CN115806534A - Preparation method of 5-hydroxymethylfurfural - Google Patents
Preparation method of 5-hydroxymethylfurfural Download PDFInfo
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 87
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000005715 Fructose Substances 0.000 claims abstract description 40
- 229930091371 Fructose Natural products 0.000 claims abstract description 40
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 36
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 63
- 238000000605 extraction Methods 0.000 claims description 34
- 238000004821 distillation Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000012295 chemical reaction liquid Substances 0.000 claims description 27
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
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- 239000006227 byproduct Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
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- -1 5-hydroxymethylfurfural carbon Chemical compound 0.000 description 1
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The application discloses a preparation method of 5-hydroxymethylfurfural, which comprises the following steps: reacting a solution containing fructose under the catalytic action of a catalyst to obtain the 5-hydroxymethylfurfural; the catalyst comprises hydrogen peroxide; the mass ratio of the catalyst to the fructose is 0.01-1; the mass of the catalyst is calculated by the mass of hydrogen peroxide. The method takes hydrogen peroxide as a catalyst, can effectively control the occurrence of side reactions, avoids the generation of black rot, improves the selectivity of the reaction, and greatly reduces the equipment maintenance and labor cost.
Description
Technical Field
The application relates to a preparation method of 5-hydroxymethylfurfural, and belongs to the field of preparation and synthesis of 5-hydroxymethylfurfural.
Background
In the past century, the fossil industry opened the door to modern times, not only increasing the economy, but also advancing our culture and science. With this global development, industrial chemistry has been consolidated, playing an important role in ensuring the safety of fuels, fertilizers/agrochemicals, detergents, pharmaceuticals, food additives, polymers and textiles. In the imagination of people, fossil resources present the characteristics of endless, readily available and low cost, thereby creating a disposable idea. Today, we are paying a price for widespread utilization of fossil resources, and we are dealing with the necessity of protecting global resources. Furthermore, the increase in total product weight (GDP) in the world population and everyone is expected to have a profound impact on global economy and cumulative energy demand. In this case, the real challenge of industrial chemistry is to ensure the production of chemicals and materials that can improve our daily lives, while reducing its impact on the environment according to the "12-item green chemistry principle" and the "benign design philosophy", an economically feasible and environmentally friendly chemical process.
The efficient use of biomass has recently received widespread attention as a potential alternative to petroleum in the production of fuels and chemicals. Due to its inedibility, richness and worldwide distribution, one of the most demanding processes is the conversion of lignocellulosic biomass, the depolymerisation of cellulose to give abundant monosaccharides, which are converted by isomerization to fructose and subsequent dehydration to further 5-hydroxymethylfurfural (5-HMF), which is considered as an important intermediate for the synthesis of various chemicals and alternative fuels. Therefore, the selective production of 5-hydroxymethylfurfural is highly desirable for establishing a successful biorefinery. Traditional 5-hydroxymethylfurfural is selectively produced from fructose by dehydration in the presence of a liquid or solid acid. However, this process usually requires a large amount of organic solvent or a catalyst containing heavy metals such as chromium, but the selectivity of the reaction is low, and by-products such as black rot which may damage the equipment and process are easily produced. Meanwhile, the treatment of the reaction wastewater after the reaction is difficult and requires a large number of complicated operations, which is not favorable for industrial scale-up production.
Disclosure of Invention
The application provides a preparation method of 5-hydroxymethylfurfural, which can effectively control side reactions by using hydrogen peroxide as a catalyst, avoid the generation of black rot, improve the selectivity of the reaction and greatly reduce the equipment maintenance and labor cost.
A preparation method of 5-hydroxymethylfurfural comprises the following steps:
reacting a solution containing fructose under the catalytic action of a catalyst to obtain the 5-hydroxymethylfurfural;
the catalyst comprises hydrogen peroxide;
the mass ratio of the catalyst to the fructose is 0.01-1;
the mass of the catalyst is calculated by the mass of hydrogen peroxide.
Optionally, the catalyst is hydrogen peroxide.
Optionally, H in the hydrogen peroxide 2 O 2 10 to 30wt%.
Optionally, the mass ratio of the catalyst to the fructose is 0.01-1;
the mass of the catalyst is calculated by the mass of hydrogen peroxide.
Optionally, the mass ratio of the catalyst to the fructose is 0.12-1.
