CN112679454A - Continuous preparation and purification method and device of 5-hydroxymethylfurfural - Google Patents
Continuous preparation and purification method and device of 5-hydroxymethylfurfural Download PDFInfo
- Publication number
- CN112679454A CN112679454A CN201910995858.9A CN201910995858A CN112679454A CN 112679454 A CN112679454 A CN 112679454A CN 201910995858 A CN201910995858 A CN 201910995858A CN 112679454 A CN112679454 A CN 112679454A
- Authority
- CN
- China
- Prior art keywords
- acid
- hydroxymethylfurfural
- reactor
- extractant
- reaction solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
Discloses a method for continuously preparing and purifying 5-hydroxymethylfurfural, which comprises the following steps: the reaction solution is in countercurrent contact with an extractant in the reactor; the extractant is selected from one or more organic extractants with the boiling point lower than 120 ℃, and the reaction solution at least contains biomass reaction raw materials containing six-carbon sugar structural units. According to the invention, the extraction agent is in countercurrent contact with the reaction solution, so that the generated HMF can be extracted timely and efficiently, the selectivity of the HMF is ensured, side reactions are avoided, and the continuous preparation and separation of the 5-hydroxymethylfurfural are realized. Meanwhile, the extracting agent adopted by the invention has low boiling point, so that the temperature of a reaction system and a separation process can be reduced, the occurrence of side reactions is further reduced, and the yield and the purity of the HMF are high. Therefore, the production cost is reduced, and the method is beneficial to industrialization and practical application.
Description
Technical Field
The invention relates to the technical field of chemical reaction, and particularly relates to a method for continuously preparing, separating and purifying 5-hydroxymethylfurfural.
Background
With the continuous consumption of non-renewable fossil energy and the increasing severity of environmental pollution, the development of environment-friendly renewable resources is imperative. Among various renewable resources, biomass resources have the characteristics of wide sources, abundant reserves, environmental friendliness and the like, and can be used as an effective substitute for fossil energy. Biomass resources produced every year all over the world can reach hundreds of billions of tons, only a small part of the biomass resources are used in industries such as papermaking, feed, buildings and the like, and most of the biomass resources are decomposed by microorganisms and even directly burned, so that not only is the resource waste caused, but also serious environmental pollution is brought. Therefore, the method has great significance for fully utilizing the biomass resources of China and developing fine chemical raw materials with high added values. However, biomass is complex in composition and difficult to directly convert into specific fine chemical products, and thus, it is an important approach to solve this problem as a bridge via a platform compound.
5-Hydroxymethylfurfural (HMF) is one of important platform compounds issued by the U.S. energy agency, HMF molecules contain furan rings, hydroxyl groups, aldehyde groups and the like with high activity, can be further converted through the processes of hydrogenation, esterification, halogenation, polymerization, hydrolysis and the like, and has important effects in the fields of monomer synthesis as a high polymer material, macrocyclic compound synthesis raw materials, pharmaceutical and pesticide intermediates and the like. While HMF has significant potential application value, its practical application is limited by the higher price. The high price of the HMF is mainly caused by two aspects, namely, the HMF has low reaction selectivity and is easy to generate side reaction in the reaction process to reduce the yield, and the HMF is difficult to separate and purify and is difficult to obtain a high-purity product at a low cost. At present, the preparation and separation processes of HMF are batch processes or only partial continuous processes, which are not beneficial to industrial scale-up. And the separation and purification process of the HMF is difficult to consider both the purity and the scale.
Disclosure of Invention
In order to overcome the defects, the invention provides a method and a device for continuously preparing and purifying 5-hydroxymethylfurfural.
The invention provides a method for continuously preparing and purifying 5-hydroxymethylfurfural, which comprises the following steps: the reaction solution is in countercurrent contact with an extractant in the reactor; the extractant is selected from one or more organic extractants with the boiling point lower than 120 ℃, and the reaction solution at least contains biomass reaction raw materials containing six-carbon sugar structural units.
According to an embodiment of the present invention, the temperature in the reactor is 100-200 ℃, and the pressure is 0.2-4 MPa; the preferred temperature is 120 ℃ and 180 ℃ and the pressure is 1-3 MPa.
According to an embodiment of the invention, the flow rate ratio of the extraction agent to the reaction solution is greater than 1: 1; preferably 2:1 to 5: 1; more preferably from 3:1 to 5: 1.
