CN102964319A - Preparation method of 5-hydroxymethylfurfural - Google Patents
Preparation method of 5-hydroxymethylfurfural Download PDFInfo
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Abstract
The invention relates to the technical field of hydroxymethylfurfural preparation, particularly a preparation method of 5-hydroxymethylfurfural, which comprises the following steps: dissolving a saccharide raw material in a dimethylsulfoxide solvent, heating to 80-160 DEG C, adding chromium chloride to react, and detecting the reaction yield of the 5-hydroxymethylfurfural; and when the yield is greater than 90%, quenching the reaction, carrying out vacuum distillation to remove the solvent, diluting the residual liquid with a saturated sodium chloride water solution to obtain a solution to be extracted, extracting with an organic solvent, and drying by distillation to obtain the 5-hydroxymethylfurfural. The mass ratio of the saccharide raw material to the dimethylsulfoxide is 1:(1.5-20), and the addition amount of chromium chloride is 5-20 wt% of the saccharide raw material. The synthetic route is easy and simple to operate, and does not need any inert gas protective atmosphere; the total mass yield is up to higher than 90%, and the purity is up to higher than 96%; and the invention is suitable for industrial production, and enhances the solid content of the reaction to 33%, thereby greatly enhancing the reaction efficiency.
Description
Technical field
The present invention relates to the hydroxymethylfurfural preparing technical field, particularly a kind of preparation method of 5 hydroxymethyl furfural.
Background technology
Along with the day by day minimizing of petrochemical industry resource reserve, the price of petrochemical industry derived product raises increasingly, and the substitute of seeking Sustainable development becomes more and more important.In recent years, biomass receive increasing concern as the renewable resources that is expected to substitute in future fossil energy.Wherein, synthetic furans product is one of significant process of Wood Adhesives from Biomass utilization take glucose, fructose and sucrose as raw material.Studies show that fructose is through catalytic and dehydration reaction, losing the 5 hydroxymethyl furfural that generates behind the trihyarol is the Important Platform chemical that connects Wood Adhesives from Biomass and heavy industrialization process.It can pass through hydrogenation, oxydehydrogenation, esterification, halogenation, polymerization, hydrolysis and other chemical reactions, for the synthesis of many high value added products and novel high polymer material, comprises medicine, resene plastics, diesel oil fuel additive etc.In addition, consider from green chemistry angle, use glucose, fructose or sucrose to have economic worth height, environmentally friendly and advantage that sustainability is strong as raw material.Therefore, the research of the synthetic 5 hydroxymethyl furfural of catalysis glucose, fructose or sucrose has important scientific meaning and using value, has become one of study hotspot of chemical field.
Producing the 5 hydroxymethyl furfural field by carbohydrate; reaction medium is generally selected expensive ionic liquid or ammonium salt, glycerine, ethylene glycol, oxalic acid, propanedioic acid; catalyzer is generally selected mineral acid, organic acid, Lewis acid, solid acid, acidic oxide, acid anhydrides, metal chloride; during reaction; need protection of inert gas; guarantee reaction fully carry out purity with reaction product, organic solvent extraction or supercritical CO are generally adopted in the aftertreatment of reaction solution
2Extraction, production cost is higher, and operating procedure is complicated, is difficult to realize industrialization.And for fully carrying out of guaranteeing to react, consolidating of carbohydrate contains lowlyer in the reaction solution of setting, in industrialization, causes production capacity low in the prior art, and production cost is higher.
Summary of the invention
In order to solve the reaction process that exists in the preparation of above prior art 5 hydroxymethyl furfural and the aftertreatment cost is high, reaction is liquid-solid contains the problem that the low industrialization cost that causes is high, yield is low, the invention provides a kind of cost low, be suitable for the liquid-solid preparation method who contains height, 5 hydroxymethyl furfural that yield is high of industrialization, reaction.
The present invention is achieved by the following measures:
A kind of preparation method of 5 hydroxymethyl furfural, saccharide raw material is dissolved in the dimethyl sulfoxide solvent, be warming up to 80 ~ 160 ℃, adding chromium chloride reacts, detect the reaction yield of 5 hydroxymethyl furfural, when yield cancellation reaction greater than 90% time, underpressure distillation desolventizing, remaining liq dilutes to such an extent that treat extraction liquid with saturated sodium-chloride water solution, with evaporate to dryness behind the organic solvent extraction and get final product;
The mass ratio of saccharide raw material and dimethyl sulfoxide (DMSO) 1: 1.5 ~ 20;
The chromium chloride add-on is 5 ~ 20% of saccharide raw material quality.