Optionally, the mass ratio of the catalyst to the fructose is 0.15-1.
Optionally, the mass ratio of the catalyst to the fructose is 0.15-1.
Optionally, the solvent of the solution comprises water;
optionally, the mass ratio of the fructose to the solvent in the solution is 0.1-10.
Optionally, in the solution, the mass ratio of fructose to solvent is 5-10.
Optionally, in the solution, the mass ratio of fructose to solvent is 8-10.
Optionally, in the solution, the mass ratio of fructose to solvent is 8-10.
Optionally, the solvent of the solution is water.
Optionally, the conditions of the reaction include: the reaction temperature is 60-180 ℃.
Optionally, the upper limit of the reaction temperature is selected from 70 ℃, 80 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 175 ℃ or 180 ℃; the lower limit is selected from 60 deg.C, 70 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, and 175 deg.C.
Optionally, the conditions of the reaction include: the reaction time is 2 to 10 hours.
Alternatively, the upper reaction time limit is selected from 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours; the lower limit is selected from 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or 9 hours.
Optionally, after the reaction is finished, the method further comprises a purification step:
adding an extracting agent into the reaction liquid for extraction to obtain upper-layer extraction liquid, and carrying out reduced pressure distillation on the upper-layer extraction liquid to obtain the 5-hydroxymethylfurfural.
Optionally, the volume ratio of the extractant to the reaction solution is 1 to 3;
optionally, the extractant comprises at least one of ethyl acetate and dimethyl carbonate.
Optionally, the number of extractions is 2 to 5.
Optionally, the conditions of the reduced pressure distillation comprise:
the vacuum degree is 0.01-5 KPa, the temperature is 30-70 ℃, and the time is 0.5-3 hours.
Optionally, the upper limit of the vacuum is selected from 0.02KPa, 0.05KPa, 0.1KPa, 0.5KPa, 1KPa, 2KPa, 3KPa, 4KPa, 4.5KPa, or 5KPa; the lower limit is selected from 0.01KPa, 0.02KPa, 0.05KPa, 0.1KPa, 0.5KPa, 1KPa, 2KPa, 3KPa, 4KPa or 4.5KPa.
Optionally, the upper temperature limit is selected from 60 ℃, 55 ℃, 50 ℃, 45 ℃, 40 ℃, or 35 ℃; the lower limit is selected from 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C or 55 deg.C.
Alternatively, the upper time limit is selected from 0.6 hours, 0.8 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, or 3 hours; the lower limit is selected from 2.5 hours, 2 hours, 1.5 hours, 1 hour, 0.8 hour, 0.6 hour, or 0.5 hour.
In order to achieve green and sustainable chemistry, the present application develops a more environmentally friendly 5-hydroxymethylfurfural production system. Aiming at the defects in the prior art, the application provides an efficient solution. The application provides a method for catalytically converting fructose aqueous solution into 5-hydroxymethylfurfural under the catalytic action of hydrogen peroxide. The solvent used in the method is water, the reaction catalyst is hydrogen peroxide, and the byproduct of the hydrogen peroxide after catalysis is water, so that no pollutant is generated after reaction, and the method is green, environment-friendly and efficient. The added hydrogen peroxide can effectively avoid the side reaction of the 5-hydroxymethylfurfural, the reaction solution after the reaction is clear and transparent, has higher conversion rate and selectivity, is environment-friendly, has lower economic cost, is beneficial to industrial production amplification, has low equipment maintenance cost, and can efficiently produce the high-purity 5-hydroxymethylfurfural.
As an embodiment, the present application discloses a method for preparing 5-hydroxymethylfurfural, comprising: mixing fructose and water in proportion, and adding hydrogen peroxide as a catalyst; the method comprises the steps of adopting an intermittent kettle type reactor to generate 5-hydroxymethylfurfural, extracting the 5-hydroxymethylfurfural by using an extracting agent after reaction, and realizing separation of the 5-hydroxymethylfurfural and recycling of the extracting agent by adopting a reduced pressure distillation method. The hydrogen peroxide added in the method can effectively improve the selectivity of the reaction, and simultaneously, the problems of product yield reduction and large equipment maintenance cost increase caused by the formation of black rot substances due to the side reaction of the 5-hydroxymethylfurfural are solved. The system for synthesizing 5-hydroxymethylfurfural used in the method has the advantages of high economic benefit, low system cost, low environmental pollution, simple operation, easy repetition, low equipment maintenance cost and capability of efficiently producing high-purity 5-hydroxymethylfurfural.
