CN112094187A - Method for preparing and separating levulinic acid from fructose - Google Patents

Method for preparing and separating levulinic acid from fructose Download PDF

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CN112094187A
CN112094187A CN202011176763.3A CN202011176763A CN112094187A CN 112094187 A CN112094187 A CN 112094187A CN 202011176763 A CN202011176763 A CN 202011176763A CN 112094187 A CN112094187 A CN 112094187A
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fructose
acid
levulinic acid
choline chloride
reaction
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CN112094187B (en
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侯相林
胡楠
邓天昇
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Shanxi Institute of Coal Chemistry of CAS
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
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Abstract

The invention belongs to the field of biomass catalytic conversion, and particularly relates to a method for preparing and separating levulinic acid from fructose. Aiming at the problems of low sugar concentration, low production efficiency, difficult product separation, difficult system recycling and the like in the existing reaction system for preparing levulinic acid from fructose, the invention directly utilizes part of reaction substrate fructose and choline chloride to form a fructose-choline chloride eutectic solvent, then adds an organic solvent, and strongly adds the organic solvent
Figure DDA0002748913940000011
The method has the advantages of simple operation, easy product separation, good economy, high production efficiency and environment-friendly and recyclable eutectic solvent.

Description

Method for preparing and separating levulinic acid from fructose
Technical Field
The invention belongs to the field of biomass catalytic conversion, and particularly relates to a method for preparing and separating levulinic acid from fructose.
Background
The biomass is the most abundant renewable resource on the earth, is efficiently and cleanly utilized, and has profound significance for replacing non-renewable fossil resources, reducing environmental pollution and energy crisis.
Levulinic Acid (LA) has potential as a fuel additive as one of 12 high-value platform chemicals from biomass, is a multifunctional compound containing carbonyl, alpha-hydrogen and carboxyl, can be synthesized into a plurality of high-value chemicals through aldol condensation, esterification, hydrogenation and other reactions, and has wide use value in a plurality of fields. Therefore, the production and use of LA has been an effort by researchers.
The technology for preparing LA by taking common hexose and pentose as raw materials is widely concerned, and fructose is an ideal raw material for preparing LA due to low price, easy obtaining, easy dehydration and strong controllability. At present, a reaction solvent system for preparing LA mainly comprises water, an organic solvent, an ionic liquid, a eutectic solvent (DESS) and the like, but most of reported systems have low substrate sugar concentration, generally below 20%, high viscosity, low production efficiency, high energy consumption, difficult product separation and other practical problems. The eutectic reaction system with high sugar concentration developed at present consumes the same energy, more levulinic acid can be obtained, and raw material fructose is cheap and easy to obtain, so that the production efficiency and the economy are greatly improved. Research shows that the sulfamic acid-choline chloride DES can catalyze fructose to dehydrate to prepare 5-HMF in high selectivity, and 100% of fructose conversion rate and 90.4% of yield can be obtained under the optimized condition of reaction at 140 ℃ for 180min in a MIBK-water two-phase system. Inspired by the above, the levulinic acid is further synthesized by using a simple and environment-friendly DESs system, and the appropriate reaction conditions are used, so that the reaction cost and the separation energy consumption are reduced, and the production of the levulinic acid is expected to realize new industrialization.
Disclosure of Invention
Aiming at the problems of low sugar concentration, low production efficiency, difficult product separation, difficult system recycling and the like in the existing reaction system for preparing levulinic acid from fructose, the invention provides a method for preparing and separating levulinic acid from fructose.
In order to achieve the purpose, the invention adopts the following technical scheme:
mixing fructose and choline chloride to form eutectic solvents (DESs), adding a catalyst and the solvent to react, extracting the levulinic acid generated by the reaction by using an organic solvent, and separating and recovering the solvent after the reaction is finished to obtain the levulinic acid.
A process for the preparation and isolation of levulinic acid from fructose, comprising the steps of:
step 1, mixing fructose and choline chloride in a reaction container, and completely melting the mixture into liquid to obtain fructose-choline chloride DES;
step 2, adding strong amino acid into the fructose-choline chloride DES obtained in the step 1
Figure BDA0002748913920000021
Heating an acid catalyst and an organic solvent to react them;
step 3, collecting the reacted organic phase, separating and recovering the organic solvent in the organic phase, and obtaining levulinic acid;
and 4, washing, filtering and drying the solid after the reaction is finished, and recycling. The fructose-choline chloride DES system has the advantage of being recyclable, the catalyst in the DES system can be recycled, the treatment operation is simple, and the DES system is economical and environment-friendly.
