CN102453007A - Method for preparing 5-hydroxymethylfurfural - Google Patents
Method for preparing 5-hydroxymethylfurfural Download PDFInfo
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- CN102453007A CN102453007A CN2010105157523A CN201010515752A CN102453007A CN 102453007 A CN102453007 A CN 102453007A CN 2010105157523 A CN2010105157523 A CN 2010105157523A CN 201010515752 A CN201010515752 A CN 201010515752A CN 102453007 A CN102453007 A CN 102453007A
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Abstract
The invention discloses a method for preparing 5-hydroxymethylfurfural, which comprises the following steps: 1) selecting raw materials: under the normal pressure, selecting carbohydrate as a raw material, selecting water or a mixture of water and an organic solvent as a solvent; 2) fully filling nitrogen protection gas in water or the mixture of water and an organic solvent, adding carbohydrate in water or the mixture of water and an organic solvent, then adding a catalyst and stirring for reaction for 0.5-12 hours at the temperature of 70 DEG C-280 EDG C, wherein the catalyst is solid superacid, cooling the reacted solution to room temperature after the reaction is finished, then adjusting the pH value of the reacted solution to alkalescent environment, then filtering the adjusted solution and carrying out pressure reduction and distillation to obtain 5-hydroxymethylfurfural. The invention has the advantages of small corrosivity during the preparation process and low production cost.
Description
Technical field
The present invention relates to a kind of method for preparing 5 hydroxymethyl furfural.
Background technology
5 hydroxymethyl furfural (HMF) be because of carrying out the synthetic useful compound of multiple reactions such as esterification, redox, polymerization, therefore is expected to become new " hardware and software platform compound " and receives much concern.Simultaneously since this be a kind of can be by the organic molecule of biomass material preparation, be proved and can be used under the condition of not transforming existing chemical industry equipment, part replaces crude oil as Organic Chemicals.At present; The 5 hydroxymethyl furfural production technique of report mainly is to use organic solvent completely; Under pressurized conditions, adopt liquid strong acid as catalyzer; This production technique mainly exists following problem: (1) can produce corrosive nature to equipment when suitability for industrialized production, and the organic solvent that (2) are a large amount of and the use of pressurized vessel make that preparation 5 hydroxymethyl furfural cost is too high.
Summary of the invention
The invention provides a kind of method for preparing 5 hydroxymethyl furfural, it not only in the process of preparation corrodibility little, and cost of manufacture is low.
The present invention has adopted following technical scheme: a kind of method for preparing 5 hydroxymethyl furfural, and it may further comprise the steps: step 1, select raw material for use: under normal pressure, the selection carbohydrate is a raw material, and water or water-organic solvent mixed system is as solvent; Step 2; In water or water-organic solvent mixed system, be full of nitrogen protection gas; Saccharide raw material is added in entry or the water-organic solvent mixed system; And then to add catalyzer be to carry out stirring reaction 0.5-12 hour under 70 ℃-280 ℃ the condition in temperature, and catalyzer is a solid super-strong acid, and question response is cooled to room temperature with reacted solution after finishing; Then the pH value of solution is to weakly alkaline environment behind the conditioned reaction, and the solution after will regulating obtains 5 hydroxymethyl furfural after filtering, reduce pressure, distilling then.
The weight of described carbohydrate is about 2.98-3.02g, and solvent is 8-10ml, and the weight of solid super-strong acid is 0.600g-0.605g.Described carbohydrate is the Mierocrystalline cellulose with hexose structure that glucose, fructose, sorbose, seminose or the method through cellulose hydrolysis obtain.
What the present invention was adopted when solvent is water is deionized water.Described water-organic solvent mixed system is the mixing solutions of water and organic solvent, and the organic solvent in water-organic solvent mixed system is ETHYLE ACETATE, methyl-sulphoxide, terepthaloyl moietie, acetonitrile, acetone, benzene, toluene, chloroform, sherwood oil or ether.Described water-organic solvent mixed system is the mixing solutions of water and organic solvent, and the organic solvent in water-organic solvent mixed system is two kinds of perhaps combinations of two or more materials in ETHYLE ACETATE, methyl-sulphoxide, terepthaloyl moietie, acetonitrile, acetone, benzene, toluene, chloroform, sherwood oil and the ether.
Described solid super-strong acid is SO42-/ZrO2 solid super-strong acid, SO42-/Fe2O3 solid super-strong acid or SO42-/Al2O3 solid super-strong acid.Described solid super-strong acid be after the combination of two kinds or two or more materials in SO42-/ZrO2 solid super-strong acid, SO42-/Fe2O3 solid super-strong acid and the SO42-/Al2O3 solid super-strong acid through coprecipitation method make mixed catalyst.