The preparation method comprises the following steps:
(1) Reacting a raw material of a fructose-containing aqueous solution under the catalytic action of hydrogen peroxide to generate 5-hydroxymethylfurfural;
(2) Extracting 5-hydroxymethylfurfural by using an extracting agent after the reaction, and recovering and separating the extracting solvent and the product by adopting a reduced pressure distillation method.
Optionally, the mass ratio of fructose to water satisfies: fructose: water =1, 0.8 to 10.
Optionally, the addition amount of the catalyst is 0.1wt% to 5wt% of the addition amount of the fructose.
Optionally, the reaction conditions are: the reaction temperature is 60-180 ℃, and the reaction time is 2-10 hours.
Optionally, the detection method of the yield of 5-hydroxymethylfurfural is high performance liquid chromatography, and deionized water is added for mixing and fixing the volume during detection.
Optionally, the extractant is one of ethyl acetate or dimethyl carbonate, and the extraction process is to add the reaction solution obtained after the reaction into the extractant to perform extraction operation; after standing and shaking up, layering the solution, wherein the upper layer is an organic solution phase containing 5-hydroxymethylfurfural, after separating the upper layer, adding ethyl acetate or dimethyl carbonate into the remaining lower layer solution again for extraction, and repeating the operations for multiple times in sequence;
the volume ratio of the extracting agent to the reaction liquid is as follows: 1 to 3;
optionally, the number of times of repeating the extraction process is 2-5 times.
Optionally, the conditions of the reduced pressure distillation comprise: the vacuum degree is 0.01-5 KPa, the temperature is 30-60 deg.C, the decompression operation is carried out for 0.5-3 hours.
Compared with the traditional method, the preparation method provided by the application does not need an organic solvent in the preparation process, the reaction is carried out in an aqueous solution, the catalyst is hydrogen peroxide, and the hydrogen peroxide is decomposed into water after the catalytic action is exerted, so that the system is green and environment-friendly. Meanwhile, the side reaction can be effectively controlled, the generation of black rot is avoided, the reaction selectivity is improved, and the equipment maintenance and labor cost are greatly reduced.
The preparation route of the application is that the raw material of the aqueous solution containing fructose is adopted, 5-hydroxymethylfurfural is obtained through dehydration reaction under the catalytic action of hydrogen peroxide, and only byproduct water is generated after the reaction of the added hydrogen peroxide, and organic solvents and the like are not needed, so that the system is green and environment-friendly. Meanwhile, the further side reaction of the 5-hydroxymethylfurfural can be effectively inhibited, no other impurities or black rot is generated after the reaction, the 5-hydroxymethylfurfural is extracted by using dimethyl carbonate or ethyl acetate as an extracting agent after the reaction, and the recovery and separation of an extraction solvent and a product are realized by adopting a reduced pressure distillation method, while the traditional preparation process of the 5-hydroxymethylfurfural usually discharges a large amount of waste water, the side reaction is difficult to control, and the generated black rot easily causes the corrosion and the blockage of equipment.
The preparation method of the 5-hydroxymethylfurfural is characterized by comprising the following steps: the raw material of the aqueous solution containing fructose is subjected to dehydration reaction under the catalytic action of hydrogen peroxide to obtain the 5-hydroxymethylfurfural.
Optionally, the catalyst is hydrogen peroxide, and the mass fraction of the hydrogen peroxide is 30%.
Optionally, the mass ratio of fructose to water satisfies:
fructose: water =1, 0.8-10;
alternatively, the upper limit of the mass ratio of fructose to water is selected from 1; the lower limit is selected from 1.
Optionally, the addition amount of the catalyst is 0.1wt% to 5wt% of the addition amount of the fructose.
Optionally, the catalyst is added in an amount such that the upper limit of the fructose addition amount in percentage by mass is selected from 0.2wt%, 0.5wt%, 0.8wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt%, 4.5wt% or 5.0wt%; the lower limit is selected from 0.1wt%, 0.2wt%, 0.5wt%, 0.8wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt%, or 4.5wt%.
Optionally, the reaction conditions are: the reaction temperature is 60-180 ℃, the reaction time is 2-10 hours, and reaction liquid is obtained after the reaction.
