CN110407778A - A kind of storage method of 5 hydroxymethyl furfural, the alcoholic solution of 5 hydroxymethyl furfural and the composition containing 5 hydroxymethyl furfural - Google Patents
A kind of storage method of 5 hydroxymethyl furfural, the alcoholic solution of 5 hydroxymethyl furfural and the composition containing 5 hydroxymethyl furfural Download PDFInfo
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- CN110407778A CN110407778A CN201810391105.2A CN201810391105A CN110407778A CN 110407778 A CN110407778 A CN 110407778A CN 201810391105 A CN201810391105 A CN 201810391105A CN 110407778 A CN110407778 A CN 110407778A
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- hydroxymethyl furfural
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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
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Abstract
The present invention provides a kind of storage method of 5 hydroxymethyl furfural and the alcoholic solution of 5 hydroxymethyl furfural and the composition containing 5 hydroxymethyl furfural.The storage method of 5 hydroxymethyl furfural provided by the invention, comprising: low-carbon alcohols are added into the container equipped with 5 hydroxymethyl furfural, makes it dissolve, then seals container, be kept in dark place.The present invention can react the characteristic for generating stable two acetal of 5 hydroxymethyl furfural using HMF with low-carbon alcohols, reduce the oxidation of aldehyde radical in HMF and air contact process, reduce after HMF is dissolved because strong hygroscopicity causes to absorb water and side reaction occurs.When needing using HMF crystal, can be easy to remove alcohol by the method for vacuum distillation or rotary evaporation, during removing alcohol, therefore acetal, which gradates, will not introduce other impurity for HMF crystal.
Description
Technical field
The present invention relates to a kind of storage methods of 5 hydroxymethyl furfural, belong to biological chemical field.
Background technique
5-HMF is one of the Important Platform compound of american energy office publication, is connection biomass resource and petrochemistry
Important bridge.Furan nucleus, hydroxyl and aldehyde radical in HMF molecule containing high activity etc., can be by adding hydrogen, esterification, halogenation, polymerization
With hydrolysis etc. processes further converted, as synthesis of polymer material monomer, macrocyclic compound synthesis material and
The fields such as medicine, pesticide intermediate have important potential using value, or even can match in excellence or beauty with terephthalic acid (TPA), but many simultaneously
Potential application also to the purity of HMF, more stringent requirements are proposed.But since the light of HMF itself, hot equistability are poor, need low temperature
It is kept in dark place, and HMF hygroscopicity is extremely strong, interior can absorb water of 1min becomes solution in air for exposure, and the stabilized aqueous solution of HMF
Property it is also very poor, further reaction can generate levulic acid and formic acid, meanwhile, during contacting with air, aldehyde radical is unstable,
Easily it is oxidized.Therefore, it explores and can effectively avoid HMF generation side reaction, and the simpler storage mode used convenient for HMF very must
It wants.
Currently, being still protected from light and being sealed for 2-8 DEG C there is no the report about the research of HMF storing mode.In use process
Middle discovery, after multiple corkage sampling, although sample time is very short, gradually moisture absorption becomes solution to remaining HMF in reagent bottle,
If putting back to refrigerator not in time, HMF color can gradually become brown by yellow.On the one hand the purity of HMF is caused to reduce, another party
Face, the HMF after moisture absorption are difficult to measure when in use, and to use after drying, since the boiling point of water is high, the thermal stability of HMF is poor,
Going bad for HMF is easily caused in the drying process.There is researcher to propose HMF being converted into the stable downstream product of performance,
Such as 2,5-furandicarboxylic acid, but HMF, as platform chemicals, product is varied downstream, is such as translated into one of which,
It is difficult to for HMF being converted back into again when carrying out the preparation of other compounds.Therefore, ideal storage method is the storage that can widen HMF
Condition is deposited, and guarantees its stability during HMF storage, is easy to use simultaneously.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of storage method of 5 hydroxymethyl furfural, this method utilizes 5-
It is with good stability that the acetal that reversible reaction generates occurs between hydroxymethylfurfural and alcoholic solvent, so that 5 hydroxymethyl furfural can
It stores at normal temperature, while side reaction occurs during it can be effectively prevent to use and store.