Temperature when carrying out stirring reaction in the step 2 of the present invention is 70 ℃-180 ℃; Optimal reaction temperature is 150 ℃; Time when carrying out stirring reaction in the step 2 is 0.5-3 hour; Optimum reacting time is 0.5 hour, and the reaction conditions when decompression, distillatory is: pressure is 5Pa-5Kpa, and temperature is 70 ℃-100 ℃.In solution, adding deionized water and ethanol in the step 2 of the present invention dilutes and regulates pH value to weakly alkaline environment.
The present invention has following beneficial effect: the present invention adopts suitable solvent, temperature of reaction, reaction times, uses mixed solvent can obtain the highest productive rate, and single organic solvent perhaps makes water also can obtain better products as solvent.Operable organic solvent is ETHYLE ACETATE, methyl-sulphoxide, terepthaloyl moietie, acetonitrile, acetone, benzene, toluene.The mixture of one or more in chloroform, sherwood oil or the ether.Consider cost and follow-up separation purification and liquid waste disposal, making water is to select preferably as solvent.Reduction when remedying water as solvent on the transformation efficiency can consider that the waste water of collecting after with underpressure distillation recycles.The control of temperature and time: temperature needs the long time could obtain satisfied yield when low; Temperature is too high then to be unfavorable for the selectivity of reacting; At 70 ℃-280 ℃, can speed of response and selectivity on obtain a rational balance between 0.5-12 hour through test.Through using solid super-strong acid to be catalyzer, strong acid is difficult to shortcomings such as maintenance to the loss and the pressure exerting device of the burn into catalyzer of industrial equipments in the time of can having avoided like this using, and it is high to have improved productive rate.Solvent of the present invention adopts water or water-organic solvent mixed system, can make reaction conditions gentle like this, and cost is low, pollutes little.The present invention obtains 5 hydroxymethyl furfural after adopting separation methods such as filtration, decompression, distillation, realizes with continuous or semicontinuous method when being beneficial to suitability for industrialized production like this, makes things convenient for the recovery of solvent simultaneously, has improved the solvent utilization ratio.The present invention adopts the carbohydrate with hexose structure that glucose, fructose, sorbose, seminose or the method through cellulose hydrolysis obtain as raw material, and wherein the transformation efficiency of fructose and productive rate are the highest.The present invention regulated pH to weakly alkaline environment before collecting product, can prevent when alkalescence is strong, can cause the generation of side reaction like this, and influencing productive rate makes troubles to separation simultaneously, thereby helps purified product.
Embodiment
The invention provides a kind of method for preparing 5 hydroxymethyl furfural; It may further comprise the steps: step 1; Select raw material for use: under normal pressure, the selection carbohydrate is a raw material, and carbohydrate is the Mierocrystalline cellulose with hexose structure that glucose, fructose, sorbose, seminose or the method through cellulose hydrolysis obtain; The weight of carbohydrate is 2.98-3.02g; Solvent is 8-10ml, and the weight of solid super-strong acid is 0.600g-0.605g, and water or water-organic solvent mixed system is as solvent; What when solvent is water, adopted is deionized water; Water-organic solvent mixed system is the mixing solutions of water and organic solvent, and the organic solvent in water-organic solvent mixed system is ETHYLE ACETATE, methyl-sulphoxide, terepthaloyl moietie, acetonitrile, acetone, benzene, toluene, chloroform, sherwood oil or ether, and the organic solvent in water-organic solvent mixed system also can be two kinds of perhaps combinations of two or more materials in ETHYLE ACETATE, methyl-sulphoxide, terepthaloyl moietie, acetonitrile, acetone, benzene, toluene, chloroform, sherwood oil and the ether; Step 2; In water or water-organic solvent mixed system, be full of nitrogen protection gas; Saccharide raw material is added in entry or the water-organic solvent mixed system; And then to add catalyzer be to carry out stirring reaction 0.5-3 hour under 70 ℃-180 ℃ the condition in temperature; Catalyzer is a solid super-strong acid, and solid super-strong acid is SO42-/ZrO2 solid super-strong acid, SO42-/Fe2O3 solid super-strong acid or SO42-/Al2O3 solid super-strong acid, solid super-strong acid also can be in SO42-/ZrO2 solid super-strong acid, SO42-/Fe2O3 solid super-strong acid and the SO42-/Al2O3 solid super-strong acid after the combination of two kinds or two or more materials through coprecipitation method make mixed catalyst; To react back solution after question response finishes and be cooled to room temperature; Then the pH value of solution is to weakly alkaline environment behind the conditioned reaction, and the method for adjusting is in solution, to add deionized water and ethanol to dilute and regulate pH value to weakly alkaline environment, and the solution after will regulating obtains 5 hydroxymethyl furfural after filtering, reduce pressure, distilling then; Reaction conditions when decompression, distillatory is: pressure is 5Pa-5Kpa, and temperature is 70 ℃-100 ℃.