Optionally, the reaction to produce 5-hydroxymethylfurfural is carried out under stirring conditions.
Optionally, the upper temperature limit of the reaction is selected from 70 ℃, 80 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 175 ℃ or 180 ℃; the lower limit is selected from 60 deg.C, 70 deg.C, 90 deg.C, 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C or 175 deg.C.
Alternatively, the upper limit of time for the reaction is selected from 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours; the lower limit is selected from 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, or 9 hours.
Optionally, after the reaction is finished, a certain amount of reaction liquid after the reaction is taken, deionized water is added for mixing and constant volume, and the yield of the 5-hydroxymethylfurfural is detected.
Alternatively, the detection method used is high performance liquid chromatography: obtaining the peak area of a liquid chromatogram by configuring the content of 5-hydroxymethylfurfural in a standard solution, and obtaining a standard curve by taking the peak area as a horizontal coordinate and the concentration of 5-hydroxymethylfurfural as a vertical coordinate; further, the concentration of 5-hydroxymethylfurfural in the reaction solution after the reaction can be calculated, and the yield of 5-hydroxymethylfurfural can be calculated according to the concentration.
Optionally, the reaction solution obtained after the reaction is added with ethyl acetate or dimethyl carbonate for extraction. After standing and shaking up, the solution is layered, the upper layer is an organic solution phase containing 5-hydroxymethylfurfural, after the upper layer is separated, ethyl acetate or dimethyl carbonate is added into the remaining lower layer solution again for extraction, and the operations are repeated for a plurality of times in sequence.
Optionally, the volume ratio of the ethyl acetate or the dimethyl carbonate as the extractant to the reaction liquid is: 1 to 3.
Alternatively, the upper limit of the volume ratio of the extractant to the reaction liquid is selected from 3; the lower limit is selected from 1, 1.5.
Optionally, the number of times of repeating the extraction process is 2-5 times.
Optionally, the upper limit of the number of extraction operations is selected from 5, 4 or 3; the lower limit is selected from 2, 3 or 4 times.
Optionally, the extract of the upper layer of ethyl acetate or dimethyl carbonate is subjected to a reduced pressure distillation method, the solvent ethyl acetate or dimethyl carbonate for extraction is recovered, and simultaneously the product 5-hydroxymethylfurfural is obtained.
Optionally, the conditions of the reduced pressure distillation comprise: the vacuum degree is 0.01-5 KPa, the temperature is 30-60 ℃, and the decompression operation is 0.5-3 hours.
Optionally, in the vacuum distillation process, the upper limit of the vacuum degree of the system is selected from 0.02KPa, 0.05KPa, 0.1KPa, 0.5KPa, 1KPa, 2KPa, 3KPa, 4KPa, 4.5KPa or 5KPa; the lower limit is selected from 0.01KPa, 0.02KPa, 0.05KPa, 0.1KPa, 0.5KPa, 1KPa, 2KPa, 3KPa, 4KPa or 4.5KPa.
Optionally, in the reduced pressure distillation process, the upper limit of the reaction temperature is selected from 60 ℃, 55 ℃, 50 ℃, 45 ℃, 40 ℃ or 35 ℃; the lower limit is selected from 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C or 55 deg.C.
Alternatively, in the vacuum distillation process, the upper limit of the time of the vacuum distillation operation is selected from 0.6 hour, 0.8 hour, 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours; the lower limit is selected from 2.5 hours, 2 hours, 1.5 hours, 1 hour, 0.8 hour, 0.6 hour, or 0.5 hour.
The yield of the 5-hydroxymethylfurfural in the reaction process is 80-95%.
Alternatively, the yield of 5-hydroxymethylfurfural during the reaction is greater than 80%.
Optionally, the method comprises:
a) Mixing fructose, water and catalyst, stirring and reacting at 60-180 deg.c for 2-10 hr;
b) Extracting the reaction liquid obtained after the reaction in the step a) for multiple times by using ethyl acetate or dimethyl carbonate, and performing reduced pressure distillation on the ethyl acetate or dimethyl carbonate after multiple extractions. Controlling the vacuum degree of the system at 0.01-5 KPa, the reaction temperature at 30-60 ℃, and the reduced pressure distillation operation time at 0.5-3 hours to obtain the product 5-hydroxymethylfurfural.
