CN109485622A - A method of synthesis 5 hydroxymethyl furfural - Google Patents
A method of synthesis 5 hydroxymethyl furfural Download PDFInfo
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- CN109485622A CN109485622A CN201811506300.1A CN201811506300A CN109485622A CN 109485622 A CN109485622 A CN 109485622A CN 201811506300 A CN201811506300 A CN 201811506300A CN 109485622 A CN109485622 A CN 109485622A
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
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Abstract
A method of synthesis 5 hydroxymethyl furfural belongs to 5 hydroxymethyl furfural preparation technical field.Cellobiose, solvent pairs saturated salt solution and methyl iso-butyl ketone (MIBK), niobium modified Montmorillonites are added in pressure bottle reactor, and place it in constant temperature oil bath and reacted, agitating device in reactor carries out dehydration at a certain temperature；After reaction, be cooled to room temperature to gained mixture temperature, filtered in, after gained filtrate stratification, 5 hydroxymethyl furfural is in solvent pairs；Continue on for next round reaction after filtering resulting solid catalyst.The invention has the advantages that: low in cost, easy to operate, small to the corrosion of equipment, catalyst is Ke Xunhuanliyong, product yield high, up to 60% or more.
Description
Technical field
The present invention is a kind of new method that niobium modified Montmorillonites synthesize 5 hydroxymethyl furfural in biphasic solvent, is belonged to
In 5 hydroxymethyl furfural preparation technical field.
Background technique
5 hydroxymethyl furfural, English name 5-hydroxymethylfurfural are abbreviated as 5-HMF, faint yellow acicular crystal,
Molecular formula C6H6O3, molecular weight 126.11,28-34 DEG C of fusing point, 114-116 DEG C of boiling point, density 1.243g/mL (25 DEG C), maximum is inhaled
Receipts wavelength is 284nm, is a kind of important industrial chemicals.5-HMF is soluble easily in water, ethyl alcohol, methanol, ethyl acetate, methyl tert-butyl
Base ketone, acetone, dimethylformamide, dimethyl sulfoxide etc.；Dissolve in chloroform, benzene, ether etc.；It is slightly soluble in carbon tetrachloride；Indissoluble
In petroleum ether.It is acknowledged as one of most potential Novel platform compound in recent years, and chemical property is active, can be with
By being esterified, add hydrogen, oxidation, dehydrogenation, halogenation, polymerization and other chemical reactive synthesis multiple compounds and high molecular material, shape
At large quantities of world energy sources and Chemical Industry based on fossil feedstock.
Originally, preparing the catalyst of 5-HMF use by biomass is mostly inorganic acid cheap and easy to get, such as sulfuric acid, hydrochloric acid, phosphorus
Acid etc. achieves certain research achievement, but inorganic acid has very strong corrosivity, will cause biggish pollution to environment.
Organic acid, inorganic salts, Lewis acid, solid acid, ionic liquid [10], molecular sieve, ion exchange resin etc. is gradually developed to later to urge
Agent.However, inorganic acid, organic acid, Lewis acid, inorganic salts, ionic liquid etc. are homogeneous catalyst, although they can be very
It is contacted with reactant well, but product is difficult to separate, the recycling of catalyst is not easy to realize, and will cause one to equipment
Fixed corrosion；And the heterogeneous catalysis such as solid acid, molecular sieve are easy to separate from reaction system, and product may be implemented
Separation and catalyst recycle, but catalytic effect be not very well, so find it is a kind of it is can be recycled, effect is good
Heterogeneous catalysis is most important.
Other than finding efficient catalyst, select suitable reaction system be also promote carbohydrate Efficient Conversion for
The effective measures of 5-HMF.With the continuous deepening of research, multi-solvents system has been developed to turn for carbohydrate
Change, there is researcher to generate 5 hydroxymethyl furfural in simple water phase or organic phase, compared to pure water phase, the carbon in having solvent
The result of hydrate hydrolysis is ideal, to find out its cause, mainly since 5-HMF is degraded to the pair of the lower acids such as levulic acid
Reaction can be suppressed to a certain extent in organic solvent, but so the boiling point of solvent is usually higher, so that the separation of 5-HMF
Relative difficulty is made in purification.Therefore developing new dicyandiamide solution is also a research emphasis from now on.