The present invention further specifies the method for preparing 5 hydroxymethyl furfural through following examples:
Embodiment one; Raw materials of glucose 3.01g and catalyst S O42-/ZrO2 solid super-strong acid 0.601g joined among the solvent dimethyl sulfoxide solution 10ml that is full of nitrogen in being equipped with TM, churned mechanically there-necked flask, carried out stirring reaction 0.5 hour; When reaction, temperature is heated to 150 ℃; Question response is cooled to room temperature with reacted solution after finishing; Adding pH value that deionized water and ethanol dilutes solution behind the conditioned reaction then to weakly alkaline environment, is 5Pa at pressure at last, and temperature obtains 5 hydroxymethyl furfural after filtering, reduce pressure, distill under 70 ℃ the condition; To the 5 hydroxymethyl furfural 10ml that takes a sample, adopting the productive rate of high effective liquid chromatography for measuring 5 hydroxymethyl furfural is 47%.
Embodiment two; Raw materials of glucose 3.02g and catalyst S O42-/ZrO2 solid super-strong acid 0.600g joined among the solvent methyl-sulphoxide that is full of nitrogen and 1: 1 blended solution of the acetonitrile 10ml in being equipped with TM, churned mechanically there-necked flask, carried out stirring reaction 0.5 hour; When reaction, temperature is heated to 150 ℃; To react back solution after question response finishes and be cooled to room temperature; Adding pH value that deionized water and ethanol dilutes solution behind the conditioned reaction then to weakly alkaline environment, is 5Pa at pressure at last, and temperature obtains 5 hydroxymethyl furfural after filtering, reduce pressure, distill under 70 ℃ the condition; To the 5 hydroxymethyl furfural 10ml that takes a sample, adopting the productive rate of high effective liquid chromatography for measuring 5 hydroxymethyl furfural is 51%.
Embodiment three; Raw materials of glucose 3.00g and catalyst S O42-/ZrO2 solid super-strong acid 0.605g joined among the solvent deionized water 10ml that is full of nitrogen in being equipped with TM, churned mechanically there-necked flask, carried out stirring reaction 0.5 hour; When reaction, temperature is heated to 150 ℃; To react back solution after question response finishes and be cooled to room temperature; Adding pH value that deionized water and ethanol dilutes solution behind the conditioned reaction then to weakly alkaline environment, is 5Pa at pressure at last, and temperature obtains 5 hydroxymethyl furfural after filtering, reduce pressure, distill under 70 ℃ the condition; To the 5 hydroxymethyl furfural 10ml that takes a sample, adopting the productive rate of high effective liquid chromatography for measuring 5 hydroxymethyl furfural is 46%.
Embodiment four; The Mierocrystalline cellulose 3.00g of raw material hexose structure and catalyst S O42-/ZrO2 solid super-strong acid 0.601g joined among the solvent methyl-sulphoxide that is full of nitrogen and 1: 1 blended solution of the acetonitrile 10ml in being equipped with TM, churned mechanically there-necked flask, carried out stirring reaction 2 hours; When reaction, temperature is heated to 180 ℃; To react back solution after question response finishes and be cooled to room temperature; Adding pH value that deionized water and ethanol dilutes solution behind the conditioned reaction then to weakly alkaline environment, is 5Pa at pressure at last, and temperature obtains 5 hydroxymethyl furfural after filtering, reduce pressure, distill under 70 ℃ the condition; To the 5 hydroxymethyl furfural 10ml that takes a sample, adopting the productive rate of high effective liquid chromatography for measuring 5 hydroxymethyl furfural is 36%.
Embodiment five; The Mierocrystalline cellulose 2.99g of raw material hexose structure and catalyst S O42-/ZrO2 solid super-strong acid 0.603g joined among the solvent methyl-sulphoxide that is full of nitrogen and 1: 1 blended solution of the acetonitrile 10ml in being equipped with TM, churned mechanically there-necked flask, carried out stirring reaction 2 hours; When reaction, temperature is heated to 180 ℃; To react back solution after question response finishes and be cooled to room temperature; Adding pH value that deionized water and ethanol dilutes solution behind the conditioned reaction then to weakly alkaline environment, is 5Pa at pressure at last, and temperature obtains 5 hydroxymethyl furfural after filtering, reduce pressure, distill under 70 ℃ the condition; To the 5 hydroxymethyl furfural 10ml that takes a sample, adopting the productive rate of high effective liquid chromatography for measuring 5 hydroxymethyl furfural is 35%.
