CN104844543A - Method for preparing 5-hydroxymethylfurfural from fructose - Google Patents
Method for preparing 5-hydroxymethylfurfural from fructose Download PDFInfo
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- CN104844543A CN104844543A CN201510277971.5A CN201510277971A CN104844543A CN 104844543 A CN104844543 A CN 104844543A CN 201510277971 A CN201510277971 A CN 201510277971A CN 104844543 A CN104844543 A CN 104844543A
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- fructose
- hydroxymethyl furfural
- hydroxymethylfurfural
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- choline chloride
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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 5-hydroxymethylfurfural, particularly a method for preparing 5-hydroxymethylfurfural from fructose. The method has the advantages of low cost, high yield, simple steps and environment friendliness. The method comprises the following steps: mixing fructose and choline chloride, adding hydrochloric acid as a catalyst, heating to react, and adding an organic extractant to extract the reaction mixture, thereby obtaining the product 5-hydroxymethylfurfural. By using the ultralow-concentration hydrochloric acid as the catalyst, the 5-hydroxymethylfurfural can be efficiently prepared in the fructose-choline chloride eutectic system, thereby being green and environment-friendly. By using the ultralow-concentration hydrochloric acid as the catalyst, the yield of the 5-hydroxymethylfurfural can reach 92%. The eutectic formed by the cheap choline chloride and fructose has favorable economical efficiency, thereby providing a novel idea for research of 5-hydroxymethylfurfural and downstream products thereof.
Description
Technical field
The present invention relates to 5 hydroxymethyl furfural, especially relate to a kind of method being prepared 5 hydroxymethyl furfural by fructose.
Background technology
5 hydroxymethyl furfural is the middle product of a kind of important platform chemicals and chemistry, and containing a methylol and an aldehyde radical in molecule, chemical reactivity is good, has a wide range of applications in industry China such as chemical industry, medicine conjunctions.Therefore, with the biomass-based carbohydrate of nature wide material sources for 5 hydroxymethyl furfural prepared by raw material, there is certain promoter action to the research and development of new forms of energy, also have certain positive effect to social sustainable development.Current scholar to have attempted saccharide converted in medium such as, as 5 hydroxymethyl furfural, water, organic solvent, diphasic system and ionic liquid.Various types of catalyzer is also applied to promote 5 hydroxymethyl furfural productive rate in carbohydrate dehydration reaction, and common catalyzer has mineral acid, organic acid, solid acid and metal-salt etc.But all there is certain defect in conventional various catalyst system, prepares 5 hydroxymethyl furfural productive rate low in aqueous systems; Organic solvent system easily causes environmental pollution, and product separation difficulty; Ionic liquid is expensive, is difficult to realize scale operation.
Eutectic refers to two components or three components eutectic mixture that are combined by the hydrogen bond receptor of certain stoichiometric ratio (as quaternary ammonium salt) and hydrogen-bond donor (as compounds such as acid amides, carboxylic acid and polyvalent alcohols), and its zero pour is significantly lower than the fusing point of each component pure substance.By people such as Abbott in reported first in 2003.Physicochemical property and the ionic liquid of eutectic are closely similar, have good catalysis and reactivity worth.Choline chloride 60, also known as chlorination 2-hydroxyethyl TMA (TriMethylAmine), is modal hydrogen bond receptor in existing bibliographical information, and formation eutectic that can be good at a certain temperature with fructose, and this material environmental protection are cheap.Current existing literature research transforms carbohydrate and prepares 5 hydroxymethyl furfural in eutectic, disclose in Chinese patent CN101906088 B and a kind ofly form with biomass sugar and ammonium salt the method that eutectic mixture prepares 5 hydroxymethyl furfural, its catalyzer almost includes all an acidic catalysts as dense mineral acid, inorganic acid salt and acidic ion liquid, the highest 5 hydroxymethyl furfural yield of the method can reach 70%.But the mineral acids such as concentrated hydrochloric acid catalytic efficiency in eutectic system is low, easily endangers environment.Chinese patent CN 103951639 A discloses a kind of method that gentleness prepares 5 hydroxymethyl furfural fast, comprise using the metal chloride of chromium chloride, aluminum chloride as catalyzer, under the condition of the aqueous solution, jointly form mixed solution with raw materials of glucose and choline chloride 60, and mixed solution is placed in reactor react under microwave condition generate 5 hydroxymethyl furfural.The method not only complicated operation and also 5 hydroxymethyl furfural productive rate on the low side, used catalyst cannot reclaim and most of metal chloride poisonous and harmful, easily endangers environmental and human health impacts.