Summary of the invention
It is an object of the invention to overcome the shortcomings of the prior art, and provide a kind of catalytic efficiency it is higher and
It can recycle, low in cost, the new method of the synthesis 5 hydroxymethyl furfural to reduce environmental pollution.
The object of the invention can be achieved by the following measures:
1) niobium modified Montmorillonites are prepared；
2) cellobiose, solvent pairs saturated salt solution and methyl iso-butyl ketone (MIBK), niobium modified Montmorillonites are added to
In pressure bottle reactor, and places it in constant temperature oil bath and reacted, agitating device in reactor, at a certain temperature
Carry out dehydration；
3) after reaction, be cooled to room temperature to gained mixture temperature, filtered in, gained filtrate stratification it
Afterwards, upper and lower level liquid is taken to carry out collecting 5 hydroxymethyl furfural respectively, 5 hydroxymethyl furfural is in solvent pairs；
4) continue on for next round reaction after filtering resulting solid catalyst.
Niobium modified Montmorillonites described in step (1) are that columbium pentachloride ethanol solution is modified montmorillonite, will
Na between cheating engaging layer+、Ca2+Ion exchange is Nb5+Ion.It is preferred that columbium pentachloride and montmorillonite are dispersed in ethyl alcohol, at 20-60 DEG C
It is reacted；The further preferably dosage relation 2-7g:2g:100-500ml of columbium pentachloride, montmorillonite, ethyl alcohol.
Solvent described in step (2) is saturated salt solution and methyl iso-butyl ketone (MIBK) biphasic solvent；Biphasic solvent saturated common salt
Will according to a certain percentage between water and methyl iso-butyl ketone (MIBK), volume ratio 1-3.5:1.5-4.
The reaction temperature is 140-180 DEG C, preferably 160 DEG C.
The reaction time is 1-8 hours, preferably 3 hours.
Cellobiose, solvent pairs, niobium modified Montmorillonites dosage relation 7-20mg:1-10ml:1-7mg.
This method is using modified montmorillonoid as catalyst, in which: using metal niobium ion as activated centre to montmorillonite K-
10 are modified, the biphasic solvent that dicyandiamide solution is made of inorganic phase saturated salt solution and organic phase hexone,
Catalyst is Ke Xunhuanliyong, product yield high, up to 60% or more.
Compared with the prior art, the invention has the following advantages:
1, due to using niobium modified Montmorillonites, the catalytic amount used greatly reduces, and reduces production cost；
2, after present invention reaction, catalyst is easily separated, and post-processing is simple, can recycle, reduce acid catalyst pair
The pollution of environment；
3, using cellobiose as raw material, cost is reduced；
4,5-HMF is formed as system in water phase using two-phase solvent, product is constantly extracted to while reaction
In organic phase, yield is improved.
Detailed description of the invention
Fig. 1 is embodiment circulating effect figure.
Specific embodiment
Below with reference to embodiment, the present invention is further described, but is not intended to limit the present invention.
The preparation of following embodiment niobium modified Montmorillonites: columbium pentachloride and montmorillonite are dispersed in ethyl alcohol, at 40 DEG C
It is reacted；Columbium pentachloride, montmorillonite, ethyl alcohol dosage relation 10.8g:4g:400ml.
Embodiment 1
The niobium modified Montmorillonites of the cellobiose of 50mg and 25mg are added to simultaneously and fill 5mL biphasic solvent
In heavy wall pressure bottle (15mL) reactor, biphasic solvent be saturated salt solution and methyl iso-butyl ketone (MIBK), volume ratio 1.5:3.5,
And heavy wall pressure bottle is placed in constant temperature oil bath and is reacted, reaction temperature is measured by being inserted into the thermocouple of oil bath pan.Instead
Magneton built in device is answered, stirring rate is maintained at 500rpm.By certain reaction time, reaction flask is transferred to ice-water bath at once
Middle quenching reaction.Transfer it in suction funnel and filtered, filter resulting solid catalyst it is washed, it is dry at
It weighs after reason, to ensure that reaction is recycled to react the reactant being consistent, catalyst ratio with original, it is anti-to continue on for next round
It answers.After gained filtrate stratification, after respectively taking upper and lower level liquid to be diluted 250 times, using high-efficient liquid phase chromatogram technique analysis
Dilution is reacted, so that measuring 5-HMF yield is 68.52%；
Embodiment 2
The niobium modified Montmorillonites of the cellobiose of 50mg and 25mg are added to simultaneously and fill 5mL biphasic solvent
In heavy wall pressure bottle (15mL) reactor, biphasic solvent is saturated salt solution and methyl iso-butyl ketone (MIBK), volume ratio 1:4, and general
Heavy wall pressure bottle, which is placed in constant temperature oil bath, to be reacted, and reaction temperature is measured by being inserted into the thermocouple of oil bath pan.Reactor
Built-in magneton, stirring rate are maintained at 500rpm.By certain reaction time, reaction flask is transferred in ice-water bath quenches at once
It goes out reaction.Transfer it in suction funnel and filtered, filter resulting solid catalyst it is washed, be dried after
Weighing continues on for next round reaction to ensure that reaction is recycled to react the reactant being consistent, catalyst ratio with original.