Described preparation method, the mass ratio of saccharide raw material and dimethyl sulfoxide (DMSO) 1: 2;
The chromium chloride add-on is 15.04% of saccharide raw material quality, and temperature of reaction is 120 ℃.
Described preparation method, the mass ratio of saccharide raw material and dimethyl sulfoxide (DMSO) 1: 20;
The chromium chloride add-on is 15 % of saccharide raw material quality, and temperature of reaction is 120 ℃.
Described preparation method, described saccharide raw material is glucose, fructose or sucrose.
Described preparation method, the remaining liq after the underpressure distillation dilutes with 0.5 ~ 10 times saturated sodium-chloride water solution.
Described preparation method, the remaining liq after the underpressure distillation dilutes with 2 ~ 4 times saturated sodium-chloride water solution.
Described preparation method, the organic solvent that uses during extraction is acetone, ethyl acetate, butylacetate, ether, trieline, trichloromethane, toluene.
Described preparation method treats extraction liquid and the volume ratio 1:0.5 – 5 of extraction with organic solvent during extraction, this is that the ratio of often selecting in the extraction process does not have special regulation at this.
Described preparation method is characterized in that extracting 3 ~ 8 times.
Described preparation method is characterized in that extracting 4-6 time.
The present invention is take glucose, fructose and sucrose as raw material, in the dimethyl sulfoxide (DMSO) of chloride containing chromium, intramolecular dehydration occurs and generate, reaction mixture is first through the underpressure distillation desolventizing, the solvent recuperation recycling, remaining mixture dilutes with saturated sodium-chloride water solution, the 5 hydroxymethyl furfural that generates with the organic solvent extraction reaction again, evaporate to dryness, crystallization namely get product.The present invention is the high efficiency 5 hydroxymethyl furfural that synthesized take conventional solvent dimethyl sulfoxide (DMSO) as solvent, under the condition without other additives.The present invention will react solid content and bring up to 33%, in the situation of high conversion, greatly increase benefit simultaneously.The present invention does not need supercritical CO
2Extraction extracts with inexpensive saturated nacl aqueous solution and organic solvent, and percentage extraction is high, and cost is low.
Beneficial effect of the present invention:
(1) synthetic route is succinct, and is simple to operate, do not need protection of inert gas;
(2) cost is low, only uses " menstruum universale " methyl-sulphoxide, and can reach 90% above recycling, gives up expensive ionic liquid, and product does not need supercritical CO
2Extraction extracts with inexpensive saturated nacl aqueous solution and organic solvent;
(3) the total mass yield reaches more than 90%, and purity reaches more than 96%, is fit to suitability for industrialized production, will react solid content and bring up to 33%, has greatly increased reaction efficiency.
Embodiment
For a better understanding of the present invention, further specify below in conjunction with specific embodiment.If no special instructions, following percentage ratio is mass percent.
Embodiment 1:
To with throwing solvent DMSO(dimethyl sulfoxide (DMSO) in magnetic agitation and the water-bath condensation 100 mL single necked round bottom flask) 25g, add D-Fructose 12.50g(33.33% under the agitation condition), be heated to 120 ℃, add catalyzer chromium chloride 1.88g(15.04%), isothermal reaction, detect the reaction yield of 5 hydroxymethyl furfural with spectrophotometer, when yield places cold water cancellation reaction with reaction flask greater than 90% the time.
Reaction system is being lower than under the vacuum condition of 100Pa, 70 ℃ are carried out pressure distillation, behind the DMSO that deviates from the overwhelming majority, reaction system taken out and be cooled to room temperature must treat extraction liquid, add 20g saturated aqueous common salt (being about 2 times that treat extraction liquid), remaining DMSO and catalyzer etc. are dissolved in the water; Then carry out 5 extractions with the 20mL ethyl acetate, merge organic phase, spend the night with the 50g anhydrous sodium sulfate drying, ethyl acetate is removed in decompression, gets the brown thick liquid.