Further, the mass ratio of the fructose to the choline chloride in the step 1 is 1: 1-6: 1. The DES formed by the fructose and the choline chloride in the proportioning range has low viscosity and good liquid fluidity, and is more favorable for the rapid mass transfer of the generated levulinic acid.
Further, the step 1 of completely melting the fructose and the choline chloride into liquid means that the fructose and the choline chloride are completely melted by microwave radiation or grinding, stirring and other methods, wherein the stirring temperature is 50-80 ℃, and within the stirring temperature range, the fructose and the choline chloride with different proportions can form DES with low viscosity, so that the next reaction is facilitated.
Further, strong acid is added in the step 2
Figure BDA0002748913920000031
The amount of the acid catalyst is 1-10% of the mass of the added fructose, and the volume/mass ratio of the amount of the added organic solvent to the added fructose is 2: 1-20: 1. Within this ratio rangeThe method has the advantages of good effect, less side reaction, less consumption, proper solvent amount and capability of fully extracting products.
Further, the reaction temperature in the step 2 is 140-200 ℃, and the reaction time is 1-6 h. Within the reaction temperature and reaction time range, high levulinic acid yield can be obtained, and meanwhile, the production efficiency is high.
Further, the strength in the step 2
Figure BDA0002748913920000032
The acid catalyst is phosphotungstic acid, phosphomolybdic acid, perfluorinated sulfonic acid resin, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, SO4 2-/ZrO2-TiO2、SO4 2-/Al2O3、SO4 2-/ZrO2Any one of them. These strengths
Figure BDA0002748913920000033
The proton acidity of the acid catalyst is stronger, and the acid catalyst can better catalyze fructose to generate levulinic acid.
Further, the organic solvent in the step 2 is one or a mixture of at least two of ethyl propionate, ethyl butyrate, n-butanol, isobutanol, methyl isobutyl ketone, gamma-butyrolactone and gamma-valerolactone in any proportion. The organic solvents have good solubility to the product levulinic acid, can extract the product in time, have moderate boiling point and are easy to separate from the product.
Further, the levulinic acid product is separated from the organic phase in the step 3 by distillation or reduced pressure distillation, and the solvent is recovered by evaporation. The boiling point of the solvent used in the reaction system is moderate, so the solvent can be distilled out by distillation to obtain the product, the solvent and the product are convenient to separate, and the solvent is easy to recover.
Further, the total dosage of the fructose and the choline chloride DES is 1.0-6.0 g. The fructose-choline chloride DES reaction system with the dosage has good yield and economical materials.
Compared with the prior art, the invention has the following advantages:
1. the fructose-choline chloride DES is adopted to generate the levulinic acid, and the eutectic solvent is simple to prepare, environment-friendly and recyclable.
2. The method directly utilizes a part of reaction substrate fructose and choline chloride to form a eutectic solvent as a reaction system, does not need to add extra solvent for dissolving sugar, and has low reaction cost.
3. The reaction system of the invention is suitable for fructose with high concentration, the raw material handling capacity is large, the fructose is cheap and easy to obtain, the production efficiency is high, and the method is economic.
4. The operation of preparing and separating the levulinic acid is simple, the product is easy to separate, the product is separated in a distillation mode, and the energy consumption of separation treatment is low.
5. The reaction system can be recycled, and the solid after the reaction is finished can be recycled by simple treatment.
Drawings
FIG. 1 is an NMR hydrogen spectrum of levulinic acid, the product of example 1 of the invention.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying drawings and specific examples, which, however, should not be taken to limit the scope of the invention.
Example 1
1.0g of fructose and 0.5g of choline chloride were weighed into a 25mL round bottom flask and stirred at 50 ℃ until they were completely melted to a colorless transparent liquid to give fructose-choline chloride DES. Then, 0.1g of phosphomolybdic acid and 8mL of ethyl propionate were added thereto, and the mixture was stirred at 140 ℃ to react for 6 hours. After the reaction, the organic phase was collected, distilled and the solvent was recovered to obtain 0.125g of levulinic acid. Quantitative analysis by gas chromatography gave LA of 90% purity. And (3) washing, filtering and drying the solid after the reaction is finished, and recycling. The NMR spectrum of the product levulinic acid obtained in this example is shown in FIG. 1, and a chemical shift of 2.64ppm corresponds to the methylene hydrogen of levulinic acid close to acetyl, 2.37ppm corresponds to the methylene hydrogen of levulinic acid close to carboxyl, 2.08ppm corresponds to methyl hydrogen, and the other peaks are a solvent peak and an impurity peak.
Example 2
1.5g fructose and 0.5g choline chloride were weighed into a 25mL round bottom flask and stirred at 55 ℃ until they were completely melted to a colorless transparent liquid to give fructose-choline chloride DES. Then, 0.3g of sulfuric acid and 15mL of ethyl butyrate were added thereto, and the mixture was stirred at 150 ℃ to react for 5 hours. After the completion of the reaction, the organic phase was collected and distilled to recover the solvent, whereby 0.4239g of levulinic acid was obtained. Quantitative analysis by gas chromatography gave LA of 90.2% purity. And (3) washing, filtering and drying the solid after the reaction is finished, and recycling.
