CN103467419A - Method for transforming monosaccharides into high-value-added chemicals through microwave-assisted ionic liquid catalysis - Google Patents
Method for transforming monosaccharides into high-value-added chemicals through microwave-assisted ionic liquid catalysis Download PDFInfo
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- CN103467419A CN103467419A CN2013104033315A CN201310403331A CN103467419A CN 103467419 A CN103467419 A CN 103467419A CN 2013104033315 A CN2013104033315 A CN 2013104033315A CN 201310403331 A CN201310403331 A CN 201310403331A CN 103467419 A CN103467419 A CN 103467419A
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Abstract
The invention discloses a method for transforming monosaccharides into high-value-added chemicals through microwave-assisted ionic liquid catalysis. The method comprises the steps of adding monosaccharides (fructose, glucose, maltose, mannose, arabinose, xylose or the like), an ionic liquid catalyst and an organic solvent (dimethyl sulfoxide, N,N-dimethylformamide, lithium chloride-N, N-dimethylacetamide or the like) into a microwave reactor at normal pressure, introducing nitrogen gas for protecting, carrying out magnetic stirring at a constant speed, cooling for refluxing, and carrying out microwave reaction for 1-120 minutes at the power of 400-800w at the constant temperature of 100-160 DEG C. According to the method, ionic liquid is applied to the catalysis of monosaccharide transformation at normal pressure through microwave-assisted heating so as to transform monosaccharides into the high-value-added chemicals, such as furfural, formic acid, levulinic acid, 5-hydroxymethyl furfural and the like.
Description
Technical field
The invention belongs to ionic liquid and be applied to the directed transformation technology of monose field, can significantly reduce the ionic liquid consumption by the method, improve monose and be converted into the yield of high valuable chemicals, thereby be conducive to improve ionic liquid, be converted into the economy of high valuable chemicals for monose.
Background technology
Along with the exhaustion day by day of traditional fossil oil and the continuous increase of environmental protection pressure, develop continuable, free of contamination, reproducible substitute energy and day by day be subject to extensive concern.Biomass are as enormous amount, cheap a kind of sustainability resource, and being applied to chemical industry is one of effective way solved current resource and energy dilemma.Monose and derivative thereof extensively exist in nature, and be also the elementary cell that forms carbohydrate, and be easy to obtain from biomass, be to prepare the topmost raw material of high valuable chemicals, a large amount of scholars have carried out wide coverage on this basis.
mineral acid, organic acid, H type zeolite and other molecular sieves, acidic cation-exchange resin and heteropolyacid etc., be widely used in the catalyzed degradation of monose, and gained 5-HMF yield does not wait 10%~100%.
Ionic liquid, as a kind of novel environmentally friendly solvent and liquid acid alkaline catalysts, has advantages of that other solvents and traditional catalyst do not possess.That ionic liquid has is non-volatile, the liquid journey is wide, select solvability, the characteristic such as can design, ionic liquid is carried out to functionalization, can make it there is abundant, multifarious structure and show different, adjustable physical and chemical performance, in being widely used in chemical reaction research and producing.Good physico-chemical property based on above-mentioned ionic liquid, ionic liquid is applied to the monose conversion and is subject to extensive concern.Moreau (Clement Lansalot.Matras, Claude Moreau.Dehydration of fructose into5-hydroxymethylfurfural in the presence of ionic liquids.Catalysis Communications, 2003,4,517-520.) research group is used hydrophilic 1-butyl-3-Methylimidazole Tetrafluoroboric acid ([BMIM] BF
4) and hydrophobic 1-butyl-3-Methylimidazole hexafluorophosphate ([BMIM] PF
6) for fructose, be hydrolyzed.The experiment used catalyst is the Amberlyst-15 resin, by [BMIM] PF
6[BMIM] BF
4use as mixed solvent, and add a certain amount of DMSO as cosolvent, under 80 ℃ of conditions, react 24h, the productive rate of HMF can reach 80%.Zhao (Zhang, Z.H., Zhao, Z.B.K., Microwave-assisted conversion of lignocellulosic biomass into furfural in ionic liquid.Bioresour.Technol.2010,101,1111 – 1114.) etc. adopt the standby 5-HMF of 3-allyl group-1-(4-sulphur butyl) imidazoles trifluoromethyl sulfonic acid and Lewis acid derivative 3-allyl group-1-(4-sulfuryl chloride butyl) imidazoles trifluoromethyl sulfonic acid catalysis monose Dehydration thereof, in microwave heating 5min, fructose prepares the 5-HMF productive rate and reaches 86%.
Although ionic liquid prepares 5-HMF and obtained a series of gratifying achievements for carbohydrate inversion, current research mainly concentrates on usings ionic liquid and prepares 5 hydroxymethyl furfural as solvent catalysis.Because ionic liquid is expensive, and this system is unfavorable for recycling, and the cost that makes ionic liquid prepare 5-HMF as solvent is high, and industrialized utilization is difficult to realize.From economic angle, ionic liquid is more conducive to reduce costs and realization of industrialization as catalyzer.The more economical and efficient ionic liquid-catalyzed system of exploitation is used for monose to be converted into chemical imperative as can be seen here.