The present invention also provides the alcoholic solutions that one kind can be such that 5 hydroxymethyl furfural is stabilized.
The present invention also provides a kind of compositions containing 5 hydroxymethyl furfural.
First aspect present invention provides a kind of storage method of 5 hydroxymethyl furfural, comprising: to equipped with 5 hydroxymethyl furfural
Container in be added low-carbon alcohols, make it dissolve, then seal container, be kept in dark place.
The 5 hydroxymethyl furfural is preferably sterling, such as crystal, is also possible to purity not less than 92%, preferably not small
In 96% sterling.
The low-carbon alcohols are selected from or mixtures thereof methanol, ethyl alcohol, preferably methanol.The preferred chromatography of the purity of the low-carbon alcohols
It is pure.
The additional amount of the low-carbon alcohols can at least make HMF dissolution of crystals, for example, low-carbon alcohols and HMF molar ratio 2:1~
10000:1, preferably 40:1~5000:1, more preferable 100:1~1000:1.
The temperature being kept in dark place can be 0~40 DEG C, preferably 10-30 DEG C.
In use, a certain amount of HMF alcoholic solution is taken out out of container, after rotary evaporation or vacuum distillation removing alcohol
Obtain HMF crystal.
According to the method for the present invention, weak solid acid or weak solid can also be added into the container equipped with 5 hydroxymethyl furfural
Alkali.Weak solid acid or weak solid base can promote 5 hydroxymethyl furfural and low-carbon alcohols to generate acetal.The weak solid acid is weak solid
The pH value of body alkali is between 6-9, such as silica gel, TiO2、ZnO、ZnS、Al2O3, MgO etc., preferably silica gel, TiO2, Al2O3.It is weak solid
The additional amount of body acid or weak solid base is 0.1 times or more of HMF molal quantity, preferably 0.1~1.
Second aspect of the present invention provides a kind of alcoholic solution of 5 hydroxymethyl furfural, wherein contain 5 hydroxymethyl furfural, 5- hydroxyl
The acetal and low-carbon alcohols that methyl furfural and low-carbon alcohols are formed.
The low-carbon alcohols are selected from or mixtures thereof methanol, ethyl alcohol, preferably methanol.
In the alcoholic solution of the 5 hydroxymethyl furfural, molar ratio 2:1~10000:1 of low-carbon alcohols and 5 hydroxymethyl furfural,
It is preferred that 40:1~5000:1, more preferable 100:1~1000:1 (low-carbon alcohols and HMF group in acetal also count).Alcohol is molten
The content of acetal is not construed as limiting in liquid, much excessive in low-carbon alcohols because it is reversible reaction that low-carbon alcohols and HMF reaction, which generate acetal,
In the case where, reversible reaction is mobile to the direction for generating acetal, theoretically the substantially all generation acetal of HMF.
Third aspect present invention provides a kind of composition containing 5 hydroxymethyl furfural, wherein contain 5 hydroxymethyl furfural,
The acetal that 5 hydroxymethyl furfural and low-carbon alcohols are formed, weak solid acid or weak solid base and low-carbon alcohols.
The low-carbon alcohols are selected from or mixtures thereof methanol, ethyl alcohol, preferably methanol.
In the composition, molar ratio 2:1~10000:1 of low-carbon alcohols and 5 hydroxymethyl furfural, preferably 40:1~5000:
1, more preferable 100:1~1000:1 (low-carbon alcohols and HMF group in acetal also count).
The pH value of the weak solid acid or weak solid base is between 6-9, such as silica gel, TiO2、ZnO、ZnS、Al2O3、MgO
Deng, preferred silica gel, TiO2, Al2O3。
The additional amount of the weak solid acid or weak solid base is 0.1 times or more of 5 hydroxymethyl furfural molal quantity, preferably 0.1
~1.
