CN102558109A - Two-phase quick microwave synthesis method for hydroxymethylfurfural (HMF) - Google Patents
Two-phase quick microwave synthesis method for hydroxymethylfurfural (HMF) Download PDFInfo
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- CN102558109A CN102558109A CN2011104177539A CN201110417753A CN102558109A CN 102558109 A CN102558109 A CN 102558109A CN 2011104177539 A CN2011104177539 A CN 2011104177539A CN 201110417753 A CN201110417753 A CN 201110417753A CN 102558109 A CN102558109 A CN 102558109A
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Abstract
The invention relates to a two-phase quick microwave synthesis method for hydroxymethylfurfural (HMF). The method comprises the following steps of: dissolving raw materials in a water-n-butanol two-phase reaction system, regulating the pH of reaction liquid to 1-5 by using an acidic catalyst, putting into a microwave reaction kettle, and performing microwave reaction at the temperature of between 130 and 190 DEG C and the power of 300 to 1,200W for 1 to 8 minutes; and cooling after the reaction is finished, demixing, and distilling n-butanol on an upper layer under reduced pressure to obtain the HMF. The two-phase reaction system is introduced, so that the raw materials have sufficient solubility, the obtained reaction product HMF is extracted and added into an organic phase on the upper layer, and the decomposition rate of the HMF in a water phase is reduced; and a microwave heating mode is adopted, so that operation time is short, the reaction can be finished within 10 minutes, the retention time of the product HMF in the acidic reaction liquid is shortened, side reaction is greatly reduced, and efficiency is improved.
Description
Technical field
The present invention relates to a kind of preparation method of industrial chemicals, particularly a kind of preparation method of hydroxymethylfurfural.
Background technology
A large amount of uses of whole world fossil oil not only can cause the exhaustion of traditional resource, and bring the serious environmental pollution and greatly affect global climate.Research is converted into various chemical with this renewable resources of biomass, is just becoming an important component part of the strategy of sustainable development of practicing thrift traditional resource protection environment.The furfural series derivates is one of important bio-based materials monomer, and wherein the most representative is 5 hydroxymethyl furfural (HMF).Contain an aldehyde radical and a methylol in its molecule; Can pass through hydrogenation, oxydehydrogenation, esterification, halogenation, polymerization, hydrolysis and other chemical reaction; Be used for synthetic many useful compounds and novel high polymer material, comprise medicine, resene plastics, diesel oil fuel additive etc.Therefore HMF is expected to become the novel hardware and software platform compound based on biomass resource.At present; A large amount of investigators are devoted to the research of hexose dehydration preparation HMF; But because the chemical instability of HMF itself; Give birth to other side reactions at reaction process relaying supervention easily, generate the insoluble humin of part (Humins) and some polymer soluble, thereby reduced selectivity and the yield of HMF.In order to suppress the degraded of HMF; Method commonly used is in organic phase, to react; Like (150 ° of C:an NMR of Ananda S. Mechanism of the dehydration of d-fructose to 5-hydroxymethylfurfural in dimethyl sulfoxide at study. Carbohydrate Research such as DMSO 99.8MIN. (DMSO), acetone, MIBKs; 2008; 343 (18): 3021 ~ 3024), can reduce the degraded of HMF so to a certain extent, but the solubleness of carbohydrate in organic phase is less usually; The adding of organic phase simultaneously brings difficulty also will for follow-up separation and purification work; Difficulty especially when particularly separating for high boiling organic solvent as DMSO need to consume more energy, and the use of a large amount of organic solvents does not meet the fundamental principle of Green Chemistry yet.Water is a kind of green solvent of most widespread on the earth, and fructose has great solubleness in water (normal temperature is issued to 3600 gL
-1), but HMF is very unstable in acidic aqueous solution, the yield of HMF always little desirable (being usually less than 20%) in the aqueous solution.