Summary of the invention
[goal of the invention] the object of the invention is to develop industrial monose and is catalytically conveted to high valuable chemicals novel green conversion process.
[design of the present invention] microwave as a kind of emerging, efficient supplementary means be applied to the monose conversion process compared to by the material heat-conductive characteristic by traditional type of heating such as the oil bath of object heating or sand-baths, heating rate is faster, be heated evenly.Ionic liquid is as environment-friendly catalyst newly developed in recent years, with traditional inorganic, that the organic acids and base catalyzer is compared catalytic process is more green.Based on the ionic liquid thermostability stronger characteristics, the present invention has designed the reaction system that the ionic liquid-catalyzed monose of microwave-assisted is converted into high valuable chemicals.The present invention, by microwave-assisted and ionic liquid-catalyzed system are coupled, is converted into the efficiency of high valuable chemicals to improve monose, be beneficial to the high value trans-utilization of monose.
[technical solution of the present invention]
1, the present invention relates to the method that the ionic liquid-catalyzed monose of a kind of microwave-assisted is converted into high valuable chemicals, comprise following steps:
Step 1, synthetic ionic-liquid catalyst (the guanidine class ionic liquid of take is example): replacement(metathesis)reaction occurs in tetramethyl guanidine and acid solution (acetic acid, lactic acid, Tetrafluoroboric acid etc.) in ethanol, and underpressure distillation is purified, drying for standby;
Step 2, according to a certain percentage monose and catalyzer are added in organic solvent, be placed in microwave reactor, stirring and refluxing reaction under nitrogen protection, under certain microwave output power, the constant temperature reaction, obtain high valuable chemicals.
Step 3, reaction finish rear cooling, standing, centrifugal, filtration, assay products yield.
In step 1, the molar weight of tetramethyl guanidine and acid solution is 1:1.
In step 2, ionic-liquid catalyst used is selected from tetramethyl guanidine a tetrafluoro borate, tetramethyl guanidine lactic acid salt, tetramethyl guanidine acetate, 1-aminoethyl-3-methyl imidazolium tetrafluoroborate, thanomin a tetrafluoro borate, 1-hydroxyethyl-3-methyl imidazolium tetrafluoroborate; according to catalyzer and monose mass ratio, be 0.05~0.2; quantitative monose and catalyzer are added in reaction solvent; be placed in microwave reactor; stirring and refluxing reaction under nitrogen protection; be warming up to 80-160 ℃; microwave output power is 400~800w, reaction times 5~120min.
In step 2, solvent for use is: dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), n-formyl sarcolysine base pyrrolidone (NMF), methyl iso-butyl ketone (MIBK) (MIBK) and propyl carbinol, sec-butyl alcohol and isopropylcarbinol etc.
Adopt the content of high valuable chemicals in Agilent Technologies1200Series HPLC liquid chromatography external standard method monose hydrolyzed solution in step 3, the UV detector, chromatographic column is C18 post (3.9.mm * 150mm), moving phase is methanol/water=40:60 (v/v), flow velocity is 0.6ml/min, and detector temperature is 35 ℃; The RID detector, chromatographic column is Hi-PLex H post, moving phase is 5mM H
2sO
4, flow velocity is 0.6ml/min, detector temperature is 65 ℃.
The present invention has following characteristics and advantage:
1. the present invention is coupled microwave-assisted and monose conversion process, has improved the yield that monose is converted into high valuable chemicals, the reaction conditions gentleness.
2. to adopt ionic liquid be that catalyst monose is converted into high valuable chemicals in the present invention, realized monose conversion process green.
Embodiment
Below by embodiment, the present invention will be further described.
Embodiment 1
By fructose 0.5g, tetramethyl guanidine a tetrafluoro borate ([TMG] BF
4) catalyzer 0.025g, DMSO solution 50ml is placed in microwave reactor, stirring and refluxing reaction under nitrogen protection; be warming up to 100 ℃, microwave output power is 400w, reaction times 20min; timing sampling is analyzed, and furaldehyde yield is 8.35%, and the 5 hydroxymethyl furfural yield is 86.34%.
Embodiment 2
By glucose 0.4g; tetramethyl guanidine lactic acid salt ([TMG] L) catalyzer 0.04g, sec-butyl alcohol 80ml is placed in microwave reactor, stirring and refluxing reaction under nitrogen protection; be warming up to 140 ℃; microwave output power is 400w, reaction times 30min, timing sampling analysis; furaldehyde yield is 8.20%; the 5-HMF yield is 43.78%, and yield of levulinic acid is 16.31%, and the formic acid yield is 12.42%.
Embodiment 3
By pectinose 0.3g, 1-aminoethyl-3-methyl imidazolium tetrafluoroborate ([AEMIM] BF
4) catalyzer 0.045g, DMAc100ml is placed in microwave reactor, and under nitrogen protection, the stirring and refluxing reaction, be warming up to 140 ℃, and microwave output power is 400w, reaction times 60min, the timing sampling analysis, furaldehyde yield is 62.37%.
