invention discloses a 5-ethoxy methyl furfural microwave catalytic synthesis method. Sugar and alcohol are used as raw materials and react under the effect of an acid catalyst, the catalyst is the acid catalyst, the sugar and the alcohol are heated through microwaves and controlled at the temperature of 80-200 DEG C, ethyl acetate is added after the reaction is performed for a period of time, organic phases are collected, and the 5-ethoxy methyl furfural is obtained. Microwave heating has the effect of promoting a chemical reaction. The chemical reaction speed can be significantly improved and the reaction mechanism can be changed through the microwave heating effect and the electromagnetic effect. Only 10-30 min is needed to complete the reaction by means of microwave heating, the reaction time is shortened, and the highest yield of the prepared 5-ethoxy methyl furfural is 60%. In addition, the reaction is environmentally friendly in the whole process, the production cost is reduced to the maximum degree, and possibility is provided for industrial production in future.
Description
Technical field
The present invention relates to technical field of organic synthesis, be specifically related to the method for a kind of microwave catalysis synthesis 5-ethoxymethyl furfural.
Background technology
Ethoxymethyl furfural, has an ethoxymethyl and an aldehyde radical in molecule, be generally be obtained by reacting in ethanol by carbohydrate or by 5 hydroxymethyl furfural in ethanol etherificate obtain, be a kind of fuel or fuel dope of having application prospect.At room temperature, it is liquid, has good oxidative stability, and has higher 16 octane values (diesel quality bioassay standard).It is excellent potential fuel and fuel dope that these characteristics determine it.In addition, the energy density of 5-ethoxymethyl furfural is 8.7KWh/L, and the energy density of normal benzene (8.8KWh/L) closely, far above the energy density (6.1KWh/L) of ethanol.During as fuel, its high oxidation stability can also reduce the release of soot exhaust and oxynitride, oxysulfide.In addition, ethoxymethyl furfural and derivative thereof all obtain from biomass, belong to renewable energy source compound
The Another application of ethoxymethyl furfural is in aviation fuel, and aviation fuel requirements has higher energy density, burning-point and lower zero pour.Aviation fuel in ideal should be obtained as raw material by biomass or biological product, in other words, these aviation fuel should economically feasible, can accept on energy requirement.Ethoxymethyl furfural has shown these character in some aspects, different with the compound obtained from fossil oil, these compounds obtained from biomass have very high degree of unsaturation, can as the medium of the storage hydrogen of cheapness, and these biomass fuels are while providing higher energy density, flash-point is higher than 38 DEG C, zero pour is lower than-47 DEG C, and that is, these novel fuel are highly stable as aviation fuel use properties.
Prepare in the method for 5-ethoxymethyl furfural in currently available technology, in raw material reaction, usually adopt the mode of heating in water bath, the control effects of this type of heating to speed of response is unsatisfactory.
Summary of the invention
A kind of microwave catalysis is the object of the present invention is to provide to synthesize the method for 5-ethoxymethyl furfural, with sugar and alcohol for raw material, react under the effect of an acidic catalyst, environmentally friendly in whole process, and at utmost reduce production cost, for later suitability for industrialized production provides possibility.
Its technical solution comprises:
A kind of method preparing 5-ethoxymethyl furfural, it under catalysts conditions, reacts obtained with sugar and ethanol, described catalyzer is an acidic catalyst, described sugar and ethanol adopt microwave heating and control temperature is 80-200 DEG C, extraction into ethyl acetate is added after reaction 10-30min, collect organic phase, obtain 5-ethoxymethyl furfural.
As a preferred version of the present invention, above-mentioned sugar is monose, disaccharides, polysaccharide or glycan.
As another preferred version of the present invention, above-mentioned monose is glucose, and above-mentioned disaccharides is sucrose, and above-mentioned polysaccharide is inulin.
Preferably, above-mentioned sugared usable fibers usually replaces.
Above-mentioned Mierocrystalline cellulose is straw powder.
Preferably, above-mentioned an acidic catalyst CT-700 solid acid catalyst, Amberlyst-15 solid acid catalyst, hydrochloric acid or sulfuric acid.
Preferably, microwave heating temperature controls at 100-120 DEG C.