Compared with prior art, the invention has the following advantages that first is that since HMF can be generated with methanol or ethanol synthesis
Two acetal of 5 hydroxymethyl furfural of ambient stable reduces the oxidation of aldehyde radical in HMF and air contact process, enhances room temperature
The stability of storage decreases after HMF is dissolved because strong hygroscopicity causes to absorb water and side reaction occurs；Second is that when needing using HMF
When crystal, the low boiling point of methanol and ethyl alcohol can be easy to remove alcohol by the method for vacuum distillation or rotary evaporation, remove
During removing alcohol, therefore acetal, which gradates, will not introduce other impurity for HMF crystal.
HMF and methanol generate acetal, and the reaction mechanism is as follows shown in formula:
Detailed description of the invention
Attached drawing 1 is the chromatogram for the HMF methanol solution that embodiment 2 obtains.
Attached drawing 2 is the acetal for the HMF methanol solution that embodiment 2 obtains and the mass spectrogram of HMF.
Specific embodiment
To facilitate the understanding of the present invention, it is as follows to enumerate embodiment by the present invention, but the embodiment is used only for helping to understand
The present invention should not be regarded as a specific limitation of the invention.
Embodiment 1:
The 0.1g HMF that new purchase purity is 99.9% is stored in brown sample bottle, the methanol of 5ml chromatographically pure is added, makes
It obtains HMF crystal to be completely dissolved, placement is kept in dark place at room temperature, and per two weeks takes out the open 1min that places and (simulates and usually sample
Process), it keeps being sealed later, so repeat 6 months, the methanol solution color burn of HMF, carry out HPLC detection, HMF is pure
Degree is 95.4%.
Embodiment 2:
The 0.1gHMF that new purchase purity is 99.9% is stored in brown sample bottle, the methanol of 3ml chromatographically pure is added, makes
It obtains HMF sterling to be completely dissolved, and the silica gel of HMF molal quantity 10% is added, placement is kept in dark place at room temperature, and per two weeks takes out
Opening places 1min (simulating usually sampling process), keeps being sealed later, so repeat 6 months, the methanol solution of HMF is still
For transparent yellow solution, the purity that HPLC detects HMF is that 52.6%, GC-MS testing result shows that remaining is acetal.This is molten
Yellow crystals are obtained after liquid vacuum drying, the dissolution of crystals is taken to carry out GC-MS detection at once in methanol, in solution in addition to methanol
All HMF, yellow crystals are dissolved in progress HPLC detection in deionized water, and HMF purity is 99.8%.
Embodiment 3:
The 0.1gHMF that new purchase purity is 99.9% is stored in brown sample bottle, the methanol of 3ml chromatographically pure is added, makes
It obtains HMF crystal to be completely dissolved, and the Al of HMF molal quantity 15% is added2O3, place and be kept in dark place at room temperature, per two weeks takes out
Opening places 1min (simulating usually sampling process), keeps being sealed later, so repeat 6 months, the methanol solution of HMF is still
For transparent yellow solution, the purity that HPLC detects HMF is that 46.2%, GC-MS testing result shows that remaining is acetal.This is molten
Yellow crystals are obtained after liquid vacuum drying, the dissolution of crystals is taken to carry out GC-MS detection at once in methanol, in solution in addition to methanol
All HMF, yellow crystals are dissolved in progress HPLC detection in deionized water, and HMF purity is 99.8%.
Embodiment 4:
The 0.1gHMF that new purchase purity is 99.9% is stored in brown sample bottle, at room temperature avoid light place one month,
Wherein opening places 1min (simulating usually sampling process) when two weeks, and purity is down to 98.2%.The first of 8ml chromatographically pure is added
So that HMF is completely dissolved, and 20% TiO is added in alcohol2, place and be kept in dark place at room temperature, per two weeks takes out open place
1min (simulates usually sampling process), keeps being sealed later, so repeat 6 months, the methanol solution of HMF is still transparent
Yellow solution, the purity that HPLC detects HMF is that 42.9%, GC-MS testing result shows that remaining is acetal.The solution vacuum is done
Yellow crystals are obtained after dry, and the dissolution of crystals is taken to carry out GC-MS detection at once in methanol, it is all in addition to methanol in solution
HMF, yellow crystals are dissolved in progress HPLC detection in deionized water, and HMF purity is 98.0%.
