CN104628684A - Method for extracting 5-hydroxymethylfurfural from ionic liquid - Google Patents
Method for extracting 5-hydroxymethylfurfural from ionic liquid Download PDFInfo
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Abstract
Disclosed is a method for extracting 5-hydroxymethylfurfural (5-HMF) from ionic liquid. Efficient transfer of 5-HMF from an ionic liquid phase to an extraction phase is realized by adding an extraction additive into a bi-phase extraction system consisting of an extraction agent and the ionic liquid containing 5-HMF. The extraction additive together with the ionic liquid cannot form two phases for the extraction additive is soluble in the ionic liquid, but the extraction additive can significantly improve a distribution ratio of 5-HMF to the extraction phase. For example, 5-HMF is extracted from [BMIM]Cl by taking methyl isobutyl ketone (MIBK) as an extraction agent; under the same conditions, the concentration ratio of 5-HMF in the MIBK phase to 5-HMF in the [BMIM]Cl phase is 5.76:100 if an extraction additive of methanol is added, the concentration ratio is 8.87:100 if an extraction additive of ethanol is added, while the concentration ratio is only 0.96:100 if no extraction additive is added. According to the invention, an effect of extracting 5-HMF from ionic liquid is effectively improved, so that the consumption of an extraction phase is decreased.
Description
Technical field
The invention belongs to chemical industry abstraction technique field, be specifically related to a kind of method extracting 5 hydroxymethyl furfural (HMF) from ionic liquid.
Background technology
Current fossil energy is day by day exhausted, and the development and utilization of bioenergy enjoys favor, and wherein comparatively outstanding research is that Mierocrystalline cellulose, glucose, fructose etc. are catalytically conveted to 5 hydroxymethyl furfural (5-HMF).5-HMF is the Important Platform compound being become biomass fuel or chemical by Wood Adhesives from Biomass, can be synthesized by biomass material in ionic liquid, water or organic solvent.Wherein in ionic liquid, under metal salt catalyst effect, Mierocrystalline cellulose, sugar can be converted into 5-HMF efficiently, have that raw material feeding is most economical, transformation efficiency advantages of higher, in Wood Adhesives from Biomass, occupy critical role.But due to ionic liquid and 5-HMF binding ability excessively strong, and 5-HMF boiling point is 114-116 DEG C (1mmHg), and both separation are faced with stern challenge.Therefore the technology of high efficiency extraction 5-HMF from ionic liquid of developing has significant application value.
The method being separated 5-HMF at present from mixing solutions mainly contains crystallization, distillation, ion-exchange, extraction.Staahlberg Tim et al, WO2013EP66125 adopt low temperature crystallization purification 5-HMF in organic solvent; Lianmin Liu et al, CN20111180870 utilizes ionic energy transfer 5-HMF; Jinfeng Fei CN20111417753, under rapid microwave controls, utilizes water-propyl carbinol biphasic reaction system, and realization response extraction is synchronously carried out.Extracting process being separated both likely realizing with relatively low cost and higher organic efficiency, has very high application potential.Yuriy Roman-Leshkov et al, Science312,1933 (2006) add dimethyl sulfoxide (DMSO) (DMSO) and with methyl iso-butyl ketone (MIBK)/isopropylcarbinol (MIBK/2-Butanol) for extraction agent in water react, from water react system, be separated 5-HMF, but have no the report that it is separated 5-HMF from ionic liquid.Annegret Stark et al, J.Chem.Eng.Data57,2985 (2012) have studied the performance that the organic solvents such as MIBK, methyl alcohol, ethanol extract HMF from ionic liquid, found that MIBK etc. can extract 5-HMF with the immiscible organic solvent of ionic liquid from ionic liquid, and the polar organic such as methyl alcohol, ethanol small molecules is owing to dissolving each other with ionic liquid, not there is the ability from wherein extracting 5-HMF.In the present invention, methyl alcohol, ethanol etc. are not had the organic solvent extracting 5-HMF from ionic liquid and be applied in the separation method of 5-HMF and ionic liquid, achieve the efficient transfer of 5-HMF from ionic liquid to organic solvent.