As a specific embodiment, the method comprises:
1) The fructose, water and catalyst are mixed evenly in a batch reactor and react under stirring, the reaction temperature is between 60 and 180 ℃, and the reaction time is between 2 and 10 hours.
2) Taking a small amount of reaction liquid obtained after the reaction in the step 1) to perform liquid chromatography analysis, and determining the yield of the 5-hydroxymethylfurfural, wherein the yield of the 5-hydroxymethylfurfural is more than 80%. Adding ethyl acetate or dimethyl carbonate into the reaction liquid to perform extraction for 2-5 times, performing reduced pressure distillation to obtain a generated product 5-hydroxymethylfurfural, connecting the device with a water pump or an oil pump to perform reduced pressure distillation, controlling the vacuum degree of the system to be 0.01-5 KPa, controlling the reduced pressure distillation temperature to be 30-60 ℃ and controlling the reduced pressure distillation operation time to be 0.5-3 hours.
The beneficial effects that this application can produce include:
1) The application provides a preparation method of 5-hydroxymethylfurfural, which can effectively control side reactions by using hydrogen peroxide as a catalyst, avoid the generation of black rot, improve the selectivity of the reaction and greatly reduce the equipment maintenance and labor cost.
2) Compared with the traditional method, the preparation method of the 5-hydroxymethylfurfural is characterized in that the solvent used in the preparation process is water, the catalyst is hydrogen peroxide, the added hydrogen peroxide only can generate byproduct water after reaction, and the system after reaction is green and environment-friendly.
3) The system for synthesizing 5-hydroxymethylfurfural used in the method has the advantages of high economic benefit, low system cost, low environmental pollution, simple operation, easy repetition, low equipment maintenance cost and capability of efficiently producing high-purity 5-hydroxymethylfurfural.
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of the product synthesized in example 1 of the present application.
FIG. 2 is a hydrogen nuclear magnetic spectrum of a 5-hydroxymethylfurfural standard.
FIG. 3 is a carbon nuclear magnetic spectrum of the product synthesized in example 1 of the present application.
FIG. 4 is a carbon nuclear magnetic spectrum of a 5-hydroxymethylfurfural standard.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
a liquid nuclear magnetic instrument with the model of AVANCE II 400M, which is produced by Bruker company, is used for analyzing a carbon and hydrogen nuclear magnetic spectrum diagram, and the reaction solution is dissolved in a deuterated reagent.
In the examples of the present application, the yield of 5-hydroxymethylfurfural was calculated by:
obtaining the peak area of a liquid chromatogram by configuring the content of 5-hydroxymethylfurfural in a standard solution, and obtaining a standard curve by taking the peak area as a horizontal coordinate and the concentration of 5-hydroxymethylfurfural as a vertical coordinate; further, the concentration of 5-hydroxymethylfurfural in the reaction solution after the reaction can be calculated, and the yield of 5-hydroxymethylfurfural can be calculated according to the concentration.
Hydrogen peroxide solution used in examples of this application 2 O 2 Is 30wt%.
According to one embodiment of the present application, the method for preparing 5-hydroxymethylfurfural is characterized by comprising the steps of:
a) Evenly mixing fructose, water and a catalyst in an intermittent kettle type reactor, and reacting under a stirring state, wherein the reaction temperature is between 60 and 180 ℃, and the reaction time is between 2 and 10 hours.
b) Taking a small amount of reaction liquid obtained after the reaction in the step a) for liquid chromatography analysis, and determining the yield of the 5-hydroxymethylfurfural, wherein the yield of the 5-hydroxymethylfurfural is more than 80%. Adding ethyl acetate or dimethyl carbonate into the reaction liquid to perform extraction for 2-5 times, performing reduced pressure distillation to obtain a generated product 5-hydroxymethylfurfural, connecting a water pump or an oil pump to the device to perform reduced pressure distillation, controlling the vacuum degree of the system to be 0.01-5 KPa, controlling the reduced pressure distillation temperature to be 30-60 ℃ and controlling the reduced pressure distillation operation time to be 0.5-3 hours.
Optionally, the catalyst in the step a) is hydrogen peroxide, and the mass fraction of the hydrogen peroxide is 30%.
Optionally, the addition amount of the catalyst is 0.1wt% to 5wt% of the addition amount of the fructose.
Optionally, the fructose and water in the step a) have the following mass ratio:
fructose: water =1
Optionally, the reaction conditions in step a) are: the reaction temperature is 60-180 ℃, the reaction time is 2-10 hours, and reaction liquid is obtained after the reaction.
