CN105061367A - Method for preparing 5-hydroxymethylfurfural from fructose under catalysis of xylonic acid - Google Patents
Method for preparing 5-hydroxymethylfurfural from fructose under catalysis of xylonic acid Download PDFInfo
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- CN105061367A CN105061367A CN201510491500.4A CN201510491500A CN105061367A CN 105061367 A CN105061367 A CN 105061367A CN 201510491500 A CN201510491500 A CN 201510491500A CN 105061367 A CN105061367 A CN 105061367A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- 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
- C07D307/38—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 with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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Abstract
The invention belongs to the technical field of organic synthesis, and discloses a method for preparing 5-hydroxymethylfurfural from fructose under catalysis of xylonic acid. According to the method, the fructose is used as a raw material, and the 5-hydroxymethylfurfural is obtained through a reaction under catalysis of the xylonic acid. The method comprises preparation steps as follows: (1) adding a xylonic acid catalyst to a reactor containing an organic solvent, and stirring the mixture to fully dissolve the xylonic acid catalyst; (2) adding the fructose to the reactor in Step (1) for a reaction at the temperature of 70-150 DEG C for 1-24 h, and removing the organic solvent to obtain the 5-hydroxymethylfurfural. According to the method, the used catalyst is the xylonic acid which is a safe renewable catalyst, products produced by conversion of the xylonic acid are harmless, and the process for separating the catalyst and the products is omitted. The yield of the 5-hydroxymethylfurfural and the conversion rate of the fructose are high, and the preparation method has the bright application prospect.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to a kind of method utilizing xylosic acid catalysis fructose to prepare 5 hydroxymethyl furfural.
Background technology
5 hydroxymethyl furfural is as one of ten large platform compounds, and chemical property is active, and a series of important Chemicals prepared by alternative oil, such as levulinic acid, 2,5-furans dicarboxylic acid (FDCA), hydroxymethylfurfural base glycol.Meanwhile, 5 hydroxymethyl furfural is at medicine, and agricultural, the application of the aspects such as makeup is also very extensive.
The preparation of current 5 hydroxymethyl furfural also mainly rests on laboratory stage, obtains through catalytic dehydration primarily of hexose class raw material.Wherein catalyzer comprises: mineral acid, metallic compound, solid acid.Mineral acid (hydrochloric acid, sulfuric acid etc.) has corrodibility to equipment, and easily causes environmental pollution; The metallic compound prevailing price with higher catalytic activity is high and toxic; And although solid acid catalyst well solves separation and the reuse problem of catalyzer, its stability and catalytic activity poor; Therefore environmental friendliness is found and the suitability for industrialized production of catalyzer to 5 hydroxymethyl furfural with higher catalytic activity is very necessary.
As the reproducible biomass-based organic acid of one, xylosic acid can promote that human body is to the absorption of vitamin C, and gluconic acid also can be replaced as pharmaceutical intermediate, or the main component of s-generation cement.As far back as 1986, the productive rate that xylosic acid is produced in wood-sugar fermentation reached 80%, and preparation technology is simple.The report industrially applied due to current xylosic acid is also few, and its suitability for industrialized production is subject to very big restriction.The method of xylosic acid efficiency utilization is found to prepare industrial expansion to xylosic acid and biomass higher value application is very important.
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, the object of the present invention is to provide a kind of method utilizing xylosic acid catalysis fructose to prepare 5 hydroxymethyl furfural.
The object of the invention is achieved through the following technical solutions:
Utilize xylosic acid catalysis fructose to prepare a method for 5 hydroxymethyl furfural, described method take fructose as raw material, under the katalysis of xylosic acid, be obtained by reacting 5 hydroxymethyl furfural.
Described method comprises following preparation process:
(1) xylosic acid catalyzer is joined be equipped with in the reactor of organic solvent, stir and xylosic acid catalyzer is fully dissolved;
(2) fructose is added in the reactor in step (1), react 1 ~ 24h at 70 ~ 150 DEG C of temperature, remove organic solvent, obtain 5 hydroxymethyl furfural.
Preferably, described xylosic acid refers to the xylosic acid obtained by wood-sugar fermentation or the xylosic acid prepared with catalyzing by metal palladium wood sugar.
Preferably, described sources of fructose is in plant fiber material.
Preferably, described organic solvent refers to dimethyl sulfoxide (DMSO) (DMSO).
Preferably, the consumption of described xylosic acid and the mol ratio of fructose are (0.1 ~ 0.5): 1.
Preferably, described fructose mass concentration is in organic solvent 5% ~ 25%.
Above-mentioned preparation method relates to following reaction formula:
Preparation method's tool of the present invention has the following advantages and beneficial effect:
(1) catalyzer that the present invention is used is xylosic acid, and xylosic acid derives from wood-sugar fermentation, and wood sugar content in the hemicellulose of plant is huge, is a kind of safe Regenrable catalyzed dose, contributes to cleaner production;
(2) catalyzer that the present invention is used self also can transform while catalyzed reaction, and its product may generate high value-added product through further catalysis together with 5 hydroxymethyl furfural, decreases the process of catalyzer and product separation;
(3) preferred DMSO, the DMSO dissolving power of organic solvent used in the present invention is strong, fully can dissolve xylosic acid, ensures the carrying out of catalyzed reaction; The polarity of DMSO own is comparatively strong and have very strong binding ability with the hydroxyl on 5 hydroxymethyl furfural in addition, is conducive to fructose dehydration and generates 5 hydroxymethyl furfural and increase its stability.
Accompanying drawing explanation
Fig. 1 is the column comparison diagram of embodiment 15 hydroxymethyl furfural yield and fructose converting rate at differential responses temperature;
Fig. 2 is that embodiment 2 is at differential responses temperature and the 5 hydroxymethyl furfural yield graphic representation under the differential responses time;
Fig. 3 is that embodiment 2 is at differential responses temperature and the fructose converting rate curve figure under the differential responses time;
Fig. 4 is the column comparison diagram of embodiment 35 hydroxymethyl furfural yield and fructose converting rate under different xylosic acid consumption;
Fig. 5 is the column comparison diagram of embodiment 45 hydroxymethyl furfural yield and fructose converting rate under different fructose concentration.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) take 83mg xylosic acid catalyzer to join and be equipped with in the reactor of 900mgDMSO, be placed in 80 DEG C of stirred in water bath 15min and xylosic acid is fully dissolved;
(2) taking 300.0mg fructose adds in the reaction system that step (1) obtains, be placed in differing temps respectively: stirring reaction 8h at 70 DEG C, 90 DEG C, 110 DEG C, 130 DEG C and 150 DEG C, react final vacuum and removed DMSO, obtain 5 hydroxymethyl furfural.
Get the reaction solution after having reacted at different temperatures in step (2), after question response liquid temp is down to room temperature, is settled to 50mL with the dilution of 5mmol/L dilution heat of sulfuric acid, carries out the mensuration of 5 hydroxymethyl furfural content with high performance liquid chromatograph.
After measured, under 70 DEG C, 90 DEG C, 110 DEG C, 130 DEG C and 150 DEG C of temperature, 5 hydroxymethyl furfural yield is respectively: 32.20%, 36.41%, 69.65%, 81.52% and 70.69%; Fructose converting rate is respectively: 33.57%, 50.37%, 79.41%, 84.66% and 84.66%.The column comparison diagram of the above results as shown in Figure 1.
Embodiment 2
(1) take 83mg xylosic acid catalyzer to join and be equipped with in the reactor of 900mgDMSO, be placed in 80 DEG C of stirred in water bath 15min and xylosic acid is fully dissolved;
(2) taking 300.0mg fructose adds in the reaction system that step (1) obtains, and at being placed in 90 DEG C, 120 DEG C and 150 DEG C respectively, 2h, 4h, 8h, 12h and 24h are stirred in oil bath, have reacted final vacuum and have removed DMSO, obtained 5 hydroxymethyl furfural.
Get the reaction solution after having reacted under differing temps and different time in step (2), after question response liquid temp is down to room temperature, be settled to 50mL with the dilution of 5mmol/L dilution heat of sulfuric acid, carry out the mensuration of 5 hydroxymethyl furfural content with high performance liquid chromatograph.
After measured, be 90 DEG C, when the reaction times is respectively 2h, 4h, 8h, 12h and 24h in temperature of reaction, 5 hydroxymethyl furfural yield is respectively 11.52%, 32.53%, 48.96%, 59.47% and 63.68%; Fructose converting rate is respectively 34.97%, 50.37%, 79.78%, 85.03% and 84.66%; Be 120 DEG C, when the reaction times is respectively 2h, 4h, 8h, 12h and 24h in temperature of reaction, 5 hydroxymethyl furfural yield is respectively 17.11%, 38.82%, 67.87%, 79.41% and 81.88%; Fructose converting rate is respectively 43.37%, 71.71%, 89.58%, 92.39% and 92.72%; Be 150 DEG C, when the reaction times is respectively 2h, 4h, 8h, 12h and 24h in temperature of reaction, 5 hydroxymethyl furfural yield is respectively 23.06%, 52.11%, 65.42%, 72.42% and 76.63%; Fructose converting rate is respectively 47.92%, 78.03%, 93.43%, 95.53% and 95.87%.The 5 hydroxymethyl furfural yield graphic representation of the above results and fructose converting rate curve figure are respectively as shown in Figures 2 and 3.
Embodiment 3
(1) take 33.2mg, 83.0mg and 138.3mg xylosic acid catalyzer respectively to join and be equipped with in the reactor of 900mgDMSO, be placed in 80 DEG C of stirred in water bath 15min and xylosic acid is fully dissolved;
(2) take 300.0mg fructose to add in the reaction system that step (1) obtains, be placed in 120 DEG C of oil bath stirring reaction 8h, reacted final vacuum and removed DMSO, obtained 5 hydroxymethyl furfural.
Get the reaction solution after having reacted in step (2) respectively, after question response liquid temp is down to room temperature, is settled to 50mL with the dilution of 5mmol/L dilution heat of sulfuric acid, carries out the mensuration of 5 hydroxymethyl furfural content with high performance liquid chromatograph.
After measured when xylosic acid consumption is respectively 33.2mg, 83.0mg and 138.3mg, 5 hydroxymethyl furfural yield is respectively 84.13%, 70.19% and 69.80%; Fructose converting rate is respectively 95.15%, 91.12% and 75.32%.The column comparison diagram of the above results as shown in Figure 4.
Embodiment 4
(1) take 33.2mg xylosic acid catalyzer to join and be equipped with in the reactor of 900mgDMSO, be placed in 80 DEG C of stirred in water bath 15min and xylosic acid is fully dissolved;
(2) take 48.0mg, 100.0mg, 160.0mg and 300.0mg fructose respectively to add in the reaction system that step (1) obtains, be placed in 120 DEG C of oil bath stirring reaction 8h, reacted final vacuum and removed DMSO, obtained 5 hydroxymethyl furfural.
Get the reaction solution after having reacted in step (2) respectively, after question response liquid temp is down to room temperature, is settled to 50mL with the dilution of 5mmol/L dilution heat of sulfuric acid, carries out the mensuration of 5 hydroxymethyl furfural content with high performance liquid chromatograph.
After measured when the add-on of fructose is respectively 48.0mg, 100.0mg, 160.0mg and 300.0mg, 5 hydroxymethyl furfural yield is respectively 89.93%, 87.86%, 88.30% and 91.60%; Fructose converting rate is respectively 95.52%, 99.12%, 97.02% and 91.60%.The column comparison diagram of the above results as shown in Figure 5.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. utilize xylosic acid catalysis fructose to prepare a method for 5 hydroxymethyl furfural, it is characterized in that: described method take fructose as raw material, under the katalysis of xylosic acid, be obtained by reacting 5 hydroxymethyl furfural.
2. a kind of method utilizing xylosic acid catalysis fructose to prepare 5 hydroxymethyl furfural according to claim 1, is characterized in that described method comprises following preparation process:
(1) xylosic acid catalyzer is joined be equipped with in the reactor of organic solvent, stir and xylosic acid catalyzer is fully dissolved;
(2) fructose is added in the reactor in step (1), react 1 ~ 24h at 70 ~ 150 DEG C of temperature, remove organic solvent, obtain 5 hydroxymethyl furfural.
3. a kind of method utilizing xylosic acid catalysis fructose to prepare 5 hydroxymethyl furfural according to claim 1 and 2, is characterized in that: described xylosic acid refers to the xylosic acid obtained by wood-sugar fermentation or the xylosic acid prepared with catalyzing by metal palladium wood sugar.
4. a kind of method utilizing xylosic acid catalysis fructose to prepare 5 hydroxymethyl furfural according to claim 1 and 2, is characterized in that: described sources of fructose is in plant fiber material.
5. a kind of method utilizing xylosic acid catalysis fructose to prepare 5 hydroxymethyl furfural according to claim 2, is characterized in that: described organic solvent refers to dimethyl sulfoxide (DMSO).
6. a kind of method utilizing xylosic acid catalysis fructose to prepare 5 hydroxymethyl furfural according to claim 2, is characterized in that: the consumption of described xylosic acid and the mol ratio of fructose are (0.1 ~ 0.5): 1.
7. a kind of method utilizing xylosic acid catalysis fructose to prepare 5 hydroxymethyl furfural according to claim 2, is characterized in that: described fructose mass concentration is in organic solvent 5% ~ 25%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053642A (en) * | 2018-08-23 | 2018-12-21 | 南京工业大学 | Method for converting fructose into 5-hydroxymethylfurfural by inorganic salt-gluconic acid system |
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2015
- 2015-08-12 CN CN201510491500.4A patent/CN105061367A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 张秀东等: "木糖酸催化果糖转化为5-羟甲基糠醛的研究", 《2015年第十四届全国应用化学年会论文集（下）》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053642A (en) * | 2018-08-23 | 2018-12-21 | 南京工业大学 | Method for converting fructose into 5-hydroxymethylfurfural by inorganic salt-gluconic acid system |
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