Summary of the invention
The object of this invention is to provide a kind of method extracting 5 hydroxymethyl furfural (HMF) from ionic liquid, the method extraction efficiency is high, cost is low, compares with ionic liquid two-phase extraction system with traditional organic solvent, and extracting power can improve 1-20 doubly.
The invention provides a kind of method extracting 5 hydroxymethyl furfural from ionic liquid, in extraction agent and the two-phase extraction system that forms containing the ionic liquid of 5 hydroxymethyl furfural (HMF), add extraction auxiliary agent, realize HMF and efficiently shift to extraction phase from ionic liquid.
The mol ratio of described extraction auxiliary agent and ionic liquid is 0.05 ~ 5:1.
The mass ratio of described extraction agent and ionic liquid is 0.1 ~ 1000:1.
The method extracting 5 hydroxymethyl furfural from ionic liquid provided by the invention, described ionic liquid is imidazoles type ionic liquid, and its structure is as follows:
The method extracting 5 hydroxymethyl furfural from ionic liquid provided by the invention, extraction agent and extraction auxiliary agent feed postition be: extraction agent and extraction auxiliary agent synchronously add or join one by one ionic liquid mutually in, two-phase, through fully mixing mass transfer and stratification, realizes HMF from ionic liquid to the phase transition of organic solvent phase.
The method extracting 5 hydroxymethyl furfural from ionic liquid provided by the invention, extraction temperature is 0 ~ 150 DEG C.
The method extracting 5 hydroxymethyl furfural from ionic liquid provided by the invention, the HMF after extraction adopts the method for distillation to be separated from extraction agent, and distillation temperature is 25 ~ 150 DEG C, and distillation absolute pressure is 0 ~ 2atm.
The method extracting 5 hydroxymethyl furfural from ionic liquid provided by the invention, described extraction auxiliary agent is alcohol, ketone, phenol, carboxylic acid, aldehyde, acetonitrile, at least one in dimethyl sulfoxide (DMSO).
Described alcohols extraction auxiliary agent is the alkanol molecule having fine mutual solubility with ionic liquid mutually, such as methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, ethylene glycol, glycerol, chloroethanol, phenylcarbinol etc.
Described ketone extraction auxiliary agent is the ketone molecule having fine mutual solubility with ionic liquid mutually, such as acetone, butanone, 2 pentanone etc.
Described phenol extraction auxiliary agent is the phenolic molecules having fine mutual solubility with ionic liquid mutually, such as phenol, 2-chlorophenol, 2-cresols etc.
Described carboxylic-acid extraction auxiliary agent is the carboxylic-acid molecule having fine mutual solubility with ionic liquid mutually, such as formic acid, acetic acid, propionic acid etc.
Described aldehydes extraction auxiliary agent is the aldehydes molecule having fine mutual solubility with ionic liquid mutually, such as formaldehyde, acetaldehyde etc.
The method extracting 5 hydroxymethyl furfural from ionic liquid provided by the invention, described extraction agent is ketone, ester class, tetrahydrofuran (THF), benzene class, halogenated hydrocarbon, at least one in dioxane.
Described ketone extraction agent is do not dissolve each other with ionic liquid or the ketone molecule of partial miscibility, such as methyl iso-butyl ketone (MIBK) (MIBK), polyvinylpyrrolidone etc.
Described lipid extraction agent is do not dissolve each other with ionic liquid or the lipid molecule of partial miscibility, such as methyl acetate, ethyl acetate, butylacetate, diethyl malonate, ethyl succinate etc.
Described benzene kind of extractants is do not dissolve each other with ionic liquid or the benzene quasi-molecule of partial miscibility, and such as benzene class is benzene, toluene etc.
Described halogenated hydrocarbon extraction agent is do not dissolve each other with ionic liquid or the halogenated hydrocarbon molecule of partial miscibility, such as tetracol phenixin, methylene dichloride etc.
Advantage of the present invention: the invention provides a kind of method extracting 5 hydroxymethyl furfural (HMF) from ionic liquid, namely adds extraction auxiliary agent to improve the extraction efficiency of HMF in extraction agent and the two-phase extraction system that forms containing the ionic liquid of 5 hydroxymethyl furfural (HMF).Extracting power of the method and traditional organic solvent comparing with ionic liquid two-phase extraction system can improve 1-20 doubly, and extraction efficiency is high, cost is low, realize HMF from ionic liquid mutually high efficiency separation.
