CN105646402A - Preparation method of 5-hydroxymethyl furfural from fructose at room temperature - Google Patents
Preparation method of 5-hydroxymethyl furfural from fructose at room temperature Download PDFInfo
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- CN105646402A CN105646402A CN201510962494.6A CN201510962494A CN105646402A CN 105646402 A CN105646402 A CN 105646402A CN 201510962494 A CN201510962494 A CN 201510962494A CN 105646402 A CN105646402 A CN 105646402A
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- room temperature
- hydroxymethyl 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 relates to a preparation method of 5-hydroxymethyl furfural from fructose at room temperature. The method uses a binary ionic liquid as a promoter, fructose as a raw material and alcohol as a solvent, and the dehydrates fructose into 5-hydroxymethyl furfural at room temperature. By changing the ratio of binary ionic liquid, the ionic liquid type and reaction time, the yield of 5-hydroxymethyl furfural is increased, and the maximum yield of reaction for 2 h is 90%. The method greatly reduces the energy consumption of the preparation process, is environment-friendly and high in product selectivity.
Description
Technical field
The invention belongs to production of renewable energy resources technical field, it relates under a kind of room temperature, prepare the method for 5 hydroxymethyl furfural by fructose.
Background technology
Along with day by day consuming of the fossil resource such as coal, oil and being on the rise of the environmental problem thus brought, develop renewable biomass resource and become very important and urgent. Carbohydrate is the important component part of biomass, is also the emphasis that people study. By saccharide converted and 5 hydroxymethyl furfural that is that become is a kind of important novel platform chemicals, can preparing the multiple derivative with high added value by series of chemical such as hydrogenation, esterification, halogenation, polymerization, oxidations, therefore people are carrying out a lot of trial and effort by saccharide converted on 5 hydroxymethyl furfural.
Fructose is most commonly used to one of raw material preparing 5 hydroxymethyl furfural. Early stage preparation mainly carries out in aqueous systems, organic solvent system or water/organic solvent biphasic system, and the catalyzer used is generallyAcid or Lewis acid, reaction carries out substantially all at relatively high temperatures. It is low that these systems also exist 5 hydroxymethyl furfural output, the defects such as by product is many, easy contaminate environment. In recent years, consider for environment protection, it is that the fructose of medium transforms the very big interest causing people taking ionic liquid. Having many reports to show, some are containing the good solvent that halogen anion ion liquid (such as chlorination 1-butyl-3-Methylimidazole) is fructose. And report that some functionalized ion liquids (such as N-Methyl pyrrolidone mesylate) can promote that fructose is converted into 5 hydroxymethyl furfural. The fructose conversion reaction that above-mentioned ionic liquid participates in all at high temperature completes. High temperature can improve speed of reaction, but also causes the generation of by product (such as levulinic acid, humin) so that the product rate of 5 hydroxymethyl furfural and selectivity decline. In addition, its high energy consumption also limit its practical application on large-scale industrial.
In order to avoid the drawback using high temperature to bring, people start to attempt carrying out fructose at normal temperatures and transform 5 hydroxymethyl furfural. Mostly being solid due under the ionic liquid normal temperature that routine molten sugar ionic liquid and catalysis fructose transform, in order to reduce the fusing point of ionic liquid, people have attempted carrying out this conversion reaction in eutectic system.Finding Deng people, fructose can form eutectic system with choline chloride 60 as hydrogen-bond donor; The people such as Han Buxing report, choline chloride 60 can also form eutectic system with the hydrogen-bond donor such as oxalic acid, citric acid and tosic acid, and this system not only can as solvent but also can as catalyzer. Although fructose can be converted into 5 hydroxymethyl furfural preferably in these eutectic systems, but the temperature of eutectic system still higher (> 50 DEG C), reaction still needs to carry out at relatively high temperatures.
In order to realize room temperature conversion, some molecular solvent are (such as CHCl3, DMSO, acetone etc.) be used as ionic liquid solvent to carry out fructose conversion reaction. But these system solvent for use are not green, and 5 hydroxymethyl furfural product rate is not high, and reaction required time is long.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of method at room temperature preparing 5 hydroxymethyl furfural by fructose of efficient, green, environmental protection.