According to an embodiment of the present invention, the method further comprises: the reaction solution and the extractant are preheated to 40-80 ℃ before entering the reactor, and then enter the reactor.
According to another embodiment of the present invention, the reaction raw material is selected from one or more of glucose, fructose, cellulose, oligo-glucose, anhydroglucose, starch, inulin, sucrose, galactose, cellobiose.
According to another embodiment of the present invention, the reaction solution further contains an inorganic acid salt and/or an organic solvent in which the biomass reaction raw material is soluble.
According to another embodiment of the invention, the salt is selected from one or more of halide salts, sulfate salts, nitrate salts of potassium, sodium, calcium, magnesium; preferably, one or more of sodium chloride, sodium sulfate, magnesium chloride, potassium chloride and calcium chloride; the organic solvent is selected from one or more of N-methyl pyrrolidone, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide, pyridine and butyl acetate.
According to another embodiment of the invention, the extractant is selected from one or more of organic extractants having a boiling point in the range of 40 ℃ to 120 ℃.
According to another embodiment of the present invention, the extractant is selected from one or more of tetrahydrofuran, methyl isobutyl ketone, acetone, sec-butanol, 1, 4-dioxahexane, methyl isobutyl ketone, methyl isobutyl ether, acetonitrile.
According to another embodiment of the present invention, the catalyst of the reaction system is a solid acid catalyst or a liquid acid catalyst.
According to another embodiment of the invention, the solid acid catalyst is selected from one or more of acidic ion exchange resins, composite silica alumina, zirconium phosphate, sulfonated carbon, molecular sieves; one or more of acidic ion exchange resin, composite silicon aluminum oxide and sulfonated carbon are preferred.
According to another embodiment of the present invention, the liquid acid catalyst is selected from one or more of sulfuric acid, phosphoric acid, hydrochloric acid, hydroiodic acid, phosphorous acid, hypophosphorous acid, perchloric acid, formic acid, acetic acid, propionic acid, oxalic acid, levulinic acid, p-toluenesulfonic acid, succinic acid, maleic acid, fumaric acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, propanesulfonic acid, trifluoromethanesulfonic acid, phthalic acid and terephthalic acid, preferably one or more of sulfuric acid, hydrochloric acid, formic acid, sulfonic acid, acetic acid, oxalic acid, trichloroacetic acid, trifluoroacetic acid.
According to another embodiment of the present invention, the reaction solution enters the reactor through an upper feed port of the reactor, and the extractant enters the reactor through a lower feed port of the reactor.
The invention also provides a continuous preparation and purification device of 5-hydroxymethylfurfural, which comprises: a reaction solution storage tank; an extractant storage tank; the reactor is connected with the reaction solution storage tank and the extractant storage tank; the separation device is connected with the reactor and is used for collecting the extracted extractant and separating the extractant from the 5-hydroxymethylfurfural; and the product storage tank is connected with the separation device and is used for storing the separated 5-hydroxymethylfurfural product.
According to an embodiment of the present invention, the reaction solution tank and the extractant tank further include a heating unit.
According to another embodiment of the invention, the reactor further comprises a heating unit.
According to the invention, the extraction agent is in countercurrent contact with the reaction solution, so that the generated HMF can be extracted timely and efficiently, the selectivity of the HMF is ensured, side reactions are avoided, and the continuous preparation and separation of the 5-hydroxymethylfurfural are realized. Meanwhile, the extracting agent adopted by the invention has low boiling point, so that the temperature of a reaction system and a separation process can be reduced, the occurrence of side reactions is further reduced, and the yield and the purity of the HMF are high. Therefore, the production cost is reduced, and the method is beneficial to industrialization and practical application.
Drawings
The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings.
FIG. 1 is a process diagram of the method of the present invention.
Wherein the reference numerals are as follows:
1-a reaction solution storage tank with heating; 2-an extractant storage tank with heating; 3-a reaction solution feed flow path; 4-an extractant feed flow path; 5-a reactor; 6-product solution flow path; 7-a separation device; an 8-HMF solution flow path; 9-a product storage tank; 10-extractant recovery flow path
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to a method for continuously preparing and purifying 5-hydroxymethylfurfural, which comprises the following steps: the reaction solution is in countercurrent contact with an extractant in the reactor; the extractant is selected from one or more organic extractants with the boiling point lower than 120 ℃, and the reaction solution at least contains biomass reaction raw materials containing six-carbon sugar structural units.