Optionally, a certain amount of reaction liquid after the reaction in the step b) is taken, added with deionized water, mixed and subjected to constant volume, and the yield of 5-hydroxymethylfurfural is detected.
Optionally, in the step b), the reaction solution obtained after the reaction is added with ethyl acetate or dimethyl carbonate for extraction. After standing and shaking up, the solution is layered, the upper layer is an organic solution phase containing 5-hydroxymethylfurfural, after the upper layer is separated, ethyl acetate or dimethyl carbonate is added into the remaining lower layer solution again for extraction, and the operations are repeated for a plurality of times in sequence.
Optionally, the volume ratio of the ethyl acetate or the dimethyl carbonate as the extractant to the reaction liquid in the step b) is: 1 to 3.
Optionally, the number of times of repeating the extraction process in the step b) is 2-5.
Optionally, in the step b), the extract liquid of the upper layer of ethyl acetate or dimethyl carbonate is subjected to a reduced pressure distillation method, the solvent ethyl acetate or dimethyl carbonate for extraction is recovered, and the product 5-hydroxymethylfurfural is obtained at the same time.
Optionally, the conditions of the reduced pressure distillation in step b) comprise: the vacuum degree is 0.01-5 KPa, the temperature is 30-60 ℃, and the decompression operation is 0.5-3 hours.
Example 1
5g of fructose and 5g of water are added into an intermittent kettle type reactor, 0.12g of hydrogen peroxide is dropwise added as a catalyst under the stirring state, the temperature is raised to 100 ℃, the reaction time is 6 hours, and the color of the reaction liquid is gradually deepened. After the reaction is finished, taking a small amount of reaction liquid to perform high performance liquid chromatography analysis, wherein the result shows that the yield of the 5-hydroxymethylfurfural is 87% and the selectivity is 97%, adding dimethyl carbonate (the volume ratio of the dimethyl carbonate to the reaction liquid is 3: 1) into the reaction liquid to perform extraction operation for 2 times, connecting a water pump or an oil pump to perform reduced pressure distillation after the extraction is finished to obtain an extraction liquid, controlling the vacuum degree of the system to be 2KPa, controlling the reduced pressure distillation temperature to be 40 ℃, and performing the reduced pressure distillation operation for 1.5 hours, wherein the purity of the obtained 5-hydroxymethylfurfural is 97%.
Example 2
Adding 10g of fructose and 15g of water into an intermittent kettle type reactor, adding 0.5g of hydrogen peroxide as a catalyst under the stirring state, heating to 80 ℃, and reacting for 8 hours, wherein the color of the reaction liquid is gradually deepened. After the reaction is finished, taking a small amount of reaction liquid for high performance liquid chromatography analysis, and displaying that the yield of the 5-hydroxymethylfurfural is 90% and the selectivity is 98%, adding ethyl acetate (the volume ratio of the ethyl acetate to the reaction liquid is 2: 1) into the reaction liquid for multiple extraction operations, wherein the extraction times are 3, obtaining an extraction liquid after the extraction is finished, connecting the device to a water pump or an oil pump for reduced pressure distillation, controlling the vacuum degree of the system to be 0.5KPa, controlling the reduced pressure distillation temperature to be 35 ℃, and the reduced pressure distillation operation time to be 2 hours, wherein the purity of the obtained 5-hydroxymethylfurfural is 98%.
Example 3
Adding 8g of fructose and 6g of water into an intermittent kettle type reactor, adding 0.15g of hydrogen peroxide as a catalyst under the stirring state, heating to 150 ℃, and reacting for 5 hours, wherein the color of the reaction liquid is gradually deepened. After the reaction is finished, taking a small amount of reaction liquid to perform high performance liquid chromatography analysis, and the result shows that the yield of 5-hydroxymethylfurfural is 93%, the selectivity is 97%, adding dimethyl carbonate (the volume ratio of dimethyl carbonate to the reaction liquid is 3: 1) into the reaction liquid to perform extraction operation for 5 times, obtaining extract liquid after the extraction is finished, connecting the device to a water pump or an oil pump to perform reduced pressure distillation, controlling the vacuum degree of the system to be 3KPa, the reduced pressure distillation temperature to be 50 ℃, and the reduced pressure distillation operation time to be 3 hours, wherein the purity of the obtained 5-hydroxymethylfurfural is 97%.