Summary of the invention
Technical problem:The present invention is directed to above-mentioned technical problem; A kind of two-phase microwave fast synthesis method of hydroxymethylfurfural is provided, adopts the high temperature rapid reaction, through reducing the reaction times; Introduce the biphasic reaction system, reduce HMF further resolves into levulinic acid and formic acid in the aqueous solution possibility.
Technical scheme:A kind of two-phase microwave fast synthesis method of hydroxymethylfurfural comprises the steps:
(1), with raw material water-soluble-propyl carbinol biphasic reaction system in, with an acidic catalyst reaction solution is adjusted to pH in 1 ~ 5 scope;
(2), the solution in the step (1) is placed microwave reaction kettle, set microwave power 300 ~ 1200W, the microwave reaction time is 1 ~ 8min, and the microwave temperature is 130 ~ 190 ℃ of reactions;
(3), reaction accomplishes, cooling, layering gets hydroxymethylfurfural with upper strata propyl carbinol phase underpressure distillation.
Said raw material is one or several mixtures in fructose, glucose, the synanthrin.
Said an acidic catalyst is sulfuric acid, hydrochloric acid, phosphoric acid or strongly acidic cationic exchange resin.
The volume ratio of water and propyl carbinol is in the said biphasic reaction system: 5:1 ~ 1:5.
Beneficial effect:The present invention introduces microwave two-phase compound method, has following advantage:
(1), introduce the biphasic reaction system, both guaranteed that raw material had sufficient solubleness, the reaction product hydroxymethylfurfural that obtains simultaneously is extracted in the upper organic phase, reduces its decomposition at aqueous phase.
(2), adopt microwave heating, the internal heating mode that it is unique has guaranteed carrying out fast of reaction; Running time is short, and 10min accomplishes with interior i.e. reaction, reduces the product residence time of hydroxymethylfurfural in acid-reaction liquid; Significantly reduced the generation of side reaction, raised the efficiency.
(3), propyl carbinol can not dissolve each other with water below 125 ℃, can dissolve each other with water more than 125 ℃.When temperature was higher than 125 ℃ during reaction, propyl carbinol and water dissolved each other, and the hydroxymethylfurfural that forms in the continuous aqueous phase extracted; Below the reaction postcooling to 125 ℃, propyl carbinol mainly is present in the propyl carbinol phase with water layering, hydroxymethylfurfural; Reaction finishes only to need the cooling cooling, gets final product layering, and directly underpressure distillation gets hydroxymethylfurfural then; Significantly reduce process step, raise the efficiency.
Embodiment
Embodiment 1:
Getting fructose 5g and be dissolved in the water that the 24mL volume ratio is 5:1-propyl carbinol biphasic reaction system, is that catalyzer is regulated pH=1 with sulfuric acid, adds in the microwave reaction tank body, sets microwave power 300; The microwave reaction time is 1min, and the microwave temperature is at 190 ℃, and reaction finishes the back and takes out tank body; Place in the stink cupboard and cool off, venting, ice bath fast cooling; Layering gets hydroxymethylfurfural with the underpressure distillation of propyl carbinol phase, and productive rate is 72%.
Embodiment 2:
Getting glucose 5g and be dissolved in the water that the 20mL volume ratio is 1:1-propyl carbinol biphasic reaction system, is that catalyzer is regulated pH=2.5 with phosphoric acid, adds in the microwave reaction tank body, sets microwave power 600; The microwave reaction time is 4min, and the microwave temperature is at 160 ℃, and reaction finishes the back and takes out tank body; Place in the stink cupboard and cool off, venting, ice bath fast cooling; Layering gets hydroxymethylfurfural with the underpressure distillation of propyl carbinol phase, and productive rate is 79%.