Herein, the "reaction solution" contains at least a reaction raw material, and may further contain one or more of a reaction product, a liquid acid catalyst, an inorganic acid salt, an organic solvent in which HMF is easily dissolved, and the like, for example, the reaction solution first introduced into the reaction space from the feed port may include only a solution of the raw material, or a solution of the raw material and a salt, or a solution of the raw material and a liquid acid catalyst, or a solution of the raw material, a salt and a liquid acid catalyst; or the reaction solution may be a solution including only the raw material when the solid acid catalyst is used, or a solution including the raw material and the product, or a solution including the raw material, the product, and a salt, or the like.
FIG. 1 illustrates a method of an embodiment of the present invention. Referring to FIG. 1, the reaction solution may be preheated, preferably to 40-80 ℃ by a heated reaction solution reservoir 1, and then introduced into a reactor 5 from a feed port through a reaction solution feed flow path 3. The heated extractant tank 2 can preheat the extractant, preferably to 40-80 ℃, and then enters the reactor 5 from the feed inlet through an extractant feed flow path 4. As can be seen from the figure, the reaction solution including the raw material enters the reactor 5 from the upper feed inlet of the reactor 5, the extractant enters the reactor 5 from the lower feed inlet of the reactor 5, and the reaction solution and the extractant are in countercurrent contact in the reactor 5, so that the extractant is in full contact with the reaction solution during the reaction, the generated 5-hydroxymethylfurfural is timely taken out of the reactor 5, and the continuous production of 5-hydroxymethylfurfural is realized. The reactor 5 may further include a heating unit to maintain the temperature inside the reactor 5 within a predetermined temperature range. The extractant containing 5-hydroxymethylfurfural is discharged from the reactor 5 and then introduced into a separation device 7 through a product solution flow path 6. In the separation unit 7, HMF is obtained after separation of the extractant and the product, and the HMF separated from the separation unit 7 enters the HMF product storage tank through the HMF solution flow path 8. The extractant separated by the separator 7 can enter the extractant tank 2 through the extractant recovery passage 10 and can be reused.
The reaction raw material used in the production and purification method of the present invention may be biomass containing a six-carbon sugar structural unit, for example, one or more selected from glucose, fructose, cellulose, oligocellulose, oligoglucose, anhydroglucose, starch, inulin, sucrose, galactose, cellobiose, and the like.
The reaction solution may contain an inorganic acid salt. The salt is contained in the reaction solution to promote the phase separation of the extractant and the water and improve the distribution coefficient of the 5-hydroxymethylfurfural in a two-phase system. The inorganic acid salt may be one or more selected from halide, sulfate and nitrate of potassium, sodium, calcium and magnesium. Such as sodium chloride, sodium sulfate, magnesium chloride, potassium chloride, calcium chloride, and the like. For better phase separation preferably a saturated solution of salt is used.
The reaction solution may further contain an organic solvent in which the reaction raw material is soluble, and the organic solvent may be one or more selected from N-methylpyrrolidone, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide, pyridine, and butyl acetate. The particular organic solvent that facilitates HMF extraction may be selected based on the particular extractant employed.
The extractant is an organic solvent which is not completely miscible with the reaction solution and has good extraction effect on HMF, such as alcohol, ether, ketone, ester, phenol and the like with the boiling point lower than 120 ℃. For example, tetrahydrofuran, methyl isobutyl ketone, acetone, sec-butanol, methyl isobutyl ketone, 1, 4-dioxahexane, acetonitrile, methyl isobutyl ether, and the like. The extraction agent with the boiling point lower than 120 ℃ is adopted, so that the liquid state of the HMF can be maintained, the reaction and separation temperature is reduced, and the occurrence of side reactions is reduced. More preferably, the boiling point is between 40 and 120 ℃. The extractant with the boiling point between 40 and 120 ℃ can ensure that the separation temperature is lower than 100 ℃ and even lower than 80 ℃, so that the HMF is not in a high-temperature environment for a long time, and the extractant is more favorable for reducing the generation of impurities and improving the yield.