Reclaim the about 22g of DMSO, the rate of recovery about 90%.After testing, reaction product purity is more than 96%, and the extraction yield of product is about 90.8%, and reaction yield is about 91.5%.
Transferred product to brown bottle, and is deposited in the refrigerator below 5 ℃.
Embodiment 2:
To with throwing solvent DMSO 450g in magnetic agitation and the water-bath condensation 1000 mL single necked round bottom flask, add sugared 225 g(33.3% under the agitation condition), be heated to 160 ℃, add catalyzer 11.25g(5%), isothermal reaction, detect the reaction yield of 5 hydroxymethyl furfural with spectrophotometer, when yield places cold water cancellation reaction with reaction flask greater than 90% the time.
With reaction system under the vacuum condition that is lower than 100 Pa, 70 ℃ are carried out pressure distillation, behind the DMSO that deviates from the overwhelming majority, reaction system taken out and be cooled to room temperature must treat extraction liquid, add 1500g saturated aqueous common salt (being about 10 times that treat extraction liquid), remaining DMSO and catalyzer etc. are dissolved in the water; Then carry out 3 extractions with the 400mL ethyl acetate, merge organic phase, spend the night with the 500g anhydrous sodium sulfate drying, ethyl acetate is removed in decompression, gets the brown thick liquid, and purity is more than 90%.Reclaim DMSO392g, the rate of recovery about 87%, the extraction yield of product: about 89.4%, reaction yield: about 60.5%.
Transferred product to brown bottle, and is deposited in the refrigerator below 5 ℃, stand-by.
Embodiment 3:
To with throwing solvent DMSO(dimethyl sulfoxide (DMSO) in magnetic agitation and the water-bath condensation 100 mL single necked round bottom flask) 50g, add D-Fructose 25g(33.3% under the agitation condition), be heated to 80 ℃, add catalyzer chromium chloride 2.5g(10%), isothermal reaction, detect the reaction yield of 5 hydroxymethyl furfural with spectrophotometer, when yield places cold water cancellation reaction with reaction flask greater than 90% the time.
Reaction system is being lower than under the vacuum condition of 100Pa, 70 ℃ are carried out pressure distillation, behind the DMSO that deviates from the overwhelming majority, reaction system taken out and be cooled to room temperature must treat extraction liquid, add 60g saturated aqueous common salt (being about 3 times that treat extraction liquid), remaining DMSO and catalyzer etc. are dissolved in the water; Then carry out 4 extractions with the 40mL ether, merge organic phase, spend the night with the 100g anhydrous sodium sulfate drying, ethyl acetate is removed in decompression, gets the brown thick liquid.
Reclaim the about 45g of DMSO, the rate of recovery about 90%.After testing, reaction product purity is more than 96%, and the extraction yield of product is about 90.6%, and reaction yield is about 71%.
Transferred product to brown bottle, and is deposited in the refrigerator below 5 ℃.
Embodiment 4:
To with throwing solvent DMSO(dimethyl sulfoxide (DMSO) in magnetic agitation and the water-bath condensation 100 mL single necked round bottom flask) 50g, add D-Fructose 25g(33.3% under the agitation condition), be heated to 140 ℃, add catalyzer chromium chloride 5g(20%), isothermal reaction, detect the reaction yield of 5 hydroxymethyl furfural with spectrophotometer, when yield places cold water cancellation reaction with reaction flask greater than 90% the time.
Reaction system is being lower than under the vacuum condition of 100Pa, 70 ℃ are carried out pressure distillation, behind the DMSO that deviates from the overwhelming majority, reaction system taken out and be cooled to room temperature get, add 10g saturated aqueous common salt (being about 0.5 times that treats extraction liquid), remaining DMSO and catalyzer etc. are dissolved in the water; Then carry out 6 extractions with the 40mL butylacetate, merge organic phase, spend the night with the 100g anhydrous sodium sulfate drying, butylacetate is removed in decompression, gets the brown thick liquid.
Reclaim the about 45g of DMSO, the rate of recovery about 90%.After testing, reaction product purity is more than 96%, and the extraction yield of product is about 89.8%, and reaction yield is about 87.4%.
Transferred product to brown bottle, and is deposited in the refrigerator below 5 ℃.
