CN111116527A - Method for preparing 5-hydroxymethylfurfural by hydrolyzing 5-chloromethylfurfural - Google Patents
Method for preparing 5-hydroxymethylfurfural by hydrolyzing 5-chloromethylfurfural Download PDFInfo
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- CN111116527A CN111116527A CN202010017258.8A CN202010017258A CN111116527A CN 111116527 A CN111116527 A CN 111116527A CN 202010017258 A CN202010017258 A CN 202010017258A CN 111116527 A CN111116527 A CN 111116527A
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- hydroxymethylfurfural
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- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
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Abstract
The invention belongs to the technical field of preparation of 5-hydroxymethylfurfural, and particularly relates to a method for preparing 5-hydroxymethylfurfural by hydrolyzing 5-chloromethyl furfural. And adding the 5-chloromethyl furfural solution into a mixed solvent of an organic solvent and water, adding an auxiliary agent, and heating for reaction to obtain the 5-hydroxymethyl furfural. The auxiliary agent adopted in the invention has low cost and rich raw material resources, and can remove the hydrolysis byproduct hydrogen chloride. The chemical activity of the 5-hydroxymethylfurfural is regulated and controlled by using the organic solvent/water mixed solvent, no other side reaction is generated, the high-concentration 5-chloromethyl furfural can be efficiently and selectively hydrolyzed to prepare the 5-hydroxymethylfurfural, the industrial production cost is favorably reduced, and the popularization and the application of the industrial large-scale preparation of the 5-hydroxymethylfurfural are favorably realized.
Description
Technical Field
The invention belongs to the technical field of preparation of 5-hydroxymethylfurfural, and particularly relates to a method for preparing 5-hydroxymethylfurfural by hydrolyzing 5-chloromethyl furfural.
Background
The continuous excavation of non-renewable resources such as petroleum and the rapidly increasing energy demand put tremendous pressure on the environment and economy. 5-Hydroxymethylfurfural (HMF) is an important chemical raw material as an important biomass-based chemical, is a raw material for synthesizing 2, 5-furandicarboxylic acid (FDCA), and can relieve the dependence on non-renewable resources such as petroleum. The 5-hydroxymethylfurfural has a furan ring coupled with a hydroxyl group and an aldehyde group present in the chemical structure thereof, and thus has very good chemical plasticity. The hydroxyl group can undergo esterification, dehydration, oxidation and halogenation reactions, while the aldehyde group can undergo reduction, decarbonylation, reductive amination and the like. In addition, the ring structure facilitates partial chemical reactions, such as halogenation, nitration, sulfonation, alkylation or acylation, and cycloaddition reactions. This means that a series of chemicals such as pyridine, pyrrole, cyclopentenone, and thiophene derivatives, such as 5-hydroxymethyl-furoic acid, 2, 5-dicarboxylic acid, 2, 5-bis-hydroxymethylfuran, 2, 5-furandicarboxylic acid, 2, 5-furandicarboxaldehyde, furfuryl alcohol, and formic acid, can be prepared using 5-hydroxymethylfurfural as an intermediate. Some of these chemicals can replace petroleum derived compounds such as adipic acid, alkyl glycols or hexamethylenediamine in polymer production, while others have potential application in the markets of solvents, biofuels, pharmaceuticals and textiles.
The main reason why 5-hydroxymethylfurfural has not been produced on a large scale so far is that great difficulty exists in the preparation and separation processes thereof. On one hand, the preparation of the 5-hydroxymethylfurfural mainly adopts glucose and fructose with higher cost as raw materials, and is obtained through dehydration reaction, so that cellulose which is cheaper and easily obtained is difficult to utilize; on the other hand, the chemical activity of the 5-hydroxymethylfurfural is high, and various side reactions are easy to occur, so that the concentration of a conversion substrate is low, the selectivity is low, and the cost is high. Thus, Mascal et al (pharmaceutical advances in the polysaccharide to 5- (hydroxymethyl) furfural conversion reaction, ChemSusChem 2009,2, 859-861) proposed a technical solution to convert 5-Chloromethylfurfural (CMF) with cheap and easily available cellulose instead of 5-hydroxymethylfurfural, and the yield of 5-Chloromethylfurfural (CMF) based on high cellulose feed could be over 50%, which could not be achieved by preparing 5-hydroxymethylfurfural with cellulose. However, the existence of chloride ions in 5-chloromethylfurfural makes it difficult to perform chemical reactions such as oxidation and esterification of 5-chloromethylfurfural, which limits its application. Therefore, 5-chloromethyl furfural needs to be hydrolyzed to obtain 5-hydroxymethyl furfural, and then other conversion and utilization are carried out.