Embodiment
The effect further illustrating embodiment of the present invention by embodiment and comparison example and produce, but protection scope of the present invention is not limited to the content listed by embodiment.
Embodiment 1-4, illustrates the impact adding extraction auxiliary agent in ionic liquid and MIBK two-phase extraction system
Preparation containing 5-HMF ionic liquid mixed solution: take 1-butyl-3-Methylimidazole chlorate ion liquid [BMIM] Cl20g, add HMF2.00g, at 100 DEG C, heating for dissolving stirs, and is made into 100mgHMF/1g [BMIM] Cl.
Two-phase extracts: under room temperature, 100mgHMF/1g [BMIM] Cl mixed solution 1ml(1.1g is added respectively) in 4 10ml bottles, be labeled as embodiment 1,2,3 and 4, then do not add respectively in these four bottles help extraction agent, add 0.23ml methyl alcohol, 0.34ml ethanol, 0.31ml acetonitrile, finally in these four bottles, respectively add MIBK3ml.800r/min stirs 20min, static 1 hour, gets levels liquid efficient liquid phase chromatographic analysis HMF concentration respectively, and calculates the concentration partition ratio of HMF according to concentration.Obtain result as shown in table 1.
HMF concentration partition ratio is defined as: the ratio of the volumetric molar concentration of HMF in MIBK phase and the volumetric molar concentration of HMF in [BMIM] Cl phase.
The impact extracting auxiliary agent is added in table 1MIBK and [BMIM] Cl two-phase extraction system
Table 1 is known, extracts compared with auxiliary agent, after adding methyl alcohol, ethanol and acetonitrile extraction auxiliary agent with not adding, HMF improves greatly at the distribution probability of MIBK phase, wherein add methyl alcohol and ethanol builder activity obvious especially, extract compared with auxiliary agent with not adding, partition ratio improves 6 times and 9 times respectively.
Embodiment 5-8, illustrates the impact adding extraction auxiliary agent when adopting other extraction agents
Containing the preparation of 5-HMF ionic liquid mixed solution with embodiment 1-4.
Two-phase extracts: under room temperature, 100mgHMF/1g [BMIM] Cl mixed solution 1ml is added respectively in four 10ml bottles, be labeled as embodiment 5 respectively, 6,7 and 8, then in embodiment 6 and 8 bottle, add alcohol extraction auxiliary agent 0.34ml respectively, finally add ethyl acetate 3ml at embodiment 5 and 6 bottle, add tetrahydrofuran (THF) 3ml at embodiment 7 and 8 bottle.800r/min stirs 20min, static 1 hour.Get levels liquid efficient liquid phase chromatographic analysis HMF concentration respectively, and calculate the concentration partition ratio of HMF according to concentration.Obtain result as shown in table 2.
The impact extracting auxiliary agent is added in the different extraction agent of table 2 and [BMIM] Cl diphasic system
As shown in Table 2, similar with MIBK extraction agent, when adopting ethyl acetate and tetrahydrofuran (THF) as extraction agent, add extraction auxiliary agent and can promote the distribution of HMF in extraction phase equally, extract compared with auxiliary agent with not adding, HMF partition ratio all improves more than 3 times.
Claims (7)
1. from ionic liquid, extract a method for 5 hydroxymethyl furfural, it is characterized in that:
In extraction agent and the two-phase extraction system that forms containing the ionic liquid of 5 hydroxymethyl furfural, add extraction auxiliary agent, realize HMF and efficiently shift to extraction phase from ionic liquid;
The mol ratio of described extraction auxiliary agent and ionic liquid is 0.05 ~ 5:1;
The mass ratio of described extraction agent and ionic liquid is 0.1 ~ 1000:1.
2. according to the method extracting 5 hydroxymethyl furfural described in claim 1 from ionic liquid, it is characterized in that: described ionic liquid is imidazoles type ionic liquid, and its structure is as follows:
Wherein, X is Cl, Br, OAc, CH
3sO
3, NTf
2, BF
4, PF
6middle at least one; N=1-12.