Embodiment 5:
To with throwing solvent DMSO(dimethyl sulfoxide (DMSO) in magnetic agitation and the water-bath condensation 100 mL single necked round bottom flask) 50g, add D-Fructose 33.33g(40% under the agitation condition), be heated to 120 ℃, add catalyzer chromium chloride 5.01g(15.04%), isothermal reaction, detect the reaction yield of 5 hydroxymethyl furfural with spectrophotometer, when yield places cold water cancellation reaction with reaction flask greater than 90% the time.
Reaction system is being lower than under the vacuum condition of 100Pa, 70 ℃ are carried out pressure distillation, behind the DMSO that deviates from the overwhelming majority, reaction system taken out and be cooled to room temperature get, add 100g saturated aqueous common salt (being about 4 times that treat extraction liquid), remaining DMSO and catalyzer etc. are dissolved in the water; Then carry out 7 extractions with 40mL toluene, merge organic phase, spend the night with the 100g anhydrous sodium sulfate drying, toluene is removed in decompression, gets the brown thick liquid.
Reclaim the about 45g of DMSO, the rate of recovery about 90%.After testing, reaction product purity is more than 96%, and the extraction yield of product is about 89.8%, and reaction yield is about 76%.
Transferred product to brown bottle, and is deposited in the refrigerator below 5 ℃.
Embodiment 6:
To with throwing solvent DMSO(dimethyl sulfoxide (DMSO) in magnetic agitation and the water-bath condensation 100 mL single necked round bottom flask) 50g, add D-Fructose 2.5g(4.76% under the agitation condition), be heated to 120 ℃, add catalyzer chromium chloride 0.375g(15%), isothermal reaction, detect the reaction yield of 5 hydroxymethyl furfural with spectrophotometer, when yield places cold water cancellation reaction with reaction flask greater than 90% the time.
Reaction system is being lower than under the vacuum condition of 100Pa, 70 ℃ are carried out pressure distillation, behind the DMSO that deviates from the overwhelming majority, reaction system taken out and be cooled to room temperature get, add 5g saturated aqueous common salt (being about 2 times that treat extraction liquid), remaining DMSO and catalyzer etc. are dissolved in the water; Then carry out 8 extractions with the 40mL chloroform, merge organic phase, spend the night with the 100g anhydrous sodium sulfate drying, chloroform is removed in decompression, gets the brown thick liquid.
Reclaim the about 45g of DMSO, the rate of recovery about 90%.After testing, reaction product purity is more than 94%, and the extraction yield of product is about 89.8%, and reaction yield is about 90%.
Transferred product to brown bottle, and is deposited in the refrigerator below 5 ℃.
Embodiment 7:
To with throwing solvent DMSO(dimethyl sulfoxide (DMSO) in magnetic agitation and the water-bath condensation 100 mL single necked round bottom flask) 50g, add D-Fructose 5g(9.1% under the agitation condition), be heated to 120 ℃, add catalyzer chromium chloride 0.75g(15%), isothermal reaction, detect the reaction yield of 5 hydroxymethyl furfural with spectrophotometer, when yield places cold water cancellation reaction with reaction flask greater than 90% the time.
Reaction system is being lower than under the vacuum condition of 100Pa, 70 ℃ are carried out pressure distillation, behind the DMSO that deviates from the overwhelming majority, reaction system taken out and be cooled to room temperature get, add 20g saturated aqueous common salt (being about 4 times that treat extraction liquid), remaining DMSO and catalyzer etc. are dissolved in the water; Then carry out 5 extractions with the 40mL ethyl acetate, merge organic phase, spend the night with the 100g anhydrous sodium sulfate drying, ethyl acetate is removed in decompression, gets the brown thick liquid.
Reclaim the about 45g of DMSO, the rate of recovery about 90%.After testing, reaction product purity is more than 95%, and the extraction yield of product is about 89.8%, and reaction yield is about 89%.
Transferred product to brown bottle, and is deposited in the refrigerator below 5 ℃.
