CN103467277A - Method for converting carbohydrates into levulinic acid through microwave-assisted ionic liquid catalysis - Google Patents
Method for converting carbohydrates into levulinic acid through microwave-assisted ionic liquid catalysis Download PDFInfo
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- CN103467277A CN103467277A CN2013104044057A CN201310404405A CN103467277A CN 103467277 A CN103467277 A CN 103467277A CN 2013104044057 A CN2013104044057 A CN 2013104044057A CN 201310404405 A CN201310404405 A CN 201310404405A CN 103467277 A CN103467277 A CN 103467277A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a method for converting carbohydrates into levulinic acid through microwave-assisted ionic liquid catalysis. The method comprises the steps of adding carbohydrates (monosaccharides, disaccharides, soluble starch, microcrystalline cellulose, corn stalks 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 80-160 DEG C. According to the method, ionic liquid is applied to the catalysis of carbohydrate transformation at normal pressure through microwave-assisted heating for the first time so as to so as to transform carbohydrates into levulinic acid.
Description
Technical field
The invention belongs to ionic liquid and be applied to the directed transformation technology of carbohydrate field, can significantly reduce the ionic liquid consumption by the method, improve carbohydrate and be converted into the yield of levulinic acid, thereby be conducive to improve ionic liquid, be converted into the economy of levulinic acid for carbohydrate.
Background technology
The petrochemical material that coal, oil etc. are representative of take has met the energy demand of the mankind more than 90%, be also global chemical industry basis.Although the definite date of crude oil and Sweet natural gas exhaustion is difficult to prediction, accelerates development continuable fuel and carbon back raw material and obtained extensive approval with the substitute fossil fuels great development.Meanwhile, fuel, hardware and software platform compound and the high valuable chemicals that Carbon emission also requires to develop new green production made great efforts to reduce in the whole world.Hydrogenation of carbon dioxide can produce monomer and the intermediate with carbon back, in addition, by photosynthesis, can be converted into biomass.Wherein carbohydrate is regarded as the override renewable resources as the major portion of biomass, mainly with forms such as sugar, starch, Mierocrystalline cellulose, lignocelluloses, occurs.
In the levulinic acid molecule, existing carboxyl has again ketone group, there is good reactivity, produce the chemical of various functions by esterification, halogenation, hydrogenation, acetalation etc., such as spices, solvent, rubber ingredients, oil dope, medicine, agricultural chemicals, surfactant etc.Owing to can take biomass as waste, its mass-producing preparation has in recent years become the focus of research.Mainly biomass fiber is hydrolyzed to wood sugar and glucose, then under acidic conditions, further dewaters and obtain furfural and 5 hydroxymethyl furfural, latter's further acidifying again is decomposed into levulinic acid.The catalyzer used in process is mainly mineral acid, comprises sulfuric acid, hydrochloric acid, hydrofluoric acid.But these catalyzer are large to equipment corrosion, and produce a large amount of liquid and waste slag produced.
Ionic liquid (IL) is as a kind of emerging catalysts and solvents, there is very high thermostability and catalytic performance, good conductive thermal conductivity and " zero " vapour pressure, be widely used in recent years chemical reaction, as fabrication of new materials, polyreaction, organic synthesis, electrochemistry, sepn process etc.Particularly be applied to Green Chemistry cleaner production field and have a good application prospect replacing inflammable and explosive and highly corrosive organic acids and base, use it for carbohydrate inversion and prepare high valuable chemicals and become new at present study hotspot.
Summary of the invention
[goal of the invention] the object of the invention is to develop industrial carbohydrate and is catalytically conveted to levulinic acid novel green conversion process.
[design of the present invention] microwave as a kind of emerging, efficient supplementary means be applied to the carbohydrate 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 carbohydrate of microwave-assisted is converted into levulinic acid.The present invention, by microwave-assisted and ionic liquid-catalyzed system are coupled, is converted into the efficiency of levulinic acid to improve carbohydrate, be beneficial to the high value trans-utilization of carbohydrate.
[technical solution of the present invention]
1, the present invention relates to the method that the ionic liquid-catalyzed carbohydrate of a kind of microwave-assisted is converted into levulinic acid, comprise following steps:
Step 1, synthetic ionic-liquid catalyst: replacement(metathesis)reaction occurs in tetramethyl guanidine or thanomin and acid solution (acetic acid, lactic acid, Tetrafluoroboric acid etc.) in ethanol, and underpressure distillation is purified, drying for standby; N-Methylimidazole and ethylene chlorhydrin or 2-chloroethyl amine hydrochloride are replaced with excessive sodium tetrafluoroborate after metathesis in solvent again, after the oven dry of purifying after filtration, obtain 1-hydroxyethyl-3 methyl imidazolium tetrafluoroborate and 1-aminoethyl-3-methyl imidazolium tetrafluoroborate.
Step 2, according to a certain percentage carbohydrate 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; The molar weight of N-Methylimidazole and ethylene chlorhydrin or 2-chloroethyl amine hydrochloride is 1:1.1; The molar weight of gained muriate and sodium tetrafluoroborate is 1:1.05.
In step 2, ionic-liquid catalyst used is selected from the tetramethyl guanidine a tetrafluoro borate, the tetramethyl guanidine lactic acid salt, tetramethyl guanidine acetate, 1-aminoethyl-3-methyl imidazolium tetrafluoroborate, the thanomin a tetrafluoro borate, 1-hydroxyethyl-3-methyl imidazolium tetrafluoroborate etc., mass ratio according to catalyzer and carbohydrate is 0.1-0.5, carbohydrate and reaction solvent solid-to-liquid ratio are the 0.02-0.1(mass ratio), quantitative industrial carbohydrate 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: N,N-dimethylacetamide (LiCl-DMAc), dimethyl sulfoxide (DMSO) (DMSO), sec-butyl alcohol solution.
Adopt the content of levulinic acid in Agilent Technologies1200Series HPLC liquid chromatography external standard method carbohydrate inversion liquid in step 3, 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 carbohydrate conversion process, has improved the yield that carbohydrate is converted into levulinic acid, the reaction conditions gentleness.
2. to adopt ionic liquid be that the catalyst carbohydrate is converted into levulinic acid in the present invention, realized carbohydrate 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 0.05g, sec-butyl alcohol 50ml is placed in microwave reactor, and under nitrogen protection, the stirring and refluxing reaction, be warming up to 80 ℃, and microwave output power is 400w, reaction times 5min, the timing sampling analysis, yield of levulinic acid is 10.78%.
Embodiment 2
By sucrose 0.1g, tetramethyl guanidine lactic acid salt ([TMG] L) catalyzer 0.03g, DMSO100ml is placed in microwave reactor; under nitrogen protection, the stirring and refluxing reaction, be warming up to 140 ℃, and microwave output power is 600w; reaction times 20min, the timing sampling analysis, yield of levulinic acid is 16.74%
Embodiment 3
By starch 0.3g, tetramethyl guanidine acetate ([TMG] OAc) catalyzer 0.1g, DMSO60ml is placed in microwave reactor; under nitrogen protection, the stirring and refluxing reaction, be warming up to 160 ℃, and microwave output power is 800w; reaction times 60min, the timing sampling analysis, yield of levulinic acid is 14.87%.
Embodiment 4
By Microcrystalline Cellulose 0.2g, thanomin a tetrafluoro borate ([MEA] BF
4) catalyzer 0.1g, 10% LiBr-DMF solution 100ml is placed in microwave reactor, and under nitrogen protection, the stirring and refluxing reaction, be warming up to 120 ℃, and microwave output power is 600w, reaction times 40min, the timing sampling analysis, yield of levulinic acid is 8.87%
Embodiment 5
Maize straw is dried, pulverized, sieve, take 0.1g, 1-hydroxyethyl-3 methyl imidazolium tetrafluoroborate ([C
2oHMIM] BF
4) catalyzer 0.06g, DMAc solution 50ml is placed in microwave reactor, and under nitrogen protection, the stirring and refluxing reaction, be warming up to 120 ℃, and microwave output power is 400w, reaction times 10min, the timing sampling analysis, yield of levulinic acid is 6.78%.
Embodiment 6
By cellobiose 0.4g, 1-hydroxyethyl-3 methyl imidazolium tetrafluoroborate 1-aminoethyl-3-methyl imidazolium tetrafluoroborate ([AEMIM] BF
4) catalyzer 0.08g, DMSO80ml 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 10min, the timing sampling analysis, yield of levulinic acid is 6.97%.