The Advantageous Effects that the present invention brings:
Compared with prior art, choosing at raw material, the present invention selects solid acid catalyst and mineral acid, does not select organic acid, on the one hand solid acid catalyst and mineral acid simple and easy to get, the lower and pollution avoided environment of cost on the other hand; Type of heating has been selected microwave heating, microwave is the hertzian wave of frequency between 300MHz-300GHz, the ultimate principle of microwave heating is conduction and the dielectric substance polarization of charged particle, microwave heating has promoter action to chemical reaction, utilize the heat effect of microwave and magnetoresistive effect can improve the speed of chemical reaction significantly and change reaction mechanism, the present invention selects microwave heating only to need 10-30min to complete reaction, shorten the reaction times, and the maximum output of the 5-ethoxymethyl furfural prepared is 60%.
The present invention controls reaction by microwave, and reaction conditions is gentle, and energy consumption is low, does not pollute the environment in reaction process, environmentally friendly.
Embodiment
The invention discloses the method for a kind of microwave catalysis synthesis 5-ethoxymethyl furfural, in order to make advantage of the present invention, technical scheme clearly, clearly, below in conjunction with specific embodiment, the present invention being elaborated.
Part material in following embodiment selected by the present invention, if glucose, sucrose and inulin are all bought by commercial channel to obtain;
Solid acid catalyst Amberlyst-15, be a kind of SDVB multipolymer of macropore basis on the strongly acidic catalyst of sulfonation, obtain by buying;
Solid acid catalyst CT-700 a kind of adopts TiCl isomorphous substitution and by (NH
4)
2sO
4the dealuminzation silk resene strongly acidic catalyst of modification, obtains by buying.
Embodiment 1:
The present invention, the method for microwave catalysis synthesis 5-ethoxymethyl furfural, specifically comprises the following steps:
First, take fructose 1.1g (6mmol) and CT-700 solid catalyst 216mg (20wt%), join in the reactor of microwave reactor;
Add in reactor 12mL dehydrated alcohol and stir magneton, after sealing in microwave reactor 120 DEG C reaction 10min;
Finally, after reaction stops, adding a small amount of saturated aqueous common salt, after being extracted with ethyl acetate, collected organic layer, is spin-dried on a rotary evaporator, obtains liquid russet, adds quantitative sym-trimethylbenzene wherein, uses
1the productive rate that HNMR calculates ethoxymethyl furfural is 54%.
Embodiment 2:
The present invention, the method for microwave catalysis synthesis 5-ethoxymethyl furfural, specifically comprises the following steps:
First, take fructose 1.1g (6mmol) and vitriol oil 32uL (10wt%), join in the reactor of microwave reactor;
Then, in reactor, add 12mL dehydrated alcohol and stir magneton, 120 DEG C of reactions in microwave reactor after sealing
10min；
Finally, after reaction stops, adding a small amount of saturated aqueous common salt, after being extracted with ethyl acetate, collected organic layer, is spin-dried on a rotary evaporator, obtains liquid russet, adds quantitative sym-trimethylbenzene wherein, uses
1the productive rate that HNMR calculates ethoxymethyl furfural is 43%.
Embodiment 3:
The present invention, the method for microwave catalysis synthesis 5-ethoxymethyl furfural, specifically comprises the following steps:
First, take fructose 1.1g (6mmol) and phospho-molybdic acid solid catalyst 180mg (10wt%), join in the reactor of microwave reactor;
Then add in reactor 12mL dehydrated alcohol and stir magneton, after sealing in microwave reactor 100 DEG C reaction 10min;
Finally, after reaction stops, adding a small amount of saturated aqueous common salt, after being extracted with ethyl acetate, collected organic layer, is spin-dried on a rotary evaporator, obtains liquid russet, adds quantitative sym-trimethylbenzene wherein, uses
1the productive rate that HNMR calculates ethoxymethyl furfural is 29%.
Embodiment 4:
The present invention, the method for microwave catalysis synthesis 5-ethoxymethyl furfural, specifically comprises the following steps:
First, take inulin 1.0g (6mmol) and vitriol oil 32uL (10wt%), join in the reactor of microwave reactor;
Then add in reactor 12mL dehydrated alcohol and stir magneton, after sealing in microwave reactor 120 DEG C reaction 10min;
Finally, after reaction stops, adding a small amount of saturated aqueous common salt, after being extracted with ethyl acetate, collected organic layer, is spin-dried on a rotary evaporator, obtains liquid russet, adds quantitative sym-trimethylbenzene wherein, uses
1the productive rate that HNMR calculates ethoxymethyl furfural is 60%.