Embodiment 5:
The 0.1gHMF that new purchase purity is 99.9% is stored in brown sample bottle, the methanol of 2ml chromatographically pure is added, makes
It obtains HMF sterling to be completely dissolved, and 10% MgO is added, placement is kept in dark place at room temperature, and per two weeks takes out open placement
1min (simulates usually sampling process), keeps being sealed later, so repeat 6 months, the methanol solution of HMF is still transparent
Yellow solution, the purity that HPLC detects HMF is that 41.2%, GC-MS testing result shows that remaining is acetal.The solution vacuum is done
Yellow crystals are obtained after dry, and the dissolution of crystals is taken to carry out GC-MS detection at once in methanol, it is all in addition to methanol in solution
HMF, yellow crystals are dissolved in progress HPLC detection in deionized water, and HMF purity is 99.6%.
Comparative example 1:
Will new purchase purity be 99.9% HMF be stored in brown sample bottle, be placed in it is stored refrigerated in refrigerator, every half
It takes out open placement 1min (simulating usually sampling process) moon, seals put back to refrigerator later, so repeat 6 months, HMF is still in
Yellow crystalline carries out HPLC detection, and the purity that HPLC analyzes HMF is 99.8%.
Comparative example 1 illustrates that HMF is saved under low temperature, the environment for being protected from light, sealing, drying, and can effectively keep HMF's
Purity avoids the generation of by-product.
Comparative example 2:
The HMF that new purchase purity is 99.9% is stored in brown sample bottle, placement is kept in dark place at room temperature, and every half
Take out open placement 1min (simulating usually sampling process) moon, holding is sealed later, is so repeated 6 months, HMF becomes brown
Color solution carries out HPLC detection, and the purity that HPLC analyzes HMF is 86.8%.
Comparative example 2 illustrates: when HMF is saved at room temperature, repeatedly after contacting with the air, easily absorbing water, and by air
Dioxygen oxidation generate by-product so that the purity of HMF substantially reduces.
Comparative example 3
The 0.1g HMF that new purchase purity is 99.9% is stored in brown sample bottle, the methanol of 5ml chromatographically pure is added, makes
It obtains HMF crystal to be completely dissolved, and the highly acid silicon-aluminium compound of 10% Si/Al=18 is added, placement is protected from light guarantor at room temperature
It deposits, per two weeks takes out open placement 1min (simulating usually sampling process), and it keeps being sealed later, so repeat 6 months,
The methanol solution of HMF darkens, and carries out HPLC detection, and the purity of HMF is 38.4%, and another there are many impurity peaks.By the solution
Brown yellow oil liquid is obtained after vacuum drying, thus it is speculated that it is HMF, 5- methoxy-methylfurfural, levulic acid, 5- methylol chaff
The mixture of acid etc..
Comparative example 3 illustrates: when HMF is saved at room temperature, on the one hand, repeatedly after contacting with the air, easily absorbing water, and by
Dioxygen oxidation in air generates by-product；On the other hand, in the presence of having highly acid substance, HMF is easier to occur not with methanol
Reversible esterification.Two kinds of effects combine, so that the purity of HMF substantially reduces, and HMF can not restore after solvent removing.
Claims (15)
1. a kind of storage method of 5 hydroxymethyl furfural, comprising: low-carbon alcohols are added into the container equipped with 5 hydroxymethyl furfural, make
It is dissolved, and is then sealed container, is kept in dark place.
2. according to the method for claim 1, the low-carbon alcohols are selected from or mixtures thereof methanol, ethyl alcohol.
3. according to the method for claim 1, low-carbon alcohols and the molar ratio of 5 hydroxymethyl furfural are 2:1~10000:1, preferably
40:1~5000:1, more preferable 100:1~1000:1.