However, hydrogen chloride is generated as a by-product of hydrolysis of 5-chloromethylfurfural, and side reactions such as acid hydrolysis and polymerization of 5-hydroxymethylfurfural are easily caused by continuous catalysis in an aqueous solution. These side reactions are particularly pronounced in the hydrolysis of high concentrations of 5-chloromethylfurfural, which greatly limits the selectivity of the hydrolysis of 5-chloromethylfurfural to 5-hydroxymethylfurfural.
Disclosure of Invention
In view of the above technical problems in the background art, it is desirable to provide a method for preparing 5-hydroxymethylfurfural by hydrolyzing 5-chloromethylfurfural, which has the advantages of simple and easily available raw materials, low cost and simple preparation process, and is beneficial to the popularization and application of industrially preparing 5-hydroxymethylfurfural on a large scale.
In order to achieve the above object, the inventors provide a method for preparing 5-hydroxymethylfurfural by hydrolyzing 5-chloromethylfurfural, comprising the following steps: and adding the 5-chloromethyl furfural solution into a mixed solvent of an organic solvent and water, adding an auxiliary agent, and heating for reaction to obtain the 5-hydroxymethyl furfural.
Different from the prior art, the technical scheme at least has the following beneficial effects:
1. the auxiliary agent adopted in the invention has low cost and rich raw material resources, and can remove the hydrolysis by-product hydrogen chloride;
2. the chemical activity of the 5-hydroxymethylfurfural is regulated and controlled by using an organic solvent/water mixed solvent, and other side reactions are avoided;
3. the method can realize the efficient selective hydrolysis of the high-concentration 5-chloromethyl furfural to prepare the 5-hydroxymethyl furfural, is favorable for reducing the industrial production cost, and is favorable for the popularization and the application of the industrial large-scale preparation of the 5-hydroxymethyl furfural.
Drawings
FIG. 1 is a GC spectrum of 5-chloromethylfurfural CMF, 5-hydroxymethylfurfural HMF, levulinic acid LA, angelica lactone AL obtained by the specific embodiment.
Detailed Description
The method for preparing 5-hydroxymethylfurfural by hydrolyzing 5-chloromethylfurfural according to the invention is described in detail below, and comprises the following steps: and adding the 5-chloromethyl furfural solution into a mixed solvent of an organic solvent and water, adding an auxiliary agent, and heating for reaction to obtain the 5-hydroxymethyl furfural.
Preferably, the organic solvent is one of dimethylsulfoxide, N-dimethylformamide, acetonitrile, tetrahydrofuran or 1, 4-dioxane. The organic solvents listed above are polar aprotic solvents, and can play a role in stabilizing the hydrolysate 5-hydroxymethylfurfural, thereby avoiding the generation of other byproducts by further hydrolysis.
In a preferred embodiment of the present invention, the mass ratio of the organic solvent to water is 1 to 5. The hydrolysis of 5-chloromethylfurfural requires the participation of water, but if the proportion of organic solvent is too high, the hydrolysis reaction proceeds very slowly, and if the proportion of organic solvent is too low, the stabilization of the hydrolysis product 5-hydroxymethylfurfural is not utilized, with the risk of further hydrolysis to produce other by-products.
As a preferable technical scheme of the invention, the auxiliary agent is one of calcium carbonate, barium carbonate, calcium hydroxide, aluminum hydroxide, barium hydroxide or calcium oxide. Hydrolysis of 5-chloromethylfurfural produces 5-hydroxymethylfurfural and hydrogen chloride (HCl) as a byproduct, which catalyzes further hydrolysis of 5-chloromethylfurfural to produce levulinic acid and other byproducts, so that it is necessary to remove HCl, which is hydrogen chloride produced with 5-hydroxymethylfurfural, with an alkaline substance. However, the hydrolysate 5-hydroxymethylfurfural is also unstable under strong alkali conditions such as NaOH, and therefore, a relatively good effect can be achieved by using these slightly soluble basic salts or hydroxides.
As a preferable technical scheme of the invention, the molar ratio of the auxiliary agent to the 5-chloromethyl furfural is 0.5-2. Too little of an alkaline salt or hydroxide adjuvant is detrimental to the neutralization of the hydrolysis by-product, too much of an alkaline adjuvant leads to other side reactions, and at least equimolar amounts of alkaline adjuvant are required to completely neutralize the hydrolysis by-product HCl.
As a preferable technical scheme of the invention, the heating reaction temperature is 60-100 ℃, and the heating reaction time is 2-100 min.
As a preferred technical scheme of the invention, the 5-chloromethylfurfural solution contains 5-30 wt% of 5-chloromethylfurfural. The hydrolysis concentration is higher, which is beneficial to industrial production, but the concentration is too high, the byproduct HCl is more, the side reaction is promoted, and finally the selectivity of the hydrolysis product 5 hydroxymethylfurfural is low, so experiments show that the concentration of less than 30 wt% is proper, and the yield of 5 hydroxymethylfurfural HMF is lower although the concentration of 5-chloromethylfurfural solution is about 40 wt%.
According to the invention, the organic solvent capable of performing solvation with 5-hydroxymethylfurfural is utilized, the reaction activity of 5-hydroxymethylfurfural is reduced, other side reactions are avoided, and meanwhile, a cheap auxiliary agent is adopted, and a hydrolysis byproduct, namely hydrogen chloride (HCl) can be removed, so that the preparation of 5-hydroxymethylfurfural through high-concentration and high-selectivity hydrolysis of 5-chloromethylfurfural can be realized, and the industrial production from cellulose to 5-hydroxymethylfurfural is facilitated.
To explain technical contents, structural features, and objects and effects of the technical solutions in detail, the following detailed description is given with reference to the accompanying drawings in conjunction with the embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.
The instrument and the detection index adopted in the embodiment of the invention are as follows:
carrying out qualitative detection on substances such as 5-hydroxymethylfurfural by adopting GC-MS Shimadzu QP 2020;
and (3) carrying out quantitative detection on substances such as 5-hydroxymethylfurfural by adopting an Agilent GC7890 gas chromatograph.
The chemical reagents and chemicals used in the examples of the present invention, such as dimethyl sulfoxide, N-dimethylformamide, acetonitrile, tetrahydrofuran, 1, 4-dioxane, calcium carbonate, barium carbonate, calcium hydroxide, aluminum hydroxide, barium hydroxide and calcium oxide, were purchased from national chemical company ltd and were analytically pure.
The 5-chloromethyl furfural solution adopted in the embodiment of the invention is purified and prepared after cellulose hydrolysis chlorination, and the preparation method comprises the following steps:
grinding wood, corn stalk or rice straw into coarse powder or cutting cotton into pieces, placing into a reactor, adding hydrochloric acid aqueous solution containing 5% lithium chloride, heating at 65 deg.C, extracting with 1, 2-dichloroethane solvent for 30 hr, distilling organic extract to recover solvent, and continuously extracting in standard equipment to obtain 5-chloromethyl furfural (CMF). The higher the cellulose content, the higher the yield of 5-Chloromethylfurfural (CMF) was found by chromatography of the residue.
Examples 1-4 the preparation of 5-hydroxymethylfurfural was carried out using the following method:
respectively adding 5g of deionized water and 5g of dimethyl sulfoxide, N-dimethylformamide, acetonitrile and tetrahydrofuran into a 50mL round-bottom flask, respectively adding 0.5g of calcium hydroxide, aluminum hydroxide, barium hydroxide and calcium oxide, heating to boiling at 100 ℃, then adding 1g of 5-chloromethyl furfural solution, violently stirring at 500rpm, keeping the temperature at 100 ℃ for 2-8min, rapidly cooling the reaction ice water bath to room temperature after the reaction is ended, sampling, and carrying out qualitative and quantitative detection by using a GC-MS gas chromatograph and a GC gas chromatograph, wherein the experimental parameters and the detection results of the examples 1-4 are listed as the serial numbers 1-4 in the Table 1. Referring to fig. 1, the examination shows that, besides the main product 5-hydroxymethylfurfural, small amounts of byproducts such as Levulinic Acid (LA) and Angelica Lactone (AL) are detected.
Examples 5-8 the preparation of 5-hydroxymethylfurfural was carried out using the following method:
respectively adding 0.346g of calcium carbonate, 5g of deionized water and 5g of 1, 4-dioxane into a 50mL round-bottom flask, heating to boil at 100 ℃, adding 1g of 5-chloromethylfurfural solution, violently stirring at the rotating speed of 500rpm, keeping at 100 ℃ for 4-16min, finishing the reaction, rapidly cooling to room temperature by using an ice water bath, sampling, and carrying out qualitative and quantitative detection by using a GC-MS gas chromatograph and a GC gas chromatograph, wherein the experimental parameters and the detection results of the examples 5-8 are listed as the serial numbers of 5-8 in the Table 1. Detection shows that in addition to the main product 5-hydroxymethylfurfural, small amounts of byproducts such as Levulinic Acid (LA), Angelica Lactone (AL) and the like are detected.
Examples 9-11 the preparation of 5-hydroxymethylfurfural was carried out using the following method:
0.346g of calcium carbonate, 5g of deionized water and 5g of 1, 4-dioxane were added into a 50mL round-bottomed flask, the mixture was heated to boil at 100 ℃, 0.5g to 3g of 5-chloromethylfurfural solution was added, the mixture was vigorously stirred at 500rpm and kept at 100 ℃ for 6 to 10min, the reaction was terminated, the mixture was rapidly cooled to room temperature in an ice water bath and sampled, qualitative and quantitative measurements were carried out using a GC-MS gas chromatograph and a GC gas chromatograph, and the experimental parameters and the measurement results of examples 9 to 11 were numbered 9 to 11 in Table 1.
Examples 12-15 the preparation of 5-hydroxymethylfurfural was carried out using the following method:
respectively adding 0.346g of calcium carbonate, 5g of deionized water and 5g of 1, 4-dioxane into a 50mL round-bottom flask, heating at 80 ℃ for 5-10min, adding 1g of 5-chloromethylfurfural, vigorously stirring at the rotating speed of 500rpm, keeping at 80 ℃ for 15-60min, finishing the reaction, rapidly cooling an ice water bath to room temperature, sampling, and carrying out qualitative and quantitative detection by using a GC-MS gas chromatograph and a GC gas chromatograph, wherein the experimental parameters and the detection results of the examples 12-15 are listed as serial numbers 12-15 in Table 1.
Examples 16-18 the preparation of 5-hydroxymethylfurfural was carried out using the following method:
0.346g of calcium carbonate, 5g of deionized water and 5g of 1, 4-dioxane were added to a 50mL round-bottomed flask, the mixture was heated at 60 ℃ for 5-10min, 1g of 5-chloromethylfurfural was added, the mixture was vigorously stirred (500rpm) and kept at 60 ℃ for 50-80min, the reaction was terminated, an ice-water bath was rapidly cooled to room temperature, and samples were taken, and qualitative and quantitative measurements were carried out using a GC-MS gas chromatograph and a GC gas chromatograph, and the experimental parameters and the measurement results of examples 16-18 were listed as numbers 16-18 in Table 1.
Examples 19-22 the preparation of 5-hydroxymethylfurfural was carried out using the following method:
respectively adding 0.346g of calcium carbonate into a 50mL round-bottom flask, and then respectively adding 3.33g, 2.5g, 2g and 1.67g of deionized water and 6.67g, 7.5g, 8g and 8.33g of 1, 4-dioxane, wherein the mass ratio of the organic solvent to the water is 2-5; heating the mixture at 80 ℃ for 5-10min, adding 1g of 5-chloromethylfurfural, violently stirring at the rotation speed of 500rpm, keeping the temperature at 80 ℃ for 60-100min, finishing the reaction, rapidly cooling in an ice water bath to room temperature, sampling, and carrying out qualitative and quantitative detection by using a GC-MS gas chromatograph and a GC gas chromatograph, wherein the experimental parameters and the detection results of the examples 19-22 are listed as the serial numbers 19-22 in the Table 1.
Examples 23-27 the preparation of 5-hydroxymethylfurfural was carried out using the following method:
0.692g of calcium carbonate, 5g of deionized water and 5g of 1, 4-dioxane are respectively added into a 50mL round-bottom flask, the mixture is heated at 80 ℃ for 5-10min, 2g of 5-chloromethyl furfural is added, the mixture is vigorously stirred (500rpm) and kept at 80 ℃ for 40-80min, the reaction is ended, an ice water bath is rapidly cooled to room temperature and sampled, qualitative and quantitative detection is carried out by using a GC-MS gas chromatograph and a GC gas chromatograph, and experimental parameters and detection results of examples 23-27 are listed as serial numbers 23-27 in Table 1.
Examples 28-29 the preparation of 5-hydroxymethylfurfural was carried out using the following method:
0.682g of barium carbonate, 5g of deionized water and 5g of 1, 4-dioxane were added into a 50mL round-bottomed flask, the mixture was heated at 80 ℃ for 5-10min, 1g of 5-chloromethylfurfural was added, the mixture was vigorously stirred (500rpm) and kept at 80 ℃ for 50-60min, an ice-water bath was rapidly cooled to room temperature after the reaction was completed, and samples were taken, and qualitative and quantitative determinations were carried out using a GC-MS gas chromatograph and a GC gas chromatograph, and the experimental parameters and the results of examples 28-29 were listed as numbers 28-29 in Table 1.
Examples 30-32 the preparation of 5-hydroxymethylfurfural was carried out using the following method:
1.364g, 2.046g and 2.728g of barium carbonate are respectively added into a 50mL round-bottom flask, 5g of deionized water and 5g of 1, 4-dioxane are added, the mixture is heated at 80 ℃ for 5-10min, 1g of 5-chloromethyl furfural is added, the mixture is vigorously stirred (500rpm) and kept at 80 ℃ for 60min, an ice water bath is rapidly cooled to room temperature after the reaction is ended, sampling is carried out, qualitative and quantitative detection is carried out by using a GC-MS gas chromatograph-mass spectrometer and a GC gas chromatograph, and the experimental parameters and the detection results of the examples 30-32 are listed as serial numbers 30-32 in Table 1.
Table 1 examples 1-32 experimental parameters
As can be seen from the data in Table 1, the invention has a wide variety of alternative organic solvent types and adjuvant types and combinations (examples 1-5). Under the condition that the same auxiliary agent and the same organic solvent are selected and the molar ratio of the auxiliary agent to the 5-chloromethylfurfural and the mass ratio of the organic solvent to the water are kept the same, the concentration of the 5-chloromethylfurfural substrate is high, the yield of the 5-hydroxymethylfurfural HMF is relatively high (examples 10 and 11), but the change of the yield of the 5-hydroxymethylfurfural HMF is not obvious relative to the change range of the substrate concentration, and the selection of the 5-chloromethylfurfural with the substrate concentration of 20 percent is more suitable based on the cost of industrial production. When calcium carbonate is used as an auxiliary agent, the concentration of a 5-chloromethyl furfural substrate is 20%, the molar ratio of the auxiliary agent to the 5-chloromethyl furfural is 1, the organic solvent is 1, 4-dioxane, and the mass ratio of the auxiliary agent to the 5-chloromethyl furfural to water is 1 (example 25), the yield of 5-hydroxymethyl furfural HMF is the highest. The longer the retention time, the higher the yield of HMF from 5-hydroxymethylfurfural (examples 23 to 25), but above a certain retention time, the yield of HMF from 5-hydroxymethylfurfural conversely tends to decrease (examples 25 to 27).
It should be noted that, although the above embodiments have been described herein, the invention is not limited thereto. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein, or by using equivalent structures or equivalent processes performed in the content of the present specification and the attached drawings, which are included in the scope of the present invention.
Claims (7)
1. A method for preparing 5-hydroxymethylfurfural by hydrolyzing 5-chloromethylfurfural is characterized by comprising the following steps:
and adding the 5-chloromethyl furfural solution into a mixed solvent of an organic solvent and water, adding an auxiliary agent, and heating for reaction to obtain the 5-hydroxymethyl furfural.
2. The method of claim 1, wherein the organic solvent is one of dimethylsulfoxide, N-dimethylformamide, acetonitrile, tetrahydrofuran, or 1, 4-dioxane.
3. The method according to claim 1, wherein the mass ratio of the organic solvent to water is 1 to 5.
4. The method of claim 1, wherein the auxiliary agent is one of calcium carbonate, barium carbonate, calcium hydroxide, aluminum hydroxide, barium hydroxide, or calcium oxide.
5. The method according to claim 1, wherein the molar ratio of the auxiliary agent to 5-chloromethylfurfural is 0.5-2.
6. The method according to claim 1, wherein the heating reaction temperature is 60-100 ℃ and the heating reaction time is 2-100 min.
7. The method of claim 1, wherein the 5-chloromethylfurfural solution contains 5-30 wt% of 5-chloromethylfurfural.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112341414A (en) * | 2020-10-10 | 2021-02-09 | 厦门大学 | Method for preparing 2, 5-furandicarboxylic acid by two-step hydrolysis and oxidation of 5-chloromethyl furfural |
| CN112625014A (en) * | 2020-12-22 | 2021-04-09 | 国网安徽省电力有限公司电力科学研究院 | Method for preparing 2, 5-furan diformyl chloride from 5-chloromethyl furfural |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1456556A (en) * | 2003-06-03 | 2003-11-19 | 复旦大学 | Di (5-formylfurfuryl) ether derivatives, preparations thereof and their uses in medicines |
| CN102617524A (en) * | 2012-03-28 | 2012-08-01 | 中国科学院广州能源研究所 | Method for preparing 5-hydroxymethyl furfural by utilizing biomass as raw material |
| US20120302765A1 (en) * | 2011-05-25 | 2012-11-29 | James Dumesic | Method to produce, recover and convert furan derivatives from aqueous solutions using alkylphenol extraction |
| CN103242270A (en) * | 2013-05-28 | 2013-08-14 | 华东理工大学 | Method for preparing furfural compounds from biomass |
| US20130217932A1 (en) * | 2012-02-16 | 2013-08-22 | Karl A. Seck | Biorefinery for conversion of carbothdrates and lignocellulosics via primary hydrolysate cmf to liquid fuels |
| CN106467507A (en) * | 2015-08-18 | 2017-03-01 | 北京大学 | A kind of preparation method of 5 hydroxymethyl furfural |
| CN110078689A (en) * | 2018-01-25 | 2019-08-02 | 中国科学院过程工程研究所 | A kind of preparation method of 5 hydroxymethyl furfural |
| CN110511196A (en) * | 2018-05-21 | 2019-11-29 | 中国石油化工股份有限公司 | A kind of method of purification of furfural or 5 hydroxymethyl furfural |
| CN113292521A (en) * | 2021-05-21 | 2021-08-24 | 贵州理工学院 | Method for preparing 5-hydroxymethylfurfural from cellulose biomass |
-
2020
- 2020-01-08 CN CN202010017258.8A patent/CN111116527A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1456556A (en) * | 2003-06-03 | 2003-11-19 | 复旦大学 | Di (5-formylfurfuryl) ether derivatives, preparations thereof and their uses in medicines |
| US20120302765A1 (en) * | 2011-05-25 | 2012-11-29 | James Dumesic | Method to produce, recover and convert furan derivatives from aqueous solutions using alkylphenol extraction |
| US20130217932A1 (en) * | 2012-02-16 | 2013-08-22 | Karl A. Seck | Biorefinery for conversion of carbothdrates and lignocellulosics via primary hydrolysate cmf to liquid fuels |
| CN102617524A (en) * | 2012-03-28 | 2012-08-01 | 中国科学院广州能源研究所 | Method for preparing 5-hydroxymethyl furfural by utilizing biomass as raw material |
| CN103242270A (en) * | 2013-05-28 | 2013-08-14 | 华东理工大学 | Method for preparing furfural compounds from biomass |
| CN106467507A (en) * | 2015-08-18 | 2017-03-01 | 北京大学 | A kind of preparation method of 5 hydroxymethyl furfural |
| CN110078689A (en) * | 2018-01-25 | 2019-08-02 | 中国科学院过程工程研究所 | A kind of preparation method of 5 hydroxymethyl furfural |
| CN110511196A (en) * | 2018-05-21 | 2019-11-29 | 中国石油化工股份有限公司 | A kind of method of purification of furfural or 5 hydroxymethyl furfural |
| CN113292521A (en) * | 2021-05-21 | 2021-08-24 | 贵州理工学院 | Method for preparing 5-hydroxymethylfurfural from cellulose biomass |
Non-Patent Citations (1)
| Title |
|---|
| 韩广甸等: "《有机制备化学手册》", 31 May 1980 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112341414A (en) * | 2020-10-10 | 2021-02-09 | 厦门大学 | Method for preparing 2, 5-furandicarboxylic acid by two-step hydrolysis and oxidation of 5-chloromethyl furfural |
| CN112625014A (en) * | 2020-12-22 | 2021-04-09 | 国网安徽省电力有限公司电力科学研究院 | Method for preparing 2, 5-furan diformyl chloride from 5-chloromethyl furfural |
| CN112625014B (en) * | 2020-12-22 | 2023-05-23 | 国网安徽省电力有限公司电力科学研究院 | Method for preparing 2, 5-furan diformyl chloride from 5-chloromethyl furfural |
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