The method of the invention can adopt liquid acid catalyst and also can adopt solid acid catalyst. The solid acid catalyst may be one or more selected from acidic ion exchange resins, composite silica alumina, zirconium phosphate, sulfonated carbon, molecular sieves, and the like. Preferably, acidic ion exchange resins, composite silicon aluminum oxides, sulfonated carbons, and the like. The liquid acid catalyst may be an inorganic acid such as: sulfuric acid, phosphoric acid, hydrochloric acid, hydroiodic acid phosphorous acid, hypophosphorous acid, perchloric acid, and the like; organic acids are also possible, such as: formic acid, sulfonic acid, levulinic acid, p-toluenesulfonic acid, acetic acid, propionic acid, oxalic acid, succinic acid, maleic acid, fumaric acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, propanesulfonic acid, trifluoromethanesulfonic acid, phthalic acid, terephthalic acid and the like, preferably one or more of sulfuric acid, hydrochloric acid, formic acid, sulfonic acid, acetic acid, oxalic acid, trichloroacetic acid, trifluoroacetic acid.
The temperature in the reactor 5 is 100-. The reaction temperature is lower than 100 ℃, and the yield of HMF is reduced. The reaction temperature is higher than 200 ℃, a large amount of polymerization reaction can occur, a large amount of impurities are generated, the yield is reduced, and the production efficiency is reduced. The reaction pressure is less than 0.2MPa, so that part of the extractant is in a gaseous state and cannot effectively exert the extraction effect. The requirement on reaction equipment is higher when the reaction pressure is too high, so that the reaction cost is increased, and the reaction pressure is not more than 4MPa generally. Of course, the object of the present invention can be achieved by a reaction pressure of more than 4 MPa. Considering the yield and the actual conditions of the reactor, the reaction temperature is more preferably 120-180 ℃, and the reaction pressure is 1-3 MPa.
The flow rate of the countercurrent contact of the extractant and the reaction solution in the reactor 5 can be reasonably selected according to the factors such as the type of the selected extractant, the type and the concentration of the reaction solution and the like, and the flow rate ratio of the extractant to the reaction solution is preferably more than 1: 1; more preferably 2:1-5: 1; more preferably 3:1 to 5: 1.
Example 1
500g of glucose, 5000g of deionized water and 1750g of NaCl are prepared into a homogeneous solution to be used as a reaction solution. The reaction solution was preheated to 60 ℃ and pumped at a rate of 0.3Kg/h into a reactor packed with 300g of zirconium phosphate catalyst. 1, 4-dioxane is preheated to 60 ℃, then pumped into a reactor at the speed of 1Kg/h, and is in countercurrent contact with a reaction solution, namely, the reaction and the extraction are carried out simultaneously, the reaction temperature is 140 ℃, and the pressure is 2.5 MPa. And (3) the extractant with the HMF flows out of the reactor and enters a separation system for separation, and the separated 1, 4-dioxane is recycled to the reactor. The reaction solution flows out of the reactor and is also circulated back to the reactor after sugar supplement to continue the reaction. In the steady state, the conversion of glucose was 98% and the yield of HMF was 56%.
Example 2
500g of fructose and 2000g of dimethyl sulfoxide are prepared into a homogeneous solution to be used as a reaction solution. Preheated to 60 ℃ and pumped at a rate of 0.3Kg/h into a reactor packed with 250g of sulfonated carbon catalyst. Tetrahydrofuran is preheated to 60 ℃, then pumped into a reactor at the speed of 1Kg/h, and is in countercurrent contact with a reaction solution, namely, the reaction and the extraction are carried out simultaneously, the reaction temperature is 110 ℃, and the pressure is 2.5 MPa. And (3) enabling the extractant with the HMF to flow out of the reactor and then enter a separation system for separation, and recycling the separated tetrahydrofuran into the reactor. The reaction solution flows out of the reactor and is also circulated back to the reactor after sugar supplement to continue the reaction. In the steady state, the fructose conversion was 99% and the HMF yield was 72%.