Summary of the invention
Main purpose of the present invention is to provide that cost is low, productive rate is high, step is simple, a kind of eco-friendly method being prepared 5 hydroxymethyl furfural by fructose.
Concrete steps of the present invention are as follows:
By fructose and choline chloride 60 mixing, add hydrochloric acid as catalyzer, after reacting by heating, add organic extractant extractive reaction mixture, obtain product 5 hydroxymethyl furfural solution.
The add-on of described hydrochloric acid can be 0.04% ~ 6% of fructose by mass percentage.
The add-on of described fructose can be 25% ~ 100% of choline chloride 60 by mass percentage.
The temperature of described reacting by heating can be 80 ~ 110 DEG C, and the time of reacting by heating can be 30 ~ 480min.
Described organic extractant can be selected from acetonitrile or ethylene dichloride etc.
The consumption of described organic extractant can be 20 ~ 40mL/g fructose.
The invention has the advantages that:
1, mineral acid catalysis carbohydrate Dehydration dense with tradition is for compared with 5 hydroxymethyl furfural, and the present invention's application ultralow density hydrochloric acid, as catalyzer, can prepare 5 hydroxymethyl furfural efficiently, environmental protection more in fructose and choline chloride 60 eutectic system.
2, in the present invention using ultralow density hydrochloric acid as catalyzer, 5 hydroxymethyl furfural productive rate compares traditional method (aqueous systems, organic solvent system, eutectic system) higher lifting, and the highest 5 hydroxymethyl furfural productive rate can reach 92%.
3, compared to ionic liquid catalyst systems, present invention employs cheap choline chloride 60 and fructose formation eutectic, there is good economy, for 5 hydroxymethyl furfural and downstream product research thereof provide a kind of thinking of novelty.
Accompanying drawing explanation
Fig. 1 is the GC-MS collection of illustrative plates being prepared 5 hydroxymethyl furfural products therefrom by fructose.
Embodiment
Below in conjunction with embodiment, the invention will be further described, it should be noted that, embodiment does not form the restriction to application claims protection domain.
Embodiment 1
By 1g fructose, 4g choline chloride 60,6 × 10
-3g hydrochloric acid (massfraction is 38%) is placed in round-bottomed flask and mixes, 100 DEG C are heated at oil bath pan, reaction 480min, react rear question response mixture and be cooled to room temperature, with 40mL acetonitrile extraction reaction product, recording 5 hydroxymethyl furfural productive rate is 92.0% (as Fig. 1).
Embodiment 2
By 1g fructose, 1g choline chloride 60,4 × 10
-4g hydrochloric acid (massfraction is 38%) is placed in round-bottomed flask and mixes, be heated to 110 DEG C at oil bath pan, reaction 120min, has reacted rear question response mixture and has been cooled to room temperature, with 30mL ethylene dichloride extractive reaction product, recording 5 hydroxymethyl furfural productive rate is 48.2%.
Embodiment 3
By 1g fructose, 4g choline chloride 60,6 × 10
-2g hydrochloric acid (massfraction is 38%) is placed in round-bottomed flask and mixes, be heated to 80 DEG C at oil bath pan, reaction 180min, has reacted rear question response mixture and has been cooled to room temperature, with 30mL acetonitrile extraction reaction product, recording 5 hydroxymethyl furfural productive rate is 45.3%.
Embodiment 4
By 1g fructose, 4g choline chloride 60,1.2 × 10
-2g hydrochloric acid (massfraction is 38%) is placed in round-bottomed flask and mixes, be heated to 100 DEG C at oil bath pan, reaction 240min, has reacted rear question response mixture and has been cooled to room temperature, with 20mL acetonitrile extraction reaction product, recording 5 hydroxymethyl furfural productive rate is 76.5%.
Embodiment 5
By 1g fructose, 4g choline chloride 60,6 × 10
-3g hydrochloric acid (massfraction is 38%) is placed in round-bottomed flask and mixes, be heated to 100 DEG C at oil bath pan, reaction 30min, has reacted rear question response mixture and has been cooled to room temperature, with 40mL ethylene dichloride extractive reaction product, recording 5 hydroxymethyl furfural productive rate is 32.6%.