Claims (10)
1. the preparation method of a 5 hydroxymethyl furfural, it is characterized in that saccharide raw material is dissolved in the dimethyl sulfoxide solvent, be warming up to 80 ~ 160 ℃, adding chromium chloride reacts, detect the reaction yield of 5 hydroxymethyl furfural, when yield cancellation reaction greater than 90% time, underpressure distillation desolventizing, remaining liq dilutes to such an extent that treat extraction liquid with saturated sodium-chloride water solution, with evaporate to dryness behind the organic solvent extraction and get final product;
The mass ratio of saccharide raw material and dimethyl sulfoxide (DMSO) 1: 1.5 ~ 20;
The chromium chloride add-on is 5 ~ 20% of saccharide raw material quality.
2. preparation method according to claim 1 is characterized in that the mass ratio 1: 2 of saccharide raw material and dimethyl sulfoxide (DMSO);
The chromium chloride add-on is 15.04% of saccharide raw material quality, and temperature of reaction is 120 ℃.
3. preparation method according to claim 1 is characterized in that the mass ratio 1: 20 of saccharide raw material and dimethyl sulfoxide (DMSO);
The chromium chloride add-on is 15% of saccharide raw material quality, and temperature of reaction is 120 ℃.
4. each described preparation method according to claim 1-3 is characterized in that described saccharide raw material is glucose, fructose or sucrose.
5. each described preparation method according to claim 1-4 is characterized in that remaining liq after the underpressure distillation is with 0.5 ~ 10 times saturated sodium-chloride water solution dilution.
6. each described preparation method according to claim 1-4 is characterized in that remaining liq after the underpressure distillation is with 2 ~ 4 times saturated sodium-chloride water solution dilution.
7. preparation method according to claim 5, the organic solvent that uses when it is characterized in that extracting is acetone, ethyl acetate, butylacetate, ether, trieline, trichloromethane or toluene.
8. according to claim 1 or 7 described preparation methods, it is characterized in that treating that extraction liquid and extraction are with the volume ratio 1:0.5 of organic solvent ~ 5.
9. according to claim 1 or 7 described preparation methods, it is characterized in that extracting 3 ~ 8 times.
10. according to claim 1 or 7 described preparation methods, it is characterized in that extracting 4-6 time.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104628684A (en) * | 2013-11-11 | 2015-05-20 | 中国科学院大连化学物理研究所 | Method for extracting 5-hydroxymethylfurfural from ionic liquid |
| CN105153079A (en) * | 2015-06-30 | 2015-12-16 | 江苏大学 | Method for preparing glucose-based 5-hydroxymethylfurfural from dimethyl sulphoxide and trichlorate |
| CN105330623A (en) * | 2015-11-12 | 2016-02-17 | 中国石油化工股份有限公司 | Inorganic salt catalytic synthesis method for 5-hydroxy methyl furfural |
| CN115872955A (en) * | 2022-11-30 | 2023-03-31 | 常州兰陵制药有限公司 | Synthesis method of ranitidine intermediate |
| CN116082278A (en) * | 2021-11-05 | 2023-05-09 | 中国科学院宁波材料技术与工程研究所 | Method for improving selectivity of preparation of 5-hydroxymethyl-2-furaldehyde |
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2012
- 2012-11-05 CN CN201210434718.2A patent/CN102964319B/en active Active
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628684A (en) * | 2013-11-11 | 2015-05-20 | 中国科学院大连化学物理研究所 | Method for extracting 5-hydroxymethylfurfural from ionic liquid |
| CN104628684B (en) * | 2013-11-11 | 2017-09-08 | 中国科学院大连化学物理研究所 | A kind of method that 5 hydroxymethylfurfurals are extracted from ionic liquid |
| CN105153079A (en) * | 2015-06-30 | 2015-12-16 | 江苏大学 | Method for preparing glucose-based 5-hydroxymethylfurfural from dimethyl sulphoxide and trichlorate |
| CN105330623A (en) * | 2015-11-12 | 2016-02-17 | 中国石油化工股份有限公司 | Inorganic salt catalytic synthesis method for 5-hydroxy methyl furfural |
| CN116082278A (en) * | 2021-11-05 | 2023-05-09 | 中国科学院宁波材料技术与工程研究所 | Method for improving selectivity of preparation of 5-hydroxymethyl-2-furaldehyde |
| CN115872955A (en) * | 2022-11-30 | 2023-03-31 | 常州兰陵制药有限公司 | Synthesis method of ranitidine intermediate |
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| CN102964319B (en) | 2015-04-22 |
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