Example 3
500g of glucose, 5000g of deionized water and 1750g of NaCl are prepared into a homogeneous solution to be used as a reaction solution. Preheated to 60 ℃ and pumped at a rate of 0.1Kg/h into a reactor packed with 300g of a catalyst of a silicon-aluminum composite. Preheating methyl isobutyl ketone to 60 ℃, pumping the preheated methyl isobutyl ketone into a reactor at the speed of 1Kg/h, and carrying out countercurrent contact with a reaction solution, namely, carrying out reaction and extraction simultaneously, wherein the reaction temperature is 140 ℃, and the pressure is 2.5 MPa. And (3) the extractant with the HMF flows out of the reactor and then enters a separation system for separation, and the separated methyl isobutyl ketone is recycled to the reactor. The reaction solution flows out of the reactor and is also circulated back to the reactor after sugar supplement to continue the reaction. At steady state, the conversion of glucose was 99% and the yield of HMF was 64%.
Example 4
500g of fructose, 5000g of deionized water and 1750g of NaCl are prepared into a homogeneous solution to be used as a reaction solution. Preheated to 60 ℃ and pumped at a rate of 0.5Kg/h into a reactor packed with 300g of acidic ion exchange resin catalyst. Tetrahydrofuran is preheated to 60 ℃, then pumped into a reactor at the speed of 1Kg/h, and is in countercurrent contact with a reaction solution, namely, the reaction and the extraction are carried out simultaneously, the reaction temperature is 180 ℃, and the pressure is 2.5 MPa. And (3) enabling the extractant with the HMF to flow out of the reactor and then enter a separation system for separation, and recycling the separated tetrahydrofuran into the reactor. The reaction solution flows out of the reactor and is also circulated back to the reactor after sugar supplement to continue the reaction. In the steady state, the conversion of fructose was 99% and the yield of HMF was 86%.
Example 5
500g of glucose, 5000g of deionized water and 1750g of NaCl are prepared into a homogeneous solution to be used as a reaction solution. Preheated to 60 ℃ and pumped at a rate of 0.4Kg/h into a reactor packed with 200g of sulfonated carbon catalyst. Acetone is preheated to 50 ℃ and then pumped into the reactor at the speed of 1.2Kg/h to be in countercurrent contact with the reaction solution, namely, the reaction and the extraction are carried out simultaneously, the reaction temperature is 200 ℃, and the pressure is 3.5 MPa. And (3) allowing the extractant with the HMF to flow out of the reactor and enter a separation system for separation, and recycling the separated acetone back to the reactor. The reaction solution flows out of the reactor and is also circulated back to the reactor after sugar supplement to continue the reaction. In the steady state, the conversion of glucose was 99% and the yield of HMF was 62%.
Comparative example 1
A homogeneous solution prepared from 50g of glucose, 500g of deionized water and 1750g of NaCl was used as a reaction solution, and 1.6L of acetone was added to a reactor filled with 200g of sulfonated carbon catalyst. The reaction temperature is 200 ℃ and the pressure is 3.5 MPa. And after the reaction is finished, circulating water is introduced for cooling, and the reaction is finished. The conversion of glucose in the acetone phase was 99% and the yield of HMF was 48%.
Comparative example 2
500g of fructose, 5000g of deionized water and 1750g of NaCl are prepared into a homogeneous solution to be used as a reaction solution. Preheated to 60 ℃ and pumped at a rate of 0.5Kg/h into a reactor packed with 300g of acidic ion exchange resin catalyst. Tetrahydrofuran is preheated to 60 ℃, then pumped into a reactor at the speed of 1Kg/h, and is in countercurrent contact with a reaction solution, namely, the reaction and the extraction are carried out simultaneously, the reaction temperature is 250 ℃, and the pressure is 3.5 MPa. And (3) enabling the extractant with the HMF to flow out of the reactor and then enter a separation system for separation, and recycling the separated tetrahydrofuran into the reactor. The reaction solution flows out of the reactor and is also circulated back to the reactor after sugar supplement to continue the reaction. In the steady state, the conversion of fructose was 99% and the yield of HMF was 71%.
Comparing example 5 with comparative example 1, it can be seen from the results that the conversion of glucose is the same but the yield of HMF can be significantly improved by counter-current contacting of the reaction solution with the extractant.
As for example 4 and comparative example 2, it can be seen from the results that the yield of HMF is reduced when the conversion rate of fructose is the same but the reaction temperature exceeds 200 ℃, demonstrating that more impurities are generated after the reaction temperature exceeds 200 ℃, reducing the production efficiency and further increasing the production cost.