3. according to the method extracting 5 hydroxymethyl furfural described in claim 1 from ionic liquid, it is characterized in that: extraction agent and extraction auxiliary agent feed postition be: extraction agent and extraction auxiliary agent synchronously add or join one by one ionic liquid mutually in, two-phase, through fully mixing mass transfer and stratification, realizes HMF from ionic liquid to the phase transition of organic solvent phase.
4. according to the method extracting 5 hydroxymethyl furfural described in claim 1 from ionic liquid, it is characterized in that: extraction temperature is 0 ~ 150 DEG C.
5. according to the method extracting 5 hydroxymethyl furfural described in claim 1 from ionic liquid, it is characterized in that: the HMF after extraction adopts the method for distillation to be separated from extraction agent, and distillation temperature is 25 ~ 150 DEG C, and distillation absolute pressure is 0 ~ 2atm.
6. according to the method extracting 5 hydroxymethyl furfural described in claim 1 or 3 from ionic liquid, it is characterized in that: described extraction auxiliary agent is alcohol, ketone, phenol, carboxylic acid, aldehyde, acetonitrile, at least one in dimethyl sulfoxide (DMSO);
Described alcohol is methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, the trimethyl carbinol, ethylene glycol, glycerol, chloroethanol, at least one in phenylcarbinol;
Described ketone is acetone, butanone, at least one in 2 pentanone;
Described phenol is phenol, 2-chlorophenol, at least one in 2-cresols;
Described carboxylic acid is formic acid, acetic acid, at least one in propionic acid;
Described aldehyde is formaldehyde, at least one in acetaldehyde.
7. according to the method extracting 5 hydroxymethyl furfural described in claim 1 or 3 from ionic liquid, it is characterized in that: described extraction agent is ketone, ester class, tetrahydrofuran (THF), benzene class, halogenated hydrocarbon, at least one in dioxane;
Described ketone is methyl iso-butyl ketone (MIBK) (MIBK), at least one in polyvinylpyrrolidone;
Described ester class is methyl acetate, ethyl acetate, butylacetate, diethyl malonate, at least one in ethyl succinate;
Described benzene class is benzene, toluene, at least one in dimethylbenzene;
Described halogenated hydrocarbon is tetracol phenixin, trichloromethane, methylene dichloride, at least one in monochloro methane.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104829561A (en) * | 2014-02-11 | 2015-08-12 | 中国科学院大连化学物理研究所 | Method of extracting 5-hydroxymethyl furfural from ionic liquid |
| CN106075951A (en) * | 2016-06-30 | 2016-11-09 | 大连大学 | A kind of method that facilitated extraction separates |
| CN108727310A (en) * | 2018-06-29 | 2018-11-02 | 江苏大学 | A method of extracting 5 hydroxymethyl furfural using ionic liquid double-aqueous phase system |
Citations (3)
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| CN102321055A (en) * | 2011-09-30 | 2012-01-18 | 中国科学院过程工程研究所 | Method for preparing 5-hydroxymethylfurfural from woody biomasses |
| CN102952103A (en) * | 2011-08-17 | 2013-03-06 | 中国科学院过程工程研究所 | Method for preparing HMF through reaction-separation in supercritical CO2/ionic liquid two-phase system |
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| CN102952103A (en) * | 2011-08-17 | 2013-03-06 | 中国科学院过程工程研究所 | Method for preparing HMF through reaction-separation in supercritical CO2/ionic liquid two-phase system |
| CN102321055A (en) * | 2011-09-30 | 2012-01-18 | 中国科学院过程工程研究所 | Method for preparing 5-hydroxymethylfurfural from woody biomasses |
| CN102964319A (en) * | 2012-11-05 | 2013-03-13 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of 5-hydroxymethylfurfural |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829561A (en) * | 2014-02-11 | 2015-08-12 | 中国科学院大连化学物理研究所 | Method of extracting 5-hydroxymethyl furfural from ionic liquid |
| CN106075951A (en) * | 2016-06-30 | 2016-11-09 | 大连大学 | A kind of method that facilitated extraction separates |
| CN106075951B (en) * | 2016-06-30 | 2019-05-07 | 大连大学 | A kind of method of facilitated extraction separation |
| CN108727310A (en) * | 2018-06-29 | 2018-11-02 | 江苏大学 | A method of extracting 5 hydroxymethyl furfural using ionic liquid double-aqueous phase system |
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