4. according to the method for claim 1, the temperature being kept in dark place is 0~40 DEG C.
5. weak solid acid or weak solid according to the method for claim 1, is also added into the container equipped with 5 hydroxymethyl furfural
Body alkali.
6. according to the method for claim 5, the pH value of the weak solid acid or weak solid base is described weak solid between 6-9
Body acid or the preferred silica gel of weak solid base, TiO2、ZnO、ZnS、Al2O3, one or more of MgO.
7. according to the method for claim 5, the additional amount of the weak solid acid or weak solid base is rubbed for 5 hydroxymethyl furfural
0.1 times or more of that number, preferably 0.1~1.
8. a kind of alcoholic solution of 5 hydroxymethyl furfural, wherein containing 5 hydroxymethyl furfural, 5 hydroxymethyl furfural is formed with low-carbon alcohols
Acetal and low-carbon alcohols.
9. alcoholic solution according to claim 8, wherein the low-carbon alcohols are selected from or mixtures thereof methanol, ethyl alcohol.
10. alcoholic solution according to claim 8, wherein molar ratio 2:1~10000 of low-carbon alcohols and 5 hydroxymethyl furfural:
1, preferably 40:1~5000:1, more preferable 100:1~1000:1, low-carbon alcohols and 5 hydroxymethyl furfural group in acetal also calculate
Inside.
11. a kind of composition containing 5 hydroxymethyl furfural, wherein contain 5 hydroxymethyl furfural, 5 hydroxymethyl furfural and low-carbon alcohols
The acetal of formation, weak solid acid or weak solid base and low-carbon alcohols.
12. composition according to claim 11, wherein the low-carbon alcohols are selected from or mixtures thereof methanol, ethyl alcohol.
13. composition according to claim 11, wherein the molar ratio 2:1 of low-carbon alcohols and 5 hydroxymethyl furfural~
10000:1, preferably 40:1~5000:1, more preferable 100:1~1000:1, low-carbon alcohols and 5 hydroxymethyl furfural group in acetal
Also it counts.
14. composition according to claim 11, wherein the pH value of the weak solid acid or weak solid base between 6-9 it
Between, the weak solid acid or the preferred silica gel of weak solid base, TiO2、ZnO、ZnS、Al2O3, one or more of MgO.
15. composition according to claim 11, wherein the additional amount of the weak solid acid or weak solid base is 5- hydroxyl first
0.1 times or more of the amount of base furfural substance, preferably 0.1~1.
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| CN201810391105.2A CN110407778B (en) | 2018-04-27 | 2018-04-27 | Storage method of 5-hydroxymethylfurfural, alcoholic solution of 5-hydroxymethylfurfural and composition containing 5-hydroxymethylfurfural |
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| CN201810391105.2A CN110407778B (en) | 2018-04-27 | 2018-04-27 | Storage method of 5-hydroxymethylfurfural, alcoholic solution of 5-hydroxymethylfurfural and composition containing 5-hydroxymethylfurfural |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437004A (en) * | 2020-11-06 | 2022-05-06 | 南开大学 | Method for preparing acetal and 5-hydroxymethylfurfural by relay catalysis of hexose |
| CN116178314A (en) * | 2021-11-29 | 2023-05-30 | 中国科学院宁波材料技术与工程研究所 | Method for improving storage and transportation stability of 5-hydroxymethylfurfural |
-
2018
- 2018-04-27 CN CN201810391105.2A patent/CN110407778B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 张晨: "生物质平台化合物5-羟甲基糠醛缩醛产物的合成与分离实验研究", 《中国优秀硕士学位论文工程科技1辑，北京化工大学硕士学位论文》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437004A (en) * | 2020-11-06 | 2022-05-06 | 南开大学 | Method for preparing acetal and 5-hydroxymethylfurfural by relay catalysis of hexose |
| CN116178314A (en) * | 2021-11-29 | 2023-05-30 | 中国科学院宁波材料技术与工程研究所 | Method for improving storage and transportation stability of 5-hydroxymethylfurfural |
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