Embodiment six; Mierocrystalline cellulose 2.98g and catalyst S O42-/ZrO2 solid super-strong acid and the SO42-/Al2O3 solid super-strong acid that raw material is had a hexose structure joins among the solvent methyl-sulphoxide that is full of nitrogen and 1: 1 blended solution of the acetonitrile 10ml by the mixed catalyst 0.605g that makes through coprecipitation method at 1: 2 and in being equipped with TM, churned mechanically there-necked flask, carried out stirring reaction 2 hours; When reaction, temperature is heated to 180 ℃; To react back solution after question response finishes and be cooled to room temperature; Add pH value that deionized water and ethanol dilutes solution behind the conditioned reaction then to weakly alkaline environment; Be 5Pa at pressure at last; Temperature obtains 5 hydroxymethyl furfural after filtering, reduce pressure, distill under 70 ℃ the condition, to the 5 hydroxymethyl furfural 10ml that takes a sample, adopting the productive rate of high effective liquid chromatography for measuring 5 hydroxymethyl furfural is 44%.
Embodiment seven; Mierocrystalline cellulose 3.00g and catalyst S O42-/ZrO2 solid super-strong acid and the SO42-/Al2O3 solid super-strong acid that raw material is had a hexose structure joins among the solvent deionized water solution 10ml that is full of nitrogen by the mixed catalyst 0.601g that makes through coprecipitation method at 1: 2 and in being equipped with TM, churned mechanically there-necked flask, carried out stirring reaction 3 hours; When reaction, temperature is heated to 180 ℃; To react back solution after question response finishes and be cooled to room temperature; Adding pH value that deionized water and ethanol dilutes solution behind the conditioned reaction then to weakly alkaline environment, is 5Pa at pressure at last, and temperature obtains 5 hydroxymethyl furfural after filtering, reduce pressure, distill under 70 ℃ the condition; To the 5 hydroxymethyl furfural 10ml that takes a sample, adopting the productive rate of high effective liquid chromatography for measuring 5 hydroxymethyl furfural is 50%.
Claims (10)
1. method for preparing 5 hydroxymethyl furfural, it may further comprise the steps:
Step 1, select raw material for use: under normal pressure, the selection carbohydrate is a raw material, and water or water-organic solvent mixed system is as solvent;
Step 2; In water or water-organic solvent mixed system, be full of nitrogen protection gas; Saccharide raw material is added in entry or the water-organic solvent mixed system; And then to add catalyzer be to carry out stirring reaction 0.5-12 hour under 70 ℃-280 ℃ the condition in temperature, and catalyzer is a solid super-strong acid, and question response is cooled to room temperature with reacted solution after finishing; Then the pH value of solution is to weakly alkaline environment behind the conditioned reaction, and the solution after will regulating obtains 5 hydroxymethyl furfural after filtering, reduce pressure, distilling then.
2. the method for preparing 5 hydroxymethyl furfural according to claim 1, the weight that it is characterized in that described carbohydrate is about 2.98-3.02g, and solvent is 8-10ml, and the weight of solid super-strong acid is 0.600g-0.605g.
3. the method for preparing 5 hydroxymethyl furfural according to claim 1 is characterized in that described carbohydrate is the Mierocrystalline cellulose with hexose structure that glucose, fructose, sorbose, seminose or the method through cellulose hydrolysis obtain.
4. the method for preparing 5 hydroxymethyl furfural according to claim 1, what it is characterized in that when solvent is water, being adopted is deionized water.
5. the method for preparing 5 hydroxymethyl furfural according to claim 1; It is characterized in that described water-organic solvent mixed system is the mixing solutions of water and organic solvent, the organic solvent in water-organic solvent mixed system is ETHYLE ACETATE, methyl-sulphoxide, terepthaloyl moietie, acetonitrile, acetone, benzene, toluene, chloroform, sherwood oil or ether.
6. the method for preparing 5 hydroxymethyl furfural according to claim 1; It is characterized in that described water-organic solvent mixed system is the mixing solutions of water and organic solvent, the organic solvent in water-organic solvent mixed system is two kinds of perhaps combinations of two or more materials in ETHYLE ACETATE, methyl-sulphoxide, terepthaloyl moietie, acetonitrile, acetone, benzene, toluene, chloroform, sherwood oil and the ether.