Embodiment 5:
The present invention, the method for microwave catalysis synthesis 5-ethoxymethyl furfural, specifically comprises the following steps:
First, take straw powder 1.0g (6mmol) and vitriol oil 96uL (30wt%) and a small amount of tin tetrachloride, join in the reactor of microwave reactor, then add in reactor 12mL dehydrated alcohol and stir magneton, after sealing in microwave reactor 120 DEG C reaction 30min.After reaction stops, adding a small amount of saturated aqueous common salt, after being extracted with ethyl acetate, collected organic layer, is spin-dried on a rotary evaporator, obtains liquid russet, adds quantitative sym-trimethylbenzene wherein, uses
1the productive rate that HNMR calculates ethoxymethyl furfural is 19%.
The part do not addressed in aforesaid way is taked or uses for reference prior art to realize.
It should be noted that, any equivalent way that those skilled in the art make under the instruction of this specification sheets, or obviously variant all should in protection scope of the present invention.
Claims (7)
1. prepare the method for 5-ethoxymethyl furfural for one kind, it under catalysts conditions, reacts obtained with sugar and ethanol, it is characterized in that: described catalyzer is an acidic catalyst, described sugar and ethanol adopt microwave heating and control temperature is 80-200 DEG C, extraction into ethyl acetate is added after reaction 10-30min, collect organic phase, obtain 5-ethoxymethyl furfural.
2. the method preparing 5-ethoxymethyl furfural according to claim 1, is characterized in that: described sugar is monose, disaccharides, polysaccharide or glycan.
3. the method preparing 5-ethoxymethyl furfural according to claim 2, is characterized in that: described monose is glucose, and described disaccharides is sucrose, and described polysaccharide is inulin.
4. the method preparing 5-ethoxymethyl furfural according to claim 1, is characterized in that: described sugared usable fibers usually replaces.
5. the method preparing 5-ethoxymethyl furfural according to claim 4, is characterized in that: described Mierocrystalline cellulose is straw powder.
6. the method preparing 5-ethoxymethyl furfural according to claim 1, is characterized in that: described an acidic catalyst CT-700 solid acid catalyst, Amberlyst-15 solid acid catalyst, hydrochloric acid or sulfuric acid.
7. the method preparing 5-ethoxymethyl furfural according to claim 1, is characterized in that: microwave heating temperature controls at 100-120 DEG C.
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| CN201510770684.8A CN105330622A (en) | 2015-11-12 | 2015-11-12 | 5-ethoxy methyl furfural microwave catalytic synthesis method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484539A (en) * | 2018-05-21 | 2018-09-04 | 河南农业大学 | A method of directly preparing 5- ethoxyl methyl furfurals using biomass straw |
| CN108997275A (en) * | 2018-06-20 | 2018-12-14 | 昆明理工大学 | A method of primary product distribution in control fructose-ethanol synthesis system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101400666A (en) * | 2006-03-10 | 2009-04-01 | 福兰尼克斯科技公司 | Method for the synthesis of 5-alkoxymethylfurfural ethers and their use |
| CN101809010A (en) * | 2007-09-07 | 2010-08-18 | 福兰尼克斯科技公司 | hydroxymethylfurfural ethers from sugars or hmf and mixed alcohols |
| CN102206198A (en) * | 2011-03-31 | 2011-10-05 | 中国科学院青岛生物能源与过程研究所 | Method for synthesizing 5-(alcoxylmethyl) furfural by using microwaves |
-
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- 2015-11-12 CN CN201510770684.8A patent/CN105330622A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101400666A (en) * | 2006-03-10 | 2009-04-01 | 福兰尼克斯科技公司 | Method for the synthesis of 5-alkoxymethylfurfural ethers and their use |
| CN101809010A (en) * | 2007-09-07 | 2010-08-18 | 福兰尼克斯科技公司 | hydroxymethylfurfural ethers from sugars or hmf and mixed alcohols |
| CN102206198A (en) * | 2011-03-31 | 2011-10-05 | 中国科学院青岛生物能源与过程研究所 | Method for synthesizing 5-(alcoxylmethyl) furfural by using microwaves |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484539A (en) * | 2018-05-21 | 2018-09-04 | 河南农业大学 | A method of directly preparing 5- ethoxyl methyl furfurals using biomass straw |
| CN108484539B (en) * | 2018-05-21 | 2021-07-06 | 河南农业大学 | Method for directly preparing 5-ethoxy methyl furfural by using biomass straws |
| CN108997275A (en) * | 2018-06-20 | 2018-12-14 | 昆明理工大学 | A method of primary product distribution in control fructose-ethanol synthesis system |
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Application publication date: 20160217 |