Embodiment 3:
Getting synanthrin 5g and be dissolved in the water that the 24mL volume ratio is 1:5-propyl carbinol biphasic reaction system, is that catalyzer is regulated pH=5 with the D-72 Zeo-karb, adds in the microwave reaction tank body, sets microwave power 1200; The microwave reaction time is 8min, and the microwave temperature is at 130 ℃, and reaction finishes the back and takes out tank body; Place in the stink cupboard and cool off, venting, ice bath fast cooling; Layering gets hydroxymethylfurfural with the underpressure distillation of propyl carbinol phase, and productive rate is 77%.
Claims (4)
1. the two-phase microwave fast synthesis method of a hydroxymethylfurfural is characterized in that comprising the steps:
(1), with raw material water-soluble-propyl carbinol biphasic reaction system in, with an acidic catalyst reaction solution is adjusted to pH in 1 ~ 5 scope;
(2), the solution in the step (1) is placed microwave reaction kettle, set microwave power 300 ~ 1200W, the microwave reaction time is 1 ~ 8min, and the microwave temperature is 140 ~ 190 ℃ of reactions;
(3), reaction accomplishes, cooling, layering gets hydroxymethylfurfural with upper strata propyl carbinol phase underpressure distillation.
2. the two-phase microwave fast synthesis method of hydroxymethylfurfural according to claim 1, it is characterized in that: said raw material is one or several mixtures in fructose, glucose, the synanthrin.
3. the two-phase microwave fast synthesis method of hydroxymethylfurfural according to claim 1, it is characterized in that: said an acidic catalyst is sulfuric acid, hydrochloric acid, phosphoric acid or strongly acidic cationic exchange resin.
4. the two-phase microwave fast synthesis method of hydroxymethylfurfural according to claim 1, it is characterized in that: the volume ratio of water and propyl carbinol is in the said biphasic reaction system: 5:1 ~ 1:5.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557805A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing 5-hydroxymethyl furfural |
| CN104557807A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Production process of 5-hydroxymethyl furfural |
| CN104557806A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of 5-hydroxymethylfurfural |
| JP2015526494A (en) * | 2012-09-03 | 2015-09-10 | アニッキ ゲーエムベーハーＡｎｎｉｋｋｉ Ｇｍｂｈ | Method for producing furan derivative |
| CN106146436A (en) * | 2015-04-19 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of production technology of 5 hydroxymethyl furfural |
| CN106146434A (en) * | 2015-04-19 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation technology of 5 hydroxymethyl furfural |
| CN106146437A (en) * | 2015-04-19 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of 5 hydroxymethyl furfural |
| CN106146435A (en) * | 2015-04-19 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of production method of 5 hydroxymethyl furfural |
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| CN102212047A (en) * | 2011-04-21 | 2011-10-12 | 山东省科学院能源研究所 | Method for preparing 5-hydroxymethyl furfural by jerusalem artichoke serving as raw material |
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Patent Citations (1)
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| CN102212047A (en) * | 2011-04-21 | 2011-10-12 | 山东省科学院能源研究所 | Method for preparing 5-hydroxymethyl furfural by jerusalem artichoke serving as raw material |
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| 姜楠、齐崴、黄仁亮等: "生物质制备5-羟甲基糠醛的研究进展", 《生物化工》 * |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015526494A (en) * | 2012-09-03 | 2015-09-10 | アニッキ ゲーエムベーハーＡｎｎｉｋｋｉ Ｇｍｂｈ | Method for producing furan derivative |
| CN104557805A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing 5-hydroxymethyl furfural |
| CN104557807A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Production process of 5-hydroxymethyl furfural |
| CN104557806A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of 5-hydroxymethylfurfural |
| CN106146436A (en) * | 2015-04-19 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of production technology of 5 hydroxymethyl furfural |
| CN106146434A (en) * | 2015-04-19 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation technology of 5 hydroxymethyl furfural |
| CN106146437A (en) * | 2015-04-19 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of 5 hydroxymethyl furfural |
| CN106146435A (en) * | 2015-04-19 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of production method of 5 hydroxymethyl furfural |
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Application publication date: 20120711 |