Embodiment 4
By seminose 0.2g, thanomin a tetrafluoro borate ([MEA] BF
4) catalyzer 0.025g; DMF solution 60ml is placed in microwave reactor; stirring and refluxing reaction under nitrogen protection; be warming up to 160 ℃, microwave output power is 400w, reaction times 40min; timing sampling is analyzed; the 5-HMF yield is 19.34%, and yield of levulinic acid is 12.53%, and the formic acid yield is 10.36%.
Embodiment 5
By semi-lactosi 0.1g, 1-hydroxyethyl-3 methyl imidazolium tetrafluoroborate ([C
2oHMIM] BF
4) catalyzer 0.02g, MIBK100ml is placed in microwave reactor, and under nitrogen protection, the stirring and refluxing reaction, be warming up to 120 ℃; microwave output power is 400w, reaction times 80min, timing sampling analysis; the 5-HMF yield is 19.34%, and yield of levulinic acid is 12.53%, and the formic acid yield is 10.36%.
Embodiment 6
By wood sugar 0.5g, 1-aminoethyl-3-methyl imidazolium tetrafluoroborate ([AEMIM] BF
4) catalyzer 0.05g, DMSO solution 100ml is placed in microwave reactor, stirring and refluxing reaction under nitrogen protection; be warming up to 140 ℃, microwave output power is 400w, reaction times 100min; timing sampling is analyzed, and furaldehyde yield is 24.35%, and the formic acid yield is 13.14%.
Claims (6)
1. the ionic liquid-catalyzed monose of microwave-assisted is converted into the method for high valuable chemicals, it is characterized in that the catalyzer that the method adopts is ionic liquid.
2. the ionic liquid-catalyzed monose of a kind of microwave-assisted is converted into the method for high valuable chemicals as claimed in claim 1, it is characterized in that: the mode with Microwave-assisted firing substitutes conventional oil bath, salt bath or sand-bath type of heating.
3. the ionic liquid-catalyzed monose of a kind of microwave-assisted is converted into the method for high valuable chemicals as claimed in claim 1, and it is characterized in that: monose reactant used is fructose, glucose, seminose, semi-lactosi, pectinose or wood sugar.
4. the ionic liquid-catalyzed monose of a kind of microwave-assisted is converted into the method for high valuable chemicals as claimed in claim 1, it is characterized in that: ionic-liquid catalyst used is selected from tetramethyl guanidine a tetrafluoro borate, tetramethyl guanidine lactic acid salt, tetramethyl guanidine acetate, 1-aminoethyl-3 methyl imidazolium tetrafluoroborate, thanomin a tetrafluoro borate, 1-hydroxyethyl-3 methyl imidazolium tetrafluoroborate, and catalyzer and monose mass ratio are 0.05~0.2.
5. the ionic liquid-catalyzed monose of a kind of microwave-assisted is converted into the method for high valuable chemicals as claimed in claim 1, it is characterized in that: monose and catalyzer are added in reaction solvent, be placed in microwave reactor, stirring and refluxing reaction under nitrogen protection; Microwave output power is 400~800w; Reaction times 1~120min; Temperature of reaction is 100-160 ℃.
6. the ionic liquid-catalyzed monose of a kind of microwave-assisted is converted into the method for high valuable chemicals as claimed in claim 4, it is characterized in that reaction solvent used is dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), n-formyl sarcolysine base pyrrolidone (NMF), methyl iso-butyl ketone (MIBK) (MIBK) and propyl carbinol, sec-butyl alcohol and isopropylcarbinol.
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Cited By (5)
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CN104496797A (en) * | 2014-12-17 | 2015-04-08 | 浙江大学 | Method for preparing acetyl propionic acid by degrading hexamylose in ionic liquid-water medium |
CN106632164A (en) * | 2016-12-29 | 2017-05-10 | 江南大学 | Preparation and application of magnetic metallic oxide coupled acid poly-ionic liquid |
CN106674164A (en) * | 2016-12-29 | 2017-05-17 | 江南大学 | Method for preparing furfural based on magnetic metal oxide crosslinked acidic polyion liquid |
CN110606835A (en) * | 2019-10-15 | 2019-12-24 | 东北林业大学 | Preparation method of pentamethyl furfural |
CN112625013A (en) * | 2021-01-22 | 2021-04-09 | 江西农业大学 | Method for preparing furfural from xylose under microwave heating |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104496797A (en) * | 2014-12-17 | 2015-04-08 | 浙江大学 | Method for preparing acetyl propionic acid by degrading hexamylose in ionic liquid-water medium |
CN106632164A (en) * | 2016-12-29 | 2017-05-10 | 江南大学 | Preparation and application of magnetic metallic oxide coupled acid poly-ionic liquid |
CN106674164A (en) * | 2016-12-29 | 2017-05-17 | 江南大学 | Method for preparing furfural based on magnetic metal oxide crosslinked acidic polyion liquid |
CN110606835A (en) * | 2019-10-15 | 2019-12-24 | 东北林业大学 | Preparation method of pentamethyl furfural |
CN112625013A (en) * | 2021-01-22 | 2021-04-09 | 江西农业大学 | Method for preparing furfural from xylose under microwave heating |
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