After gained filtrate stratification, after respectively taking upper and lower level liquid to be diluted 250 times, reacted using high-efficient liquid phase chromatogram technique analysis
Dilution, so that measuring 5-HMF yield is 63.39%.
Embodiment 3
The niobium modified Montmorillonites of the cellobiose of 50mg and 25mg are added to simultaneously and fill 5mL biphasic solvent
In heavy wall pressure bottle (15mL) reactor, biphasic solvent is saturated salt solution and methyl iso-butyl ketone (MIBK), volume ratio 2:3, and general
Heavy wall pressure bottle, which is placed in constant temperature oil bath, to be reacted, and reaction temperature is measured by being inserted into the thermocouple of oil bath pan.Reactor
Built-in magneton, stirring rate are maintained at 500rpm.By certain reaction time, reaction flask is transferred in ice-water bath quenches at once
It goes out reaction.Transfer it in suction funnel and filtered, filter resulting solid catalyst it is washed, be dried after
Weighing continues on for next round reaction to ensure that reaction is recycled to react the reactant being consistent, catalyst ratio with original.
After gained filtrate stratification, after respectively taking upper and lower level liquid to be diluted 250 times, reacted using high-efficient liquid phase chromatogram technique analysis
Dilution, so that measuring 5-HMF yield is 57.86%.
Embodiment 4
The niobium modified Montmorillonites of the cellobiose of 50mg and 25mg are added to simultaneously and fill 5mL biphasic solvent
In heavy wall pressure bottle (15mL) reactor, biphasic solvent be saturated salt solution and methyl iso-butyl ketone (MIBK), volume ratio 2.5:2.5,
And heavy wall pressure bottle is placed in constant temperature oil bath and is reacted, reaction temperature is measured by being inserted into the thermocouple of oil bath pan.Instead
Magneton built in device is answered, stirring rate is maintained at 500rpm.By certain reaction time, reaction flask is transferred to ice-water bath at once
Middle quenching reaction.Transfer it in suction funnel and filtered, filter resulting solid catalyst it is washed, it is dry at
It weighs after reason, to ensure that reaction is recycled to react the reactant being consistent, catalyst ratio with original, it is anti-to continue on for next round
It answers.After gained filtrate stratification, after respectively taking upper and lower level liquid to be diluted 250 times, using high-efficient liquid phase chromatogram technique analysis
Dilution is reacted, so that measuring 5-HMF yield is 52.6%.
Embodiment 5
The niobium modified Montmorillonites of the cellobiose of 50mg and 25mg are added to simultaneously and fill 5mL biphasic solvent
In heavy wall pressure bottle (15mL) reactor, biphasic solvent be saturated salt solution and methyl iso-butyl ketone (MIBK), volume ratio 3.5:1.5,
And heavy wall pressure bottle is placed in constant temperature oil bath and is reacted, reaction temperature is measured by being inserted into the thermocouple of oil bath pan.Instead
Magneton built in device is answered, stirring rate is maintained at 500rpm.By certain reaction time, reaction flask is transferred to ice-water bath at once
Middle quenching reaction.Transfer it in suction funnel and filtered, filter resulting solid catalyst it is washed, it is dry at
It weighs after reason, to ensure that reaction is recycled to react the reactant being consistent, catalyst ratio with original, it is anti-to continue on for next round
It answers.After gained filtrate stratification, after respectively taking upper and lower level liquid to be diluted 250 times, using high-efficient liquid phase chromatogram technique analysis
Dilution is reacted, so that measuring 5-HMF yield is 47.25%.
Embodiment 6
The niobium modified Montmorillonites of the cellobiose of 50mg and 25mg are added to simultaneously and fill 5mL biphasic solvent
In heavy wall pressure bottle (15mL) reactor, biphasic solvent be saturated salt solution and methyl iso-butyl ketone (MIBK), volume ratio 1.5:3.5,
And heavy wall pressure bottle is placed in constant temperature oil bath and is reacted, reaction temperature is measured by being inserted into the thermocouple of oil bath pan.Instead
Magneton built in device is answered, stirring rate is maintained at 500rpm.By certain reaction time, reaction flask is transferred to ice-water bath at once
Middle quenching reaction.Transfer it in suction funnel and filtered, filter resulting solid catalyst it is washed, it is dry at
It weighs after reason, to ensure that reaction is recycled to react the reactant being consistent, catalyst ratio with original, it is anti-to continue on for next round
It answers.After gained filtrate stratification, after respectively taking upper and lower level liquid to be diluted 250 times, using high-efficient liquid phase chromatogram technique analysis
Dilution is reacted, to measure 5-HMF yield.After same operation circulation 5 times, gained 5-HMF yield is as shown in Figure 1.
Claims (7)
1. a kind of method for synthesizing 5 hydroxymethyl furfural, which comprises the following steps:
1) niobium modified Montmorillonites are prepared；
2) cellobiose, solvent pairs saturated salt solution and methyl iso-butyl ketone (MIBK), niobium modified Montmorillonites are added to pressure resistance
It in bottle reactor, and places it in constant temperature oil bath and is reacted, agitating device in reactor carries out at a certain temperature
Dehydration；
3) after reaction, be cooled to room temperature to gained mixture temperature, filtered in, after gained filtrate stratification,
Upper and lower level liquid is taken to carry out collecting 5 hydroxymethyl furfural respectively, 5 hydroxymethyl furfural is in solvent pairs；
4) continue on for next round reaction after filtering resulting solid catalyst.
2. a kind of method for synthesizing 5 hydroxymethyl furfural described in accordance with the claim 1, which is characterized in that described in step (1)
Niobium modified Montmorillonites are that columbium pentachloride ethanol solution is modified montmorillonite, by Na between cheating engaging layer+、Ca2+Ion
It is exchanged for Nb5+Ion.
3. a kind of method for synthesizing 5 hydroxymethyl furfural according to claim 2, which is characterized in that by columbium pentachloride and illiteracy
De- soil is dispersed in ethyl alcohol, is reacted at 20-60 DEG C；Columbium pentachloride, montmorillonite, ethyl alcohol dosage relation 2-7g:2g:100-
500ml。
4. a kind of method for synthesizing 5 hydroxymethyl furfural described in accordance with the claim 1, which is characterized in that step (2) is described double
Volume ratio is 1-3.5:1.5-4 between phase solvent saturated salt solution and methyl iso-butyl ketone (MIBK).
5. a kind of method for synthesizing 5 hydroxymethyl furfural described in accordance with the claim 1, which is characterized in that the reaction of step (2)
Temperature is 140-180 DEG C, preferably 160 DEG C.
6. a kind of method for synthesizing 5 hydroxymethyl furfural described in accordance with the claim 1, which is characterized in that the reaction of step (2)
Time is 1-8 hours, preferably 3 hours.
7. a kind of method for synthesizing 5 hydroxymethyl furfural described in accordance with the claim 1, which is characterized in that cellobiose, double molten
Agent, niobium modified Montmorillonites dosage relation 7-20mg:1-10ml:1-7mg.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845497A (en) * | 2021-11-01 | 2021-12-28 | 沈阳化工大学 | Method for synthesizing 5-hydroxymethylfurfural at low temperature |
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2018
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| CN102101851A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院大连化学物理研究所 | Method for catalytic preparation of 5-hydroxymethyl furfural from carbohydrates |
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| CN113845497A (en) * | 2021-11-01 | 2021-12-28 | 沈阳化工大学 | Method for synthesizing 5-hydroxymethylfurfural at low temperature |
| CN113845497B (en) * | 2021-11-01 | 2023-09-15 | 沈阳化工大学 | Method for synthesizing 5-hydroxymethylfurfural at low temperature |
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