The above examples and comparative examples further demonstrate that the continuous preparation and separation method of 5-hydroxymethylfurfural of the present invention realizes a fully continuous process of preparation and separation, and on the other hand, the generated HMF is extracted out of the reaction solution in time, thereby ensuring the selectivity of HMF. In addition, the yield and the purity of the HMF are high, the solvent can be recycled, the cost is low, and the method is beneficial to industrialization and practical application.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (20)
1. A method for continuously preparing and purifying 5-hydroxymethylfurfural comprises the following steps: the reaction solution is in countercurrent contact with an extractant in the reactor; the extractant is selected from one or more organic extractants with the boiling point lower than 120 ℃, and the reaction solution at least contains biomass reaction raw materials containing six-carbon sugar structural units.
2. The continuous preparation and purification process of 5-hydroxymethylfurfural according to claim 1, wherein the temperature inside the reactor is 100 ℃ and 200 ℃ and the pressure is 0.2 to 4 MPa.
3. The continuous preparation and purification process of 5-hydroxymethylfurfural according to claim 2, wherein the temperature inside the reactor is 120-180 ℃ and the pressure is 1-3 MPa.
4. The continuous 5-hydroxymethylfurfural production and purification process according to claim 1, wherein a flow rate ratio of the extractant to the reaction solution is greater than 1: 1; preferably 2:1 to 5: 1; more preferably from 3:1 to 5: 1.
5. The continuous preparation and purification process of 5-hydroxymethylfurfural according to claim 1, further comprising: the reaction solution and the extractant are preheated to 40-80 ℃ before entering the reactor, and then enter the reactor.
6. The continuous production and purification method of 5-hydroxymethylfurfural according to claim 1, wherein the reaction raw material is selected from one or more of glucose, fructose, cellulose, oligocellulose, oligoglucose, anhydroglucose, starch, inulin, sucrose, galactose and cellobiose.
7. The continuous production and purification process of 5-hydroxymethylfurfural according to claim 1, wherein the reaction solution further contains an inorganic acid salt and/or an organic solvent in which the biomass reaction raw material is soluble.
8. The continuous 5-hydroxymethylfurfural production and purification process according to claim 7, wherein the inorganic acid salt is selected from one or more of halide salts, sulfate salts and nitrate salts of potassium, sodium, calcium and magnesium.
9. The continuous preparation and purification process of 5-hydroxymethylfurfural according to claim 8, wherein the inorganic acid salt is selected from one or more of sodium chloride, sodium sulfate, magnesium chloride, potassium chloride, and calcium chloride.
10. The continuous preparation and purification process of 5-hydroxymethylfurfural according to claim 7, wherein the organic solvent is selected from one or more of N-methylpyrrolidone, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide, pyridine, butyl acetate.
11. The continuous 5-hydroxymethylfurfural production and purification process according to claim 1, wherein the extractant is selected from one or more of organic extractants having a boiling point of 40 ℃ to 120 ℃.
12. The continuous preparation and purification process of 5-hydroxymethylfurfural according to claim 1, wherein the extractant is selected from one or more of tetrahydrofuran, methyl isobutyl ketone, acetone, sec-butanol, 1, 4-dioxahexane, methyl isobutyl ketone, methyl isobutyl ether and acetonitrile.
13. The continuous preparation and purification process of 5-hydroxymethylfurfural according to claim 1, wherein the catalyst of the reaction system is a solid acid catalyst or a liquid acid catalyst.
14. The continuous 5-hydroxymethylfurfural production and purification process according to claim 13, wherein the solid acid catalyst is selected from one or more of acidic ion exchange resins, composite silica alumina, zirconium phosphate, sulfonated carbon, molecular sieves.
15. The continuous 5-hydroxymethylfurfural production and purification process according to claim 14, wherein the solid acid catalyst is selected from one or more of acidic ion exchange resin, composite silicon aluminum oxide, sulfonated carbon.
16. The continuous preparation and purification process of 5-hydroxymethylfurfural according to claim 13, wherein the liquid acid catalyst is selected from one or more of sulfuric acid, phosphoric acid, hydrochloric acid, hydroiodic acid, phosphorous acid, hypophosphorous acid, perchloric acid, formic acid, acetic acid, propionic acid, oxalic acid, levulinic acid, p-toluenesulfonic acid, succinic acid, maleic acid, fumaric acid, trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, propanesulfonic acid, trifluoromethanesulfonic acid, phthalic acid and terephthalic acid, preferably one or more of sulfuric acid, hydrochloric acid, formic acid, sulfonic acid, acetic acid, oxalic acid, trichloroacetic acid, trifluoroacetic acid.