Embodiment 6
By 1g fructose, 4g choline chloride 60,6 × 10
-3g hydrochloric acid (massfraction is 38%) is placed in round-bottomed flask and mixes, be heated to 100 DEG C at oil bath pan, reaction 240min, has reacted rear question response mixture and has been cooled to room temperature, with 40mL acetonitrile extraction reaction product, recording 5 hydroxymethyl furfural productive rate is 90.1%.
Fructose and choline chloride 60 are formed eutectic by the present invention at a certain temperature, using the hydrochloric acid of super low loading as catalyzer, react at 80 ~ 110 DEG C, after reaction terminates, be down to room temperature, carry out extractive reaction mixture with organic solvent, obtain target product 5 hydroxymethyl furfural.The highest yield of the present invention can reach 92%.The present invention prepares 5 hydroxymethyl furfural from the fructose of biomass source, there is the features such as method is simple, condition is gentleer, charging capacity is high, productive rate is high, catalyzer is cheap and easy to get, environmentally friendly, provide the new way of a biomass-based high value added product of preparation.
Claims (6)
1. prepared a method for 5 hydroxymethyl furfural by fructose, it is characterized in that its concrete steps are as follows:
By fructose and choline chloride 60 mixing, add hydrochloric acid as catalyzer, after reacting by heating, add organic extractant extractive reaction mixture, obtain product 5 hydroxymethyl furfural solution.
2. a kind of method being prepared 5 hydroxymethyl furfural by fructose as claimed in claim 1, is characterized in that the add-on of described hydrochloric acid is 0.04% ~ 6% of fructose by mass percentage.
3. a kind of method being prepared 5 hydroxymethyl furfural by fructose as claimed in claim 1, is characterized in that the add-on of described fructose is 25% ~ 100% of choline chloride 60 by mass percentage.
4. a kind of method being prepared 5 hydroxymethyl furfural by fructose as claimed in claim 1, it is characterized in that the temperature of described reacting by heating is 80 ~ 110 DEG C, the time of reacting by heating is 30 ~ 480min.
5. a kind of method being prepared 5 hydroxymethyl furfural by fructose as claimed in claim 1, is characterized in that described organic extractant is selected from acetonitrile or ethylene dichloride.
6. a kind of method being prepared 5 hydroxymethyl furfural by fructose as claimed in claim 1, is characterized in that the consumption of described organic extractant is 20 ~ 40mL/g fructose.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254601A (en) * | 2015-10-29 | 2016-01-20 | 厦门大学 | Method for preparing 5-HMF(hydroxymethylfurfural) from glucose |
| CN106220592A (en) * | 2016-07-29 | 2016-12-14 | 厦门大学 | A kind of method being prepared 5 bromomethyl furfurals by fructose in eutectic/hexone diphasic system |
| CN106995423A (en) * | 2017-06-01 | 2017-08-01 | 厦门大学 | A kind of method that 5 formyloxymethyl furfurals are prepared from fructose |
| CN108440462A (en) * | 2018-04-12 | 2018-08-24 | 厦门大学 | A method of 5 hydroxymethyl furfural being prepared by fructose under no acid system |
| CN108440463A (en) * | 2018-05-24 | 2018-08-24 | 厦门大学 | A method of preparing 5 hydroxymethyl furfural with load type metal molecular sieve catalyst catalysis |
| CN109651307A (en) * | 2019-01-16 | 2019-04-19 | 中国科学院广州能源研究所 | A kind of method that fiber-like Chinese medicine slag prepares furan derivatives |
| CN110305083A (en) * | 2019-06-03 | 2019-10-08 | 厦门大学 | A kind of technique that 5- chloromethyl furfural is prepared with fructose |
| WO2019229080A1 (en) * | 2018-05-29 | 2019-12-05 | Südzucker AG | Preparation of hmf catalyzed by a mixture of salt and acid |
| CN111087372A (en) * | 2019-12-26 | 2020-05-01 | 长春工业大学 | Method for preparing 5-HMF by catalyzing fructose dehydration through low eutectic solvent |
| CN112574143A (en) * | 2021-01-22 | 2021-03-30 | 安徽省天助纺织科技集团股份有限公司 | Method for preparing 5-hydroxymethylfurfural from waste cotton fabrics |
| CN112574142A (en) * | 2020-11-27 | 2021-03-30 | 浙江大学 | Method for preparing 2, 5-furandimethanol from biomass sugar |
| CN114805254A (en) * | 2022-04-11 | 2022-07-29 | 合肥利夫生物科技有限公司 | Preparation method of 5-hydroxymethylfurfural |
| CN115785035A (en) * | 2023-02-03 | 2023-03-14 | 中国农业科学院农业环境与可持续发展研究所 | Method for preparing furfural and 5-hydroxymethylfurfural from straws |
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| CN101906088A (en) * | 2010-08-24 | 2010-12-08 | 中国科学院青岛生物能源与过程研究所 | Method for preparing 5-hydroxymethylfurfural |
| US20130023679A1 (en) * | 2011-07-21 | 2013-01-24 | Industrial Technology Research Institute | Preparation of furfural compounds, and mixture for preparing the same |
| CN103951639A (en) * | 2014-03-27 | 2014-07-30 | 中国科学院宁波材料技术与工程研究所 | Method for mildly and rapidly preparing 5-hydroxymethylfurfural |
-
2015
- 2015-05-27 CN CN201510277971.5A patent/CN104844543A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101906088A (en) * | 2010-08-24 | 2010-12-08 | 中国科学院青岛生物能源与过程研究所 | Method for preparing 5-hydroxymethylfurfural |
| US20130023679A1 (en) * | 2011-07-21 | 2013-01-24 | Industrial Technology Research Institute | Preparation of furfural compounds, and mixture for preparing the same |
| CN103951639A (en) * | 2014-03-27 | 2014-07-30 | 中国科学院宁波材料技术与工程研究所 | Method for mildly and rapidly preparing 5-hydroxymethylfurfural |
Non-Patent Citations (8)
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254601A (en) * | 2015-10-29 | 2016-01-20 | 厦门大学 | Method for preparing 5-HMF(hydroxymethylfurfural) from glucose |
| CN106220592A (en) * | 2016-07-29 | 2016-12-14 | 厦门大学 | A kind of method being prepared 5 bromomethyl furfurals by fructose in eutectic/hexone diphasic system |
| CN106995423A (en) * | 2017-06-01 | 2017-08-01 | 厦门大学 | A kind of method that 5 formyloxymethyl furfurals are prepared from fructose |
| CN108440462A (en) * | 2018-04-12 | 2018-08-24 | 厦门大学 | A method of 5 hydroxymethyl furfural being prepared by fructose under no acid system |
| CN108440463A (en) * | 2018-05-24 | 2018-08-24 | 厦门大学 | A method of preparing 5 hydroxymethyl furfural with load type metal molecular sieve catalyst catalysis |
| US11548863B2 (en) | 2018-05-29 | 2023-01-10 | Südzucker AG | Preparation of HMF catalyzed by a mixture of salt and acid |
| WO2019229080A1 (en) * | 2018-05-29 | 2019-12-05 | Südzucker AG | Preparation of hmf catalyzed by a mixture of salt and acid |
| CN109651307A (en) * | 2019-01-16 | 2019-04-19 | 中国科学院广州能源研究所 | A kind of method that fiber-like Chinese medicine slag prepares furan derivatives |
| CN110305083A (en) * | 2019-06-03 | 2019-10-08 | 厦门大学 | A kind of technique that 5- chloromethyl furfural is prepared with fructose |
| CN110305083B (en) * | 2019-06-03 | 2021-12-10 | 厦门大学 | Process for preparing 5-chloromethyl furfural from fructose |
| CN111087372A (en) * | 2019-12-26 | 2020-05-01 | 长春工业大学 | Method for preparing 5-HMF by catalyzing fructose dehydration through low eutectic solvent |
| CN112574142A (en) * | 2020-11-27 | 2021-03-30 | 浙江大学 | Method for preparing 2, 5-furandimethanol from biomass sugar |
| CN112574143A (en) * | 2021-01-22 | 2021-03-30 | 安徽省天助纺织科技集团股份有限公司 | Method for preparing 5-hydroxymethylfurfural from waste cotton fabrics |
| CN114805254A (en) * | 2022-04-11 | 2022-07-29 | 合肥利夫生物科技有限公司 | Preparation method of 5-hydroxymethylfurfural |
| CN115785035A (en) * | 2023-02-03 | 2023-03-14 | 中国农业科学院农业环境与可持续发展研究所 | Method for preparing furfural and 5-hydroxymethylfurfural from straws |
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Application publication date: 20150819 |