Claims (5)
1. the ionic liquid-catalyzed carbohydrate of microwave-assisted is converted into the method for levulinic acid, it is characterized in that the catalyzer that the method adopts is ionic liquid.
2. the ionic liquid-catalyzed carbohydrate of a kind of microwave-assisted is converted into the method for levulinic acid 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 carbohydrate of a kind of microwave-assisted is converted into the method for levulinic acid 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 etc., and the mass ratio of catalyzer and carbohydrate is 0.1-0.6.
4. the ionic liquid-catalyzed carbohydrate of a kind of microwave-assisted is converted into the method for levulinic acid as claimed in claim 1, it is characterized in that: carbohydrate 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 80~160 ℃.
5. the ionic liquid-catalyzed carbohydrate of a kind of microwave-assisted is converted into the method for levulinic acid as claimed in claim 4, it is characterized in that: reaction solvent used is N, the N-N,N-DIMETHYLACETAMIDE, lithium chloride-N,N-dimethylacetamide (LiCl-DMAc), dimethyl sulfoxide (DMSO) (DMSO), sec-butyl alcohol solution.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104016853A (en) * | 2014-06-09 | 2014-09-03 | 大连理工大学 | Method for preparing acetylpropionic acid by catalytically converting lignocelluloses |
CN104163762A (en) * | 2014-07-29 | 2014-11-26 | 中国农业大学 | Method for synthesis of acetyl propionate through microwave assisted liquefaction of biomass straw |
CN108948380A (en) * | 2018-07-18 | 2018-12-07 | 贵州大学 | The poly- proton type ionic liquid gel/nano metal composite material and preparation method of cellulose and application |
CN109678688A (en) * | 2018-12-26 | 2019-04-26 | 瑞孚信江苏药业股份有限公司 | A kind of new preparation process of cyclopropyl ketone |
CN110426481A (en) * | 2019-09-16 | 2019-11-08 | 亚太星原农牧科技海安有限公司 | The method of lactic acid content and the measurement extracting method of prepare liquid in a kind of measurement fermented bean dregs |
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CN101914011A (en) * | 2010-07-27 | 2010-12-15 | 浙江农林大学 | Method for preparing levulinic acid by catalyzing bamboo shoot shells through functional ionic liquid |
CN103044237A (en) * | 2011-10-13 | 2013-04-17 | 中国科学院大连化学物理研究所 | Method for preparing levulinic acid by converting cellulose efficiently |
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CN101914011A (en) * | 2010-07-27 | 2010-12-15 | 浙江农林大学 | Method for preparing levulinic acid by catalyzing bamboo shoot shells through functional ionic liquid |
CN103044237A (en) * | 2011-10-13 | 2013-04-17 | 中国科学院大连化学物理研究所 | Method for preparing levulinic acid by converting cellulose efficiently |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104016853A (en) * | 2014-06-09 | 2014-09-03 | 大连理工大学 | Method for preparing acetylpropionic acid by catalytically converting lignocelluloses |
CN104163762A (en) * | 2014-07-29 | 2014-11-26 | 中国农业大学 | Method for synthesis of acetyl propionate through microwave assisted liquefaction of biomass straw |
CN108948380A (en) * | 2018-07-18 | 2018-12-07 | 贵州大学 | The poly- proton type ionic liquid gel/nano metal composite material and preparation method of cellulose and application |
CN108948380B (en) * | 2018-07-18 | 2021-11-12 | 贵州大学 | Cellulose proton type ionic liquid gel/nano metal composite material and preparation method and application thereof |
CN109678688A (en) * | 2018-12-26 | 2019-04-26 | 瑞孚信江苏药业股份有限公司 | A kind of new preparation process of cyclopropyl ketone |
CN109678688B (en) * | 2018-12-26 | 2022-01-25 | 瑞孚信江苏药业股份有限公司 | Novel preparation method of cyclopropane ketone |
CN110426481A (en) * | 2019-09-16 | 2019-11-08 | 亚太星原农牧科技海安有限公司 | The method of lactic acid content and the measurement extracting method of prepare liquid in a kind of measurement fermented bean dregs |
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