Example 3
2.0g of fructose and 0.5g of choline chloride were weighed into a 50mL round bottom flask and stirred at 60 ℃ until they were completely melted to a colorless transparent liquid to give fructose-choline chloride DES. 0.6g of phosphotungstic acid and 25mL of n-butanol were added thereto, and the mixture was stirred at 160 ℃ to react for 4 hours. After the reaction, the organic phase was collected and distilled to recover the solvent, whereby 0.798g of levulinic acid was obtained. Quantitative analysis by gas chromatography gave LA of 90.1% purity. And (3) washing, filtering and drying the solid after the reaction is finished, and recycling.
Example 4
2.5g fructose and 0.5g choline chloride were weighed into a 100mL round bottom flask and stirred at 66 ℃ until they were completely melted to a colorless transparent liquid to give fructose-choline chloride DES. 1.0g of methanesulfonic acid and 40mL of methyl isobutyl ketone (MIBK) were further added thereto, and the mixture was stirred at 170 ℃ to react for 3 hours. After the reaction, the organic phase was collected and distilled to recover the solvent, whereby 1.226g of levulinic acid was obtained. Quantitative analysis by gas chromatography gave a purity of 92% for LA. And (3) washing, filtering and drying the solid after the reaction is finished, and recycling.
Example 5
3.0g of fructose and 0.5g of choline chloride were weighed into a 100mL round bottom flask and stirred at 70 ℃ until they were completely melted to a colorless transparent liquid to give fructose-choline chloride DES. Thereto was further added 1.5g of SO4 2-/ZrO2And 60mL of isobutanol at 180 ℃ for 2 hours. After the reaction, the organic phase was collected, distilled and the solvent was recovered to obtain 1.75g of levulinic acid. By gas phaseQuantitative analysis by chromatography gave a LA purity of 91%. And (3) washing, filtering and drying the solid after the reaction is finished, and recycling.
Example 6
2.0g of fructose and 1.0g of choline chloride were weighed into a 50mL round bottom flask and stirred at 75 ℃ until they were completely melted to a colorless transparent liquid to give fructose-choline chloride DES. Thereto was further added 0.2g of SO4 2-/Al2O3And 20mL of gamma-butyrolactone, and reacting for 1h with stirring at 190 ℃. After the reaction, the organic phase was collected and distilled to recover the solvent, whereby 1.225g of levulinic acid was obtained. Quantitative analysis by gas chromatography gave LA of 90.5% purity. And (3) washing, filtering and drying the solid after the reaction is finished, and recycling.
Example 7
4.0g of fructose and 1.0g of choline chloride were weighed into a 100mL round bottom flask and stirred at 80 ℃ until they were completely melted to a colorless transparent liquid to give fructose-choline chloride DES. Thereto was further added 1.6g of SO4 2-/ZrO2-TiO2And 50mL of gamma-valerolactone, and reacting for 5h at 200 ℃ with stirring. After the completion of the reaction, the organic phase was collected and distilled to recover the solvent, whereby 2.635g of levulinic acid was obtained. Quantitative analysis by gas chromatography gave LA of 90.2% purity. And (3) washing, filtering and drying the solid after the reaction is finished, and recycling.
Example 8
5.0g of fructose and 1.0g of choline chloride were weighed into a 250mL round bottom flask and stirred at 80 ℃ until they were completely melted to a colorless transparent liquid to give fructose-choline chloride DES. Then, 0.2g of perfluorosulfonic acid resin and 100mL of γ -butyrolactone were added thereto, and the mixture was stirred at 195 ℃ to react for 6 hours. After the completion of the reaction, the organic phase was collected and distilled to recover the solvent, whereby 3.3645g of levulinic acid was obtained. Quantitative analysis by gas chromatography gave a LA purity of 91.8%. And (3) washing, filtering and drying the solid after the reaction is finished, and recycling.
Example 9
1.2g of fructose and 0.6g of choline chloride were weighed into a 25mL round bottom flask and stirred at 50 ℃ until they were completely melted to a colorless transparent liquid to give fructose-choline chloride DES. Then, 0.6g of 732 resin and 20mL of a mixed solvent of MIBK and gamma-butyrolactone were added thereto, and the mixture was stirred at 185 ℃ to react for 6 hours. After the reaction, the organic phase was collected, distilled and the solvent was recovered to obtain 0.73g of levulinic acid. Quantitative analysis by gas chromatography gave LA of 90.6% purity. And (3) washing, filtering and drying the solid after the reaction is finished, and recycling.
Example 10
1.8g of fructose and 0.6g of choline chloride were weighed into a 50mL round bottom flask and stirred at 56 ℃ until they were completely melted to a colorless transparent liquid to give fructose-choline chloride DES. Then, 0.6g of D001-CC resin and 30mL of a mixed solvent of MIBK and gamma-valerolactone were added thereto, and the mixture was stirred at 175 ℃ to react for 5 hours. After the reaction, the organic phase was collected and distilled to recover the solvent, whereby 1.162g of levulinic acid was obtained. Quantitative analysis by gas chromatography gave a LA purity of 91.3%. And (3) washing, filtering and drying the solid after the reaction is finished, and recycling.
It should be noted that: the embodiments described above are only a part of the embodiments of the present invention, and not all of them. It will be appreciated by those skilled in the art that various other changes, modifications, substitutions, combinations, and omissions may be made in the form and detail of the invention without departing from the spirit and scope of the invention.

Claims (9)

1. A method for preparing and separating levulinic acid from fructose is characterized by comprising the following steps:
step 1, mixing fructose and choline chloride in a reaction container, and completely melting the mixture into liquid to obtain fructose-choline chloride DES;
step 2, adding strong amino acid into the fructose-choline chloride DES obtained in the step 1
Figure FDA0002748913910000013
Heating an acid catalyst and an organic solvent to react them;
step 3, collecting the reacted organic phase, separating and recovering the organic solvent in the organic phase, and obtaining levulinic acid;
and 4, washing, filtering and drying the solid after the reaction is finished, and recycling.
2. The process of claim 1 for the preparation and isolation of levulinic acid from fructose, wherein: the mass ratio of the fructose to the choline chloride in the step 1 is 1: 1-6: 1.
3. The process of claim 1 for the preparation and isolation of levulinic acid from fructose, wherein: in the step 1, the fructose and choline chloride are completely melted into liquid by microwave radiation or grinding and stirring, wherein the stirring temperature is 50-80 ℃.
4. The process of claim 1 for the preparation and isolation of levulinic acid from fructose, wherein: adding strong in the step 2
Figure FDA0002748913910000012
The amount of the acid catalyst is 1-10% of the mass of the added fructose, and the volume/mass ratio of the amount of the added organic solvent to the added fructose is 2: 1-20: 1.
5. The process of claim 1 for the preparation and isolation of levulinic acid from fructose, wherein: the reaction temperature in the step 2 is 140-200 ℃, and the reaction time is 1-6 h.
6. The process of claim 1 for the preparation and isolation of levulinic acid from fructose, wherein: strong in said step 2
Figure FDA0002748913910000011
The acid catalyst is phosphotungstic acid, phosphomolybdic acid, perfluorinated sulfonic acid resin, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, SO4 2-/ZrO2-TiO2、SO4 2-/Al2O3、SO4 2-/ZrO2Any one of them.
7. The process of claim 1 for the preparation and isolation of levulinic acid from fructose, wherein: the organic solvent is one or a mixture of at least two of ethyl propionate, ethyl butyrate, n-butanol, isobutanol, methyl isobutyl ketone, gamma-butyrolactone and gamma-valerolactone in any proportion.
8. The process of claim 1 for the preparation and isolation of levulinic acid from fructose, wherein: the levulinic acid product is separated from the organic phase in the step 3 by distillation or reduced pressure distillation, and the solvent is recovered by evaporation.
9. The process of claim 1 for the preparation and isolation of levulinic acid from fructose, wherein: the total dosage of the fructose and the choline chloride DES is 1.0-6.0 g.
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN112851490A (en) * 2021-01-15 2021-05-28 太原工业学院 Method for producing levulinic acid by efficiently catalyzing saccharides
CN115536512A (en) * 2022-09-15 2022-12-30 北京理工大学 Method and device for continuously synthesizing levulinic acid
CN115894193A (en) * 2021-09-30 2023-04-04 中国石油化工股份有限公司 Method for decomposing hydroperoxide acid

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112851490A (en) * 2021-01-15 2021-05-28 太原工业学院 Method for producing levulinic acid by efficiently catalyzing saccharides
CN112851490B (en) * 2021-01-15 2023-03-28 太原工业学院 Method for producing levulinic acid by efficiently catalyzing saccharides
CN115894193A (en) * 2021-09-30 2023-04-04 中国石油化工股份有限公司 Method for decomposing hydroperoxide acid
CN115536512A (en) * 2022-09-15 2022-12-30 北京理工大学 Method and device for continuously synthesizing levulinic acid

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