Term illustrates:
Room temperature: envrionment temperature in room during room temperature of the present invention, temperature range is 10��30 DEG C.
The technical scheme of the present invention is as follows:
Prepare a method for 5 hydroxymethyl furfural under room temperature, comprise step as follows:
Being promotor taking binary ionic liquid, solvent made by alcohol, at room temperature makes fructose dehydration reaction be converted into 5 hydroxymethyl furfural.
According to the present invention, it is preferable that, described binary ionic liquid is chlorination 1-ethyl-3-Methylimidazole and the ionic liquid of chlorination N-Methyl pyrrolidone composition;
Preferred further, described chlorination 1-ethyl-3-Methylimidazole and the mol ratio of chlorination N-Methyl pyrrolidone are 8:3��10.5:0.5, it is more preferable to (2��10): 1.
According to the present invention, it is preferable that, described alcohol is n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol or the trimethyl carbinol.
According to the present invention, it is preferable that, the add-on of described alcohol and the mol ratio of binary ionic liquid total amount are 2:5��12:5, further preferred 8:5.
According to the present invention, it is preferable that, the add-on of described fructose and the mol ratio of binary ionic liquid total amount are 1:4��1:22, further preferably (1��2): 22;
According to the present invention, it is preferable that, temperature of reaction is 25 DEG C, and the reaction times is 10��180min;
Preferably, dehydration reaction carries out under agitation, and further preferably, stir speed (S.S.) is 100��1000rpm.
The invention has the beneficial effects as follows:
1, the ionic liquid that the present invention uses have do not volatilize, the advantage such as nonflammable, good stability, polarity are strong, liquid journey wide ranges, the solvability of sugar and converted product thereof is good; Use alcohol as solvent, not only environmental protection, and the eutectic system formed with ionic liquid makes conversion reaction at room temperature to carry out.
2, the ionic liquid that the present invention uses is binary ionic liquid, acts synergistically on fructose by hydrogen bond and to be taken off the hydroxyl removed, it is to increase sugared hydroxyl takes off the efficiency except reaction.
3, the reaction of the present invention at room temperature can carry out, it is not necessary to heating, greatly reduces the energy consumption in preparation process, decrease the pollution to environment, and side reaction does not occur substantially, selectivity of product height under room temperature, is a kind of friendly process.
Embodiment
Below in conjunction with embodiment, the invention will be further described, it is necessary to explanation, and embodiment does not form the restriction to the claimed scope of the present invention.
Embodiment 1
Taking 5.72mmol chlorination 1-ethyl-3-Methylimidazole and 0.572mmol chlorination N-Methyl pyrrolidone is dissolved in 10mmol n-propyl alcohol, then add 0.278mmol fructose, stirring reaction 60min at room temperature 25 DEG C, stir speed (S.S.) is 600rpm. Reaction samples after terminating and records 5 hydroxymethyl furfural product rate is 55.4%.
Embodiment 2
Taking 5.72mmol chlorination 1-ethyl-3-Methylimidazole and 0.572mmol chlorination N-Methyl pyrrolidone is dissolved in 10mmol Virahol, then add 0.278mmol fructose, stirring reaction 60min at room temperature 25 DEG C, stir speed (S.S.) is 600rpm.Reaction samples after terminating and records 5 hydroxymethyl furfural product rate is 75.9%.
Embodiment 3
Taking 5.72mmol chlorination 1-ethyl-3-Methylimidazole and 0.572mmol chlorination N-Methyl pyrrolidone is dissolved in the 10mmol trimethyl carbinol, then add 0.278mmol fructose, stirring reaction 60min at room temperature 25 DEG C, stir speed (S.S.) is 1000rpm. Reaction samples after terminating and records 5 hydroxymethyl furfural product rate is 67.3%.