7. the method for preparing 5 hydroxymethyl furfural according to claim 1 is characterized in that described solid super-strong acid is SO42-/ZrO2 solid super-strong acid, SO42-/Fe2O3 solid super-strong acid or SO42-/Al2O3 solid super-strong acid.
8. the method for preparing 5 hydroxymethyl furfural according to claim 1, it is characterized in that described solid super-strong acid be after the combination of two kinds or two or more materials in SO42-/ZrO2 solid super-strong acid, SO42-/Fe2O3 solid super-strong acid and the SO42-/Al2O3 solid super-strong acid through coprecipitation method make mixed catalyst.
9. the method for preparing 5 hydroxymethyl furfural according to claim 1; Temperature when it is characterized in that carrying out stirring reaction in the step 2 is 70 ℃-180 ℃; Optimal reaction temperature is 150 ℃, and the time when carrying out stirring reaction in the step 2 is 0.5-3 hour, and optimum reacting time is 0.5 hour; Reaction conditions when decompression, distillatory is: pressure is 5Pa-5Kpa, and temperature is 70 ℃-100 ℃.
10. the method for preparing 5 hydroxymethyl furfural according to claim 1 is characterized in that in the step 2 in solution, adding deionized water and ethanol and dilutes and regulate pH value to weakly alkaline environment.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105007913A (en) * | 2013-03-14 | 2015-10-28 | 阿彻丹尼尔斯米德兰德公司 | Process for making HMF from sugars with reduced byproduct formation, and improved stability HMF compositions |
| CN105251514A (en) * | 2015-09-07 | 2016-01-20 | 江苏大学 | Carbon-containing hierarchical pore Brnsted acid/Lewis acid dual-functional catalyst, preparation method and applications |
| CN105594745A (en) * | 2016-02-03 | 2016-05-25 | 广西大学 | Ustilaginoidea virens inhibitor prepared from sorbose |
| CN108484545A (en) * | 2018-04-24 | 2018-09-04 | 浙江大学 | A kind of method and system of continuous synthesis furandicarboxylic acid |
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| CN101613331A (en) * | 2009-07-23 | 2009-12-30 | 四川大学 | A kind of method for preparing 5-acetyl-o-methyl furfural by carbohydrate |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105007913A (en) * | 2013-03-14 | 2015-10-28 | 阿彻丹尼尔斯米德兰德公司 | Process for making HMF from sugars with reduced byproduct formation, and improved stability HMF compositions |
| KR20150132299A (en) * | 2013-03-14 | 2015-11-25 | 아처 다니엘 미드랜드 캄파니 | Process for making hmf from sugars with reduced byproduct formation, and improved stability hmf compositions |
| JP2016517407A (en) * | 2013-03-14 | 2016-06-16 | アーチャー−ダニエルズ−ミッドランド カンパニー | Process for making HMF from sugars with reduced by-product formation and HMF composition with improved stability |
| EP2968255A4 (en) * | 2013-03-14 | 2016-07-27 | Archer Daniels Midland Co | Process for making hmf from sugars with reduced byproduct formation, and improved stability hmf compositions |
| CN105007913B (en) * | 2013-03-14 | 2017-09-29 | 阿彻丹尼尔斯米德兰德公司 | HMF method is manufactured from sugar with the accessory substance formation of reduction and the HMF compositions of stability are improved |
| KR102001716B1 (en) | 2013-03-14 | 2019-07-18 | 아처 다니엘 미드랜드 캄파니 | Process for making hmf from sugars with reduced byproduct formation, and improved stability hmf compositions |
| CN105251514A (en) * | 2015-09-07 | 2016-01-20 | 江苏大学 | Carbon-containing hierarchical pore Brnsted acid/Lewis acid dual-functional catalyst, preparation method and applications |
| CN105251514B (en) * | 2015-09-07 | 2017-10-20 | 江苏大学 | Carbon containing multi-stage porous, bronsted acid/lewis acid difunctionalization catalyst and preparation method thereof and purposes |
| CN105594745A (en) * | 2016-02-03 | 2016-05-25 | 广西大学 | Ustilaginoidea virens inhibitor prepared from sorbose |
| CN108484545A (en) * | 2018-04-24 | 2018-09-04 | 浙江大学 | A kind of method and system of continuous synthesis furandicarboxylic acid |
| CN108484545B (en) * | 2018-04-24 | 2021-01-12 | 浙江大学 | Method and system for continuously synthesizing furan dicarboxylic acid |
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Application publication date: 20120516 |