17. The continuous 5-hydroxymethylfurfural production and purification process according to claim 1, wherein the reaction solution enters the reactor from an upper feed port of the reactor, and the extractant enters the reactor from a lower feed port of the reactor.
18. A continuous preparation and purification device of 5-hydroxymethylfurfural comprises:
a reaction solution storage tank;
an extractant storage tank;
the reactor is connected with the reaction solution storage tank and the extractant storage tank;
the separation device is connected with the reactor and is used for collecting the extracted extractant and separating the extractant from the 5-hydroxymethylfurfural; and
and the product storage tank is connected with the separation device and is used for storing the separated 5-hydroxymethylfurfural product.
19. The continuous 5-hydroxymethylfurfural production and purification plant according to claim 18, wherein the reaction solution storage tank and the extractant storage tank further comprise a heating unit.
20. The continuous 5-hydroxymethylfurfural production and purification plant according to claim 18, wherein the reactor further comprises a heating unit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910995858.9A CN112679454A (en) | 2019-10-18 | 2019-10-18 | Continuous preparation and purification method and device of 5-hydroxymethylfurfural |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910995858.9A CN112679454A (en) | 2019-10-18 | 2019-10-18 | Continuous preparation and purification method and device of 5-hydroxymethylfurfural |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112679454A true CN112679454A (en) | 2021-04-20 |
Family
ID=75445486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910995858.9A Pending CN112679454A (en) | 2019-10-18 | 2019-10-18 | Continuous preparation and purification method and device of 5-hydroxymethylfurfural |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112679454A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114315767A (en) * | 2021-11-29 | 2022-04-12 | 青岛三力本诺新材料股份有限公司 | Preparation method and preparation device of 5-hydroxymethylfurfural |
| CN114805254A (en) * | 2022-04-11 | 2022-07-29 | 合肥利夫生物科技有限公司 | Preparation method of 5-hydroxymethylfurfural |
| CN114874161A (en) * | 2022-04-22 | 2022-08-09 | 浙江恒逸石化研究院有限公司 | Method for continuously synthesizing and purifying 5-hydroxymethylfurfural by means of hollow fiber membrane tube |
| CN114907293A (en) * | 2022-04-29 | 2022-08-16 | 浙江恒逸石化研究院有限公司 | Method for conveniently producing 5-hydroxymethylfurfural by coupling reaction and extraction |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1834950A1 (en) * | 2006-03-10 | 2007-09-19 | Avantium International B.V. | Method for the synthesis of 5-alkoxymethylfurfural ethers and their use |
| CN102690248A (en) * | 2012-05-31 | 2012-09-26 | 天津大学 | Method utilizing continuous countercurrent reaction extraction of pentose solution to produce furfural |
| CN102933567A (en) * | 2010-04-07 | 2013-02-13 | 诺维信公司 | Method of producing hydroxymethylfurfural |
| CN106146439A (en) * | 2015-04-19 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of furfural |
| CN106810517A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | It is a kind of that the method that 5 hydroxymethyl furfural continuously synthesizes is realized by continuous extraction |
| US20180251439A1 (en) * | 2015-08-21 | 2018-09-06 | Brian D. Mullen | Process to Prepare Hydroxymethylfurfural Derivatives |
-
2019
- 2019-10-18 CN CN201910995858.9A patent/CN112679454A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1834950A1 (en) * | 2006-03-10 | 2007-09-19 | Avantium International B.V. | Method for the synthesis of 5-alkoxymethylfurfural ethers and their use |
| CN102933567A (en) * | 2010-04-07 | 2013-02-13 | 诺维信公司 | Method of producing hydroxymethylfurfural |
| CN102690248A (en) * | 2012-05-31 | 2012-09-26 | 天津大学 | Method utilizing continuous countercurrent reaction extraction of pentose solution to produce furfural |
| CN106146439A (en) * | 2015-04-19 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of preparation method of furfural |