Examples 4 to 13
The specific ingredients, materials and reaction conditions are shown in Table 1 below, and other operations in the synthesis process are the same as those in example 1.
TABLE 1 raw material composition, compounding ratio and reduced pressure distillation conditions of examples 4 to 13
EXAMPLE 14 liquid NMR analysis
Liquid nuclear magnetic resonance analysis was performed on 5-hydroxymethylfurfural prepared in examples 1 to 13, and typically, as shown in fig. 1 and 3, fig. 2 and 4 are standard spectra of 5-hydroxymethylfurfural. FIG. 1 is a NMR spectrum of 5-hydroxymethylfurfural prepared in example 1, and a comparison between FIG. 1 and FIG. 2 shows that 5-hydroxymethylfurfural prepared in example 1 has a typical standard hydrogen NMR spectrum of 5-hydroxymethylfurfural.
FIG. 3 is a graph of carbon nuclear magnetic resonance spectrum of 5-hydroxymethylfurfural prepared in example 1, and a comparison between FIG. 3 and FIG. 4 shows that 5-hydroxymethylfurfural prepared in example 1 has a typical standard 5-hydroxymethylfurfural carbon nuclear magnetic resonance spectrum.
Other examples the test results for 5-hydroxymethylfurfural were similar to those described above, and standard 5-hydroxymethylfurfural was obtained by the present invention.
Comparative example 1
Compared with the embodiment 1, the difference is that the dropwise added hydrogen peroxide is 0.007g, namely the mass ratio of hydrogen peroxide to fructose is 0.007:15. the results showed that the yield of 5-hydroxymethylfurfural was 13% and the selectivity was 91%.
After purification by the same method as in comparative example 1, the purity of the obtained 5-hydroxymethylfurfural was 96%.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The preparation method of 5-hydroxymethylfurfural is characterized by comprising the following steps:
reacting a solution containing fructose under the catalytic action of a catalyst to obtain the 5-hydroxymethylfurfural;
the catalyst comprises hydrogen peroxide;
the mass ratio of the catalyst to the fructose is 0.01-1;
the mass of the catalyst is calculated by the mass of hydrogen peroxide.
2. The method according to claim 1, wherein the hydrogen peroxide solution contains H 2 O 2 10 to 30wt%.
3. The method of claim 1, wherein the solvent of the solution comprises water.
4. The method according to claim 1, wherein the mass ratio of fructose to solvent in the solution is 0.1 to 10.
5. The method of claim 1, wherein the reaction conditions include: the reaction temperature is 60-180 ℃.
6. The method of claim 1, wherein the reaction conditions include: the reaction time is 2 to 10 hours.
7. The method of claim 1, further comprising a purification step after the reaction is completed:
adding an extracting agent into the reaction liquid for extraction to obtain upper-layer extraction liquid, and carrying out reduced pressure distillation on the upper-layer extraction liquid to obtain the 5-hydroxymethylfurfural.
8. The method according to claim 7, wherein the volume ratio of the extractant to the reaction solution is 1 to 3.
9. The method of claim 7, wherein the extractant comprises at least one of ethyl acetate, dimethyl carbonate;
preferably, the number of extractions is 2 to 5.
10. The method according to claim 1, wherein the conditions of the reduced pressure distillation comprise:
the vacuum degree is 0.01-5 KPa, the temperature is 30-70 ℃, and the time is 0.5-3 hours.
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| WO2010101024A1 (en) * | 2009-03-06 | 2010-09-10 | 国立大学法人北陸先端科学技術大学院大学 | Method for preparing 5-hydroxymethylfurfural |
| CN110256381A (en) * | 2019-07-25 | 2019-09-20 | 广西科学院 | One-step method cleans the method for preparing 2,5- furandicarboxylic acid |
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| WO2010101024A1 (en) * | 2009-03-06 | 2010-09-10 | 国立大学法人北陸先端科学技術大学院大学 | Method for preparing 5-hydroxymethylfurfural |
| CN110256381A (en) * | 2019-07-25 | 2019-09-20 | 广西科学院 | One-step method cleans the method for preparing 2,5- furandicarboxylic acid |
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| 武艳 等: "芬顿试剂催化糖类制备5-羟甲基糠醛", 化学工业与工程, pages 19 * |
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