Embodiment 4
Taking 5.72mmol chlorination 1-ethyl-3-Methylimidazole and 0.572mmol chlorination N-Methyl pyrrolidone is dissolved in 10mmol sec-butyl alcohol, then add 0.278mmol fructose, stirring reaction 60min at room temperature 25 DEG C, stir speed (S.S.) is 600rpm. Reaction samples after terminating and records 5 hydroxymethyl furfural product rate is 70.2%.
Embodiment 5
Taking 6.014mmol chlorination 1-ethyl-3-Methylimidazole and 0.286mmol chlorination N-Methyl pyrrolidone is dissolved in 10mmol Virahol, then add 0.278mmol fructose, stirring reaction 60min at room temperature 25 DEG C, stir speed (S.S.) is 600rpm. Reaction samples after terminating and records 5 hydroxymethyl furfural product rate is 41.2%.
Embodiment 6
Taking 5.148mmol chlorination 1-ethyl-3-Methylimidazole and 1.144mmol chlorination N-Methyl pyrrolidone is dissolved in 10mmol Virahol, then add 0.278mmol fructose, stirring reaction 30min at room temperature 25 DEG C, stir speed (S.S.) is 600rpm. Reaction samples after terminating and records 5 hydroxymethyl furfural product rate is 78.5%.
Embodiment 7
Taking 5.148mmol chlorination 1-ethyl-3-Methylimidazole and 1.144mmol chlorination N-Methyl pyrrolidone is dissolved in 10mmol Virahol, then add 0.278mmol fructose, stirring reaction 120min at room temperature 25 DEG C, stir speed (S.S.) is 600rpm. Reaction samples after terminating and records 5 hydroxymethyl furfural product rate is 90.6%.
Embodiment 8
Taking 5.148mmol chlorination 1-ethyl-3-Methylimidazole and 1.144mmol chlorination N-Methyl pyrrolidone is dissolved in 10mmol Virahol, then add 1.112mmol fructose, stirring reaction 120min at room temperature 25 DEG C, stir speed (S.S.) is 600rpm. Reaction samples after terminating and records 5 hydroxymethyl furfural product rate is 71.2%.
Claims (10)
1. prepare a method for 5 hydroxymethyl furfural under room temperature, comprise step as follows:
Being promotor taking binary ionic liquid, solvent made by alcohol, at room temperature makes fructose dehydration reaction be converted into 5 hydroxymethyl furfural.
2. under room temperature according to claim 1, prepare the method for 5 hydroxymethyl furfural, it is characterised in that, described binary ionic liquid is chlorination 1-ethyl-3-Methylimidazole and the ionic liquid of chlorination N-Methyl pyrrolidone composition.
3. under room temperature according to claim 2, prepare the method for 5 hydroxymethyl furfural, it is characterised in that, described chlorination 1-ethyl-3-Methylimidazole and the mol ratio of chlorination N-Methyl pyrrolidone are 8:3��10.5:0.5.
4. under room temperature according to claim 3, prepare the method for 5 hydroxymethyl furfural, it is characterised in that, described chlorination 1-ethyl-3-Methylimidazole and the mol ratio of chlorination N-Methyl pyrrolidone are (2��10): 1.
5. under room temperature according to claim 1, prepare the method for 5 hydroxymethyl furfural, it is characterised in that, described alcohol is n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol or the trimethyl carbinol.
6. under room temperature according to claim 1, prepare the method for 5 hydroxymethyl furfural, it is characterised in that, the add-on of described alcohol and the mol ratio of binary ionic liquid total amount are 2:5��12:5.
7. under room temperature according to claim 6, prepare the method for 5 hydroxymethyl furfural, it is characterised in that, the add-on of described alcohol and the mol ratio of binary ionic liquid total amount are 8:5.
8. under room temperature according to claim 1, prepare the method for 5 hydroxymethyl furfural, it is characterised in that, the add-on of described fructose and the mol ratio of binary ionic liquid total amount are 1:4��1:22.
9. under room temperature according to claim 1, prepare the method for 5 hydroxymethyl furfural, it is characterised in that, temperature of reaction is 25 DEG C, and the reaction times is 10��180min.
10. under room temperature according to claim 1, prepare the method for 5 hydroxymethyl furfural, it is characterised in that, dehydration reaction carries out under agitation, and stir speed (S.S.) is 100��1000rpm.
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| CN201510962494.6A CN105646402A (en) | 2015-12-17 | 2015-12-17 | Preparation method of 5-hydroxymethyl furfural from fructose at room temperature |
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| CN201510962494.6A CN105646402A (en) | 2015-12-17 | 2015-12-17 | Preparation method of 5-hydroxymethyl furfural from fructose at room temperature |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110749590A (en) * | 2019-10-26 | 2020-02-04 | 中国科学院新疆理化技术研究所 | Colorimetric reagent for rapidly detecting sucrose on site and preparation method thereof |
| CN111253350A (en) * | 2020-03-20 | 2020-06-09 | 广东石油化工学院 | Method for preparing 5-hydroxymethylfurfural by using chlorohydrin to promote dehydration of saccharide compounds |
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| DE102008009933A1 (en) * | 2008-02-18 | 2009-08-20 | Friedrich-Schiller-Universität Jena | Preparing 5-hydroxymethylfurfural, useful e.g. to manufacture pharmaceutical products such as fungicides, comprises thermally reacting carbohydrates in ionic liquid and discharging formed 5-hydroxymethylfurfural using extracting agent |
| KR20130044038A (en) * | 2011-10-21 | 2013-05-02 | 부경대학교 산학협력단 | Method for preparing 5-hydroxymethylfurfural directly from cellulose |
| ES2431670A1 (en) * | 2012-05-24 | 2013-11-27 | Universidade De Vigo | Procedure for the production of hydroxymethylfurfural from hemicelluloses of pine or spruce woods (Machine-translation by Google Translate, not legally binding) |
| CN103757959A (en) * | 2014-01-08 | 2014-04-30 | 中国科学院过程工程研究所 | New method for obtaining cellulose-rich material from straws by two-step method by adopting ionic liquids |
| CN104324748A (en) * | 2014-09-15 | 2015-02-04 | 杭州师范大学 | Catalyst for conversion of fructose to 5-hydroxymethylfurfural |
-
2015
- 2015-12-17 CN CN201510962494.6A patent/CN105646402A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102008009933A1 (en) * | 2008-02-18 | 2009-08-20 | Friedrich-Schiller-Universität Jena | Preparing 5-hydroxymethylfurfural, useful e.g. to manufacture pharmaceutical products such as fungicides, comprises thermally reacting carbohydrates in ionic liquid and discharging formed 5-hydroxymethylfurfural using extracting agent |
| KR20130044038A (en) * | 2011-10-21 | 2013-05-02 | 부경대학교 산학협력단 | Method for preparing 5-hydroxymethylfurfural directly from cellulose |
| ES2431670A1 (en) * | 2012-05-24 | 2013-11-27 | Universidade De Vigo | Procedure for the production of hydroxymethylfurfural from hemicelluloses of pine or spruce woods (Machine-translation by Google Translate, not legally binding) |
| CN103757959A (en) * | 2014-01-08 | 2014-04-30 | 中国科学院过程工程研究所 | New method for obtaining cellulose-rich material from straws by two-step method by adopting ionic liquids |
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Non-Patent Citations (3)
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| JING ZHANG，等: "Room-Temperature Ionic Liquid System Converting Fructose into 5-Hydroxymethylfurfural in High Efficiency", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110749590A (en) * | 2019-10-26 | 2020-02-04 | 中国科学院新疆理化技术研究所 | Colorimetric reagent for rapidly detecting sucrose on site and preparation method thereof |
| CN111253350A (en) * | 2020-03-20 | 2020-06-09 | 广东石油化工学院 | Method for preparing 5-hydroxymethylfurfural by using chlorohydrin to promote dehydration of saccharide compounds |
| CN111253350B (en) * | 2020-03-20 | 2023-02-28 | 广东石油化工学院 | Method for preparing 5-hydroxymethylfurfural by using chlorohydrin to promote dehydration of saccharide compounds |
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