| US20180251439A1 (en) * | 2015-08-21 | 2018-09-06 | Brian D. Mullen | Process to Prepare Hydroxymethylfurfural Derivatives |
| CN106810517A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | It is a kind of that the method that 5 hydroxymethyl furfural continuously synthesizes is realized by continuous extraction |
Non-Patent Citations (2)
| Title |
|---|
| 王琼等: ""木质纤维素酸催化制备糠醛的工艺及机理研究进展"", 《农业工程学报》 * |
| 胡江叶: ""糠醛生产工艺及制备方法研究进展"", 《当代化工研究》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114315767A (en) * | 2021-11-29 | 2022-04-12 | 青岛三力本诺新材料股份有限公司 | Preparation method and preparation device of 5-hydroxymethylfurfural |
| CN114315767B (en) * | 2021-11-29 | 2023-07-28 | 青岛三力本诺新材料股份有限公司 | Preparation method and preparation device of 5-hydroxymethylfurfural |
| CN114805254A (en) * | 2022-04-11 | 2022-07-29 | 合肥利夫生物科技有限公司 | Preparation method of 5-hydroxymethylfurfural |
| CN114874161A (en) * | 2022-04-22 | 2022-08-09 | 浙江恒逸石化研究院有限公司 | Method for continuously synthesizing and purifying 5-hydroxymethylfurfural by means of hollow fiber membrane tube |
| CN114874161B (en) * | 2022-04-22 | 2024-02-02 | 浙江恒逸石化研究院有限公司 | Method for continuously synthesizing and purifying 5-hydroxymethylfurfural by means of hollow fiber membrane tube |
| CN114907293A (en) * | 2022-04-29 | 2022-08-16 | 浙江恒逸石化研究院有限公司 | Method for conveniently producing 5-hydroxymethylfurfural by coupling reaction and extraction |
| CN114907293B (en) * | 2022-04-29 | 2024-03-05 | 浙江恒逸石化研究院有限公司 | Method for conveniently producing 5-hydroxymethylfurfural through coupling reaction and extraction |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112679454A (en) | Continuous preparation and purification method and device of 5-hydroxymethylfurfural | |
| CN110204422B (en) | Method for preparing 1, 3-propylene glycol from acrolein | |
| CN110183403B (en) | Method for converting fructose into 5-hydroxymethylfurfural by using ionic liquid as catalyst | |
| CN106397368A (en) | Fatty alcohol-polyoxyethylene ether glycidyl ether and preparation method thereof | |
| CN101407445A (en) | Waste polyester material recovery method with ion liquid as reaction medium and catalyst | |
| CN114315767A (en) | Preparation method and preparation device of 5-hydroxymethylfurfural | |
| CN104557809A (en) | Method for producing furfural from pentose | |
| CN114456131A (en) | Tetrahydrofuran production system and preparation method | |
| CN110981721A (en) | Method for continuously producing n-propyl acetate | |
| CN112094187B (en) | Method for preparing and separating levulinic acid from fructose | |
| CN101979365B (en) | Method for continuously preparing dichlorohydrin | |
| CN108947774A (en) | A kind of method and device of separating isopropanol | |
| CN110483678B (en) | Catalyst for preparing isosorbide by dehydrating sorbitol and preparation method and application thereof | |
| CN109180617B (en) | Two-phase biomass pretreatment co-production chemical method based on furfural compound extractant | |
| CN109134258B (en) | Product separation process for preparing methyl glycolate by dimethyl oxalate hydrogenation | |
| CN105294393A (en) | Method for preparing 1,4-cyclohexanedimethanol through one-pot hydrogenation | |
| CN102952004A (en) | Technology for separating ethylene glycol monomethyl ether and water by use of continuous azeotropic distillation method | |
| CN212076906U (en) | Side-line reaction type dioxolane production process device | |
| CN104557812A (en) | Method for producing furfural from biomass | |
| CN104557810A (en) | Method for producing furfuraldehyde from pentose solution by adopting impinging stream reactor | |
| CN113880792A (en) | Method for synthesizing carbohydrate-based furan chemicals | |
| CN103087348A (en) | Device and method for recovering para-aramid resin washing filtrate | |
| CN113880712A (en) | Preparation method of ethyl acetate | |
| CN113480401A (en) | Synthesis method of chloro-n-pentane | |
| CN112851490A (en) | Method for producing levulinic acid by efficiently catalyzing saccharides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |