CN102153527A - Method for preparing 5-hydroxymethylfurfural with fructose - Google Patents
Method for preparing 5-hydroxymethylfurfural with fructose Download PDFInfo
- Publication number
- CN102153527A CN102153527A CN2011100478058A CN201110047805A CN102153527A CN 102153527 A CN102153527 A CN 102153527A CN 2011100478058 A CN2011100478058 A CN 2011100478058A CN 201110047805 A CN201110047805 A CN 201110047805A CN 102153527 A CN102153527 A CN 102153527A
- Authority
- CN
- China
- Prior art keywords
- fructose
- hydroxymethyl furfural
- prepare
- catalyzer
- quality
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Furan Compounds (AREA)
Abstract
The invention discloses a method for preparing 5-hydroxymethylfurfural with fructose. The method includes the following steps: taking N, N-dimethyl acetamide as solvent, lithium chloride as additive, fructose as a reaction material, and heteropoly acid loaded by titanium dioxide as a catalyst, reacting at the temperature of 80-150DEG C to generate 5-hydroxymethylfurfural. The method has the characteristics of few by-products, high yield, environment-friendly property, moderate reaction conditions, small corrosion to equipment, recyclability of catalyst, and the like, and has industrial prospect.
Description
Technical field
The present invention relates to the green synthetic compound field that transforms of biomass, be specifically related to a kind of method for preparing 5 hydroxymethyl furfural by fructose.
Background technology
The required energy and the Organic Chemicals overwhelming majority in the world derives from oil, coal and Sweet natural gas at present.These fossil class resources have been made huge contribution for the development and the prosperity of economy of society.But along with non-renewable fossil energy peter out and in order to realize the purpose of human kind sustainable development, make full use of renewable, degradable resource, it is the effective means that solves resource exhaustion and environmental pollution that the method by chemosynthesis makes it become important industrial raw material.The biomass resource reserves are big, renewable, cost is low, and the method by chemosynthesis can prepare the medicine industry intermediate of high added value and the monomer of synthesized polymer material, therefore paid attention to by people gradually.
In recent years, a kind of product 5 hydroxymethyl furfural (5-HMF) of hexose dehydration is considered to produce from biomass the key substance of fuel and industrial chemicals, it can be converted into acids, the aldehydes of various economically valuables, but and a kind of transport fuel 2 that has some commercial potential, 5-dimethyl furan (DMF).Therefore how the synthetic efficiently 5 hydroxymethyl furfural of low value becomes the focus that people study.
Prepare the more existing bibliographical informations of 5 hydroxymethyl furfural by hexose: application number is to disclose a kind of isomerase/dilute hydrochloric acid coupling and catalyzing glucose in the Chinese patent application of CN200910228921.2 to prepare the preparation method of 5 hydroxymethyl furfural, steps of the method are: at first adding Sodium Tetraborate and fixed glucose isomerase react in glucose solution, refilter, isomerase is reclaimed, obtain the mixed solution of glucose and fructose, in mixed solution, add hydrochloric acid, sodium-chlor and propyl carbinol and carry out the synthetic 5 hydroxymethyl furfural of acid catalysis; The shortcoming of this method: the price of isomerase is comparatively expensive, and in reaction process, temperature is wayward, and the active of enzyme lost efficacy easily.Application number is to disclose a kind of method for preparing 5 hydroxymethyl furfural in the Chinese patent application of CN 200810011726.X, and this patent is a reaction solvent with saturated sodium-chloride-propyl carbinol system, and phospho-wolframic acid is a catalyzer, and fructose is converted into 5 hydroxymethyl furfural; The shortcoming of this method: phosphate-tungstic acid is difficult for reclaiming, and product yield is not very high.Application number is to disclose a kind of method for preparing 5 hydroxymethyl furfural in the Chinese patent application of CN200710158825.6, this method is a reaction solvent with ionic liquid 1-methyl-3-alkyl imidazole bromine etc., with acidic ion liquid (imidazole bisulfate, 1-methyl-3-butyl imidazole hydrosulfate), mineral acid (hydrochloric acid, nitric acid, phosphoric acid) and organic acid (formic acid, acetate, citric acid) is catalyzer, and 5 hydroxymethyl furfural is produced in the dehydration of catalysis hexose; The shortcoming of this method: ion liquid viscosity is big, price is comparatively expensive, and mineral acid acidity such as hydrochloric acid, sulfuric acid are bigger, and is comparatively serious to equipment corrosion, is difficult for suitability for industrialized production.
Application number is to disclose the method that a kind of microwave promotes to prepare 5 hydroxymethyl furfural in the Chinese patent application of CN 200710158826.0, with ionic liquid 1-ethyl-3-Methylimidazole bromine etc. is solvent, under the condition of microwave power 200～2000W, 50～100 ℃ of temperature of reaction, reaction times 0.5～30min, 5 hydroxymethyl furfural is produced in the dehydration of biomass monose; The shortcoming of this method: (1) with the type of heating of microwave, can only small batch production, can not realize scale operation; (2) ion liquid viscosity is big, price is comparatively expensive, can only be confined to laboratory study as solvent.
Summary of the invention
What the invention provides a kind of yield height, energy-saving and environmental protection and have an industrial prospect prepares the method for 5 hydroxymethyl furfural by fructose.
A kind ofly prepare the method for 5 hydroxymethyl furfural, may further comprise the steps by fructose:
With N,N-dimethylacetamide (DMA) is solvent, and lithium chloride is an additive, and fructose is reaction raw materials, and the heteropolyacid of titanium dichloride load is a catalyzer, generates 5 hydroxymethyl furfural 80 ℃～150 ℃ reactions.
In order to reach better invention effect, preferably:
The quality of described lithium chloride is 5%～25% of a solvent quality, more preferably 15%～25%.
The quality of described fructose is 5%～35% of a solvent quality, more preferably 5%～25%.
The quality of described catalyzer is 2%～15% of a solvent quality.
The mass ratio of titanium dioxide and heteropolyacid is 1: 1～6 in the described catalyzer, more preferably 1: 2.
Described heteropolyacid (being called for short HPA) mainly can be selected phospho-molybdic acid (H for use
3PMo
12O
40/ TiO
2), phospho-wolframic acid (H
3PW
12O
40/ TiO
2), silicotungstic acid (H
4SiW
12O
40/ TiO
2), silicomolybdic acid (H
4SiMo
12O
40/ TiO
2) in one or more.
Described Preparation of catalysts method can adopt the preparation method of existing loaded catalyst, is generally: with TiO
2Active carrier joins in the heteropolyacid aqueous solution and floods 12h～48h, takes out at 60 ℃～100 ℃ down after the oven dry, activates 2h～5h in temperature is 100 ℃～600 ℃ retort furnace, makes catalyzer; TiO wherein
2The mass ratio of active carrier and heteropolyacid is 1: 1～6.The HPA/TiO that concentration and dipping time by control heteropolyacid solution can make the different loads amount
2Catalyzer, but drop into TiO in the catalyzer that makes under the certain situation of ratio at raw material
2The mass ratio of active carrier and heteropolyacid and raw material drop into the ratio basically identical.
Described TiO
2The preparation method of active carrier can adopt existing TiO
2The preparation method of active carrier is generally: with 1 weight part butyl (tetra) titanate (Ti (OC
4H
9)) be dissolved in 2～6 weight part dehydrated alcohols, in 0.5h～1h, add 3～8 weight parts waters and make the butyl (tetra) titanate hydrolysis, obtain stable TiO
2Gel.Then with TiO
2Gel is put into inherent 500 ℃～800 ℃ insulations (calcination) 8h～10h of retort furnace behind 60 ℃～100 ℃ dry 2h～5h, naturally cool to room temperature after the taking-up, promptly gets TiO after the grinding
2Active carrier.
Described reaction is the fructose dehydration reaction, and the deionized water of available 10mL～50mL stops reaction.
In order to improve the yield of product, described temperature of reaction is preferably 120 ℃～140 ℃.
The qualification that the described reaction times is not strict can be passed through timing sampling, and (TLC) carries out trace analysis with tlc, finishes when raw material fructose reacts, and the terminal point that is considered as reacting gets final product.Through overtesting, to carry out fully in order to make reaction, the described reaction times is generally 10min～300min, more preferably 60min～90min.
Detection method for product yield among the present invention is:
At first dispose the standard model solution of a series of 5 hydroxymethyl furfural standard substance, make absorbancy-concentration standard curve under the 284nm with ultraviolet spectrophotometry.The reaction solution of described reaction is carried out centrifugal, measures the volume of supernatant liquor, obtain the concentration of product again with the uv-spectrophotometric external standard method, calculate the mole number of product 5 hydroxymethyl furfural, calculate yield according to following formula:
5 hydroxymethyl furfural yield=(5 hydroxymethyl furfural mole number/fructose mole number) * 100%.
Compared with prior art, the present invention has following advantage:
The present invention is raw material with fructose, and N,N-dimethylacetamide is as reaction solvent, and lithium chloride is an additive, and carried heteropoly acid is a catalyzer, the preparation 5 hydroxymethyl furfural; The purpose of adding lithium chloride is in order to suppress production of by-products, to improve the productive rate of 5 hydroxymethyl furfural; With the carried heteropoly acid is catalyzer, and titanium dioxide had both guaranteed catalytic activity as the carrier of heteropolyacid, and catalyzer is easier separated, to reduce the consumption of catalyzer.
The present invention can be by further change catalyzer the ratio, starting point concentration, catalyst consumption, content of additive, temperature of reaction and the reaction times of fructose of maturing temperature, dipping time, heteropolyacid and carrier optimize reaction conditions, obtained yield and surpassed 90% 5 hydroxymethyl furfural, had significantly with respect to the yield that has the preparation method now and improved.
The inventive method has that by product is few, productive rate is high, environmental friendliness, reaction conditions gentleness,, characteristics such as catalyzer can reclaim little to equipment corrosion, has industrial prospect.
Embodiment
Embodiment 1
Preparation of catalysts: with 1 weight part butyl (tetra) titanate (Ti (OC
4H
9)) be dissolved in the 1.3 weight part dehydrated alcohols, in 0.5h, add 1 weight parts water and make the butyl (tetra) titanate hydrolysis, obtain stable TiO
2Gel.Then with TiO
2Gel is put into inherent 500 ℃ of insulations (calcination) 10h of retort furnace behind 80 ℃ of dry 3h, naturally cool to room temperature after the taking-up, promptly gets TiO after the grinding
2Active carrier.Then, with TiO
2It is to flood 36h in 15% the phospho-molybdic acid aqueous solution that active carrier joins mass percentage concentration, wherein TiO
2With the mass ratio of phospho-molybdic acid be 1: 2, take out at 80 ℃ down after the oven dry, place activation 3h in 150 ℃ of retort furnaces again, promptly get required catalyzer: the phospho-molybdic acid of titanium dichloride load, i.e. H
3PMo
12O
40/ TiO
2
Embodiment 2
Except phospho-molybdic acid is replaced to silicomolybdic acid, all the other are operated with embodiment 1, make required catalyzer: the silicomolybdic acid of titanium dichloride load, i.e. H
4SiMo
12O
40/ TiO
2
Embodiment 3
Except phospho-molybdic acid is replaced to phospho-wolframic acid, all the other are operated with embodiment 1, make required catalyzer: the phospho-wolframic acid of titanium dichloride load, i.e. H
3PW
12O
40/ TiO
2
Embodiment 4
Except phospho-molybdic acid is replaced to silicotungstic acid, all the other are operated with embodiment 1, make required catalyzer: the silicotungstic acid of titanium dichloride load, i.e. H
4SiW
12O
40/ TiO
2
Embodiment 5～8
In the small test tube of 4 band numberings, add 1g N respectively, N-N,N-DIMETHYLACETAMIDE, 0.1g lithium chloride and 0.1g fructose, stirring and dissolving is warming up to 80 ℃ respectively, 100 ℃, 120 ℃, 140 ℃, add each 60mg of catalyzer that embodiment 1 prepares then, stirring reaction 1h, the deionized water that adds 10mL at last stops reaction.Reaction solution is carried out centrifugal, measures the volume of supernatant liquor, obtain the concentration of product 5 hydroxymethyl furfural again with the uv-spectrophotometric external standard method, yield that draws such as following table 1:
The nucleus magnetic hydrogen spectrum data of product:
1H-NMR (D
2O, 400MHz) δ: 9.320 (s, 1H ,-CHO), 7.348 (d, 1H, H), 6.546 (d, 1H, H), 4.569 (s, 2H, CH
2). the nucleus magnetic hydrogen spectrum data conform to 5-HMF standard spectrogram.
The ir data of product: use coating method, the KBr compressing tablet records the infrared spectra of product.The infared spectrum data of product: 3420cm
-1(-OH), 1713cm
-1(-CHO), 1670cm
-1(C=C), 1026cm
-1(C-O-C), 2935cm
-1, 2852cm
-1(CH
2); Ir data is consistent with the ir data of 5-HMF.
The yield of 5 hydroxymethyl furfural under the table 1 differential responses temperature
| Implementation sequence number | Temperature (℃) | Yield (%) |
| 5 | 80 | 15 |
| 6 | 100 | 56 |
| 7 | 120 | 77 |
| 8 | 140 | 75 |
Embodiment 9～13
In the small test tube of 5 band numberings, add 1g N respectively, the N-N,N-DIMETHYLACETAMIDE, 0.15g lithium chloride and 0.1g fructose, stirring and dissolving is warming up to 120 ℃, adds each 80mg of catalyzer for preparing under embodiment 1 condition then, reaction times is got 0.5h, 1h, 1.5h, 2h, 5h respectively, and the deionized water that adds 10mL at last stops reaction.Reaction solution is carried out centrifugal, measures the volume of supernatant liquor, obtain the concentration of product 5 hydroxymethyl furfural again with the uv-spectrophotometric external standard method, the yield such as the table 2 that draw:
Pairing reaction yield of table 2 differential responses time
| Implementation sequence number | Time (h) | Yield (%) |
| 9 | 0.5 | 65 |
| 10 | 1 | 85 |
| 11 | 1.5 | 82 |
| 12 | 2 | 76 |
| 13 | 5 | 70 |
Embodiment 14～18
In the small test tube of 5 band numberings, add 1g N respectively, the N-N,N-DIMETHYLACETAMIDE, 0.1g lithium chloride and 0.1g fructose, stirring is dissolved, and is warming up to 120 ℃, add the catalyzer for preparing under embodiment 1 condition then, get 60mg, 80mg, 100mg, 120mg, 150mg respectively, stirring reaction 1h, the deionized water that adds 10mL at last stops reaction.Reaction solution is carried out centrifugal, measures the volume of supernatant liquor, obtain the concentration of product 5 hydroxymethyl furfural again with the uv-spectrophotometric external standard method, the yield such as the table 3 that draw:
The pairing reaction yield of table 3 different catalysts consumption
| Implementation sequence number | The amount of catalyzer (mg) | Yield (%) |
| 14 | 60 | 72 |
| 15 | 80 | 80 |
| 16 | 100 | 86 |
| 17 | 120 | 83 |
| 18 | 150 | 80 |
Embodiment 19～23
In the small test tube of 5 band numberings, add 1g N respectively, the N-N,N-DIMETHYLACETAMIDE, 0.1g fructose and 0mg, 50mg, 150mg, 200mg, 250mg lithium chloride, stirring is dissolved, and is warming up to 120 ℃, adds each 100mg of catalyzer for preparing under embodiment 1 condition then, stirring reaction 1h, the last deionized water that adds 10mL in each test tube stops reaction.Reaction solution is carried out centrifugal, measures the volume of supernatant liquor, obtain the concentration of product 5 hydroxymethyl furfural again with the uv-spectrophotometric external standard method, the yield such as the table 4 that draw:
The pairing yield of the amount of table 4 different additive
| Implementation sequence number | The consumption of lithium chloride (mg) | Yield (%) |
| 19 | / | 45 |
| 20 | 50 | 68 |
| 21 | 150 | 92 |
| 22 | 200 | 84 |
| 23 | 250 | 80 |
Embodiment 24～28
In the small test tube of 5 band numberings, add 1g N respectively, the N-N,N-DIMETHYLACETAMIDE, 0.15g lithium chloride and 0.05g, 0.1g, 0.15g, 0.2g or 0.25g fructose, stirring is dissolved, and is warming up to 100 ℃, adds each 60mg of catalyzer for preparing under embodiment 1 condition then, stirring reaction 1h, the last deionized water that adds 10mL in each test tube stops reaction.Reaction solution is carried out centrifugal, measures the volume of supernatant liquor, obtain the concentration of product 5 hydroxymethyl furfural again with the uv-spectrophotometric external standard method, the yield such as the table 5 that draw:
The yield of the different fructose original bulk of table 5 correspondence
| Implementation sequence number | The consumption of fructose (mg) | Yield (%) |
| 24 | 50 | 63 |
| 25 | 100 | 62 |
| 26 | 150 | 62 |
| 27 | 200 | 61 |
| 28 | 250 | 60 |
Embodiment 29～32
In the small test tube of 5 band numberings, add the 1g N,N-dimethylacetamide respectively, 0.15g lithium chloride and 0.1g fructose, stirring is dissolved, and is warming up to 120 ℃, adds the catalyzer H for preparing under embodiment 1 condition then respectively
3PMo
12O
40/ TiO
2, the catalyzer H for preparing under embodiment 2 conditions
4SiMo
12O
40/ TiO
2, the catalyzer H for preparing under embodiment 3 conditions
3PW
12O
40/ TiO
2, the catalyzer H for preparing under embodiment 4 conditions
4SiW
12O
40/ TiO
2Each 60mg, stirring reaction 1h, the last deionized water that adds 10mL in each test tube stops reaction.Reaction solution is carried out centrifugal, measures the volume of supernatant liquor, obtain the concentration of product 5 hydroxymethyl furfural again with the uv-spectrophotometric external standard method, the yield such as the table 6 that draw:
The pairing yield of table 6 different catalysts
| Implementation sequence number | Catalyzer | Yield (%) |
| 29 | H 3PMo 12O 4O/TiO 2 | 80 |
| 30 | H 4SiMo 12O 4O/TiO 2 | 79 |
| 31 | H 3PW 12O 4O/TiO 2 | 82 |
| 32 | H 4SiW 12O 40/TiO 2 | 76 |
Claims (10)
1. one kind prepares the method for 5 hydroxymethyl furfural by fructose, may further comprise the steps:
With the N,N-dimethylacetamide is solvent, and lithium chloride is an additive, and fructose is reaction raw materials, and the heteropolyacid of titanium dichloride load is a catalyzer, generates 5 hydroxymethyl furfural 80 ℃～150 ℃ reactions.
2. according to claim 1ly prepare the method for 5 hydroxymethyl furfural, it is characterized in that the quality of described lithium chloride is 5%～25% of a solvent quality by fructose.
3. according to claim 2ly prepare the method for 5 hydroxymethyl furfural, it is characterized in that the quality of described lithium chloride is 15%～25% of a solvent quality by fructose.
4. according to claim 1ly prepare the method for 5 hydroxymethyl furfural, it is characterized in that the quality of described fructose is 5%～35% of a solvent quality by fructose; The quality of described catalyzer is 2%～15% of a solvent quality.
5. according to claim 4ly prepare the method for 5 hydroxymethyl furfural, it is characterized in that the quality of described fructose is 5%～25% of a solvent quality by fructose.
6. describedly prepare the method for 5 hydroxymethyl furfural according to claim 1 or 4, it is characterized in that by fructose, in the described catalyzer mass ratio of titanium dioxide and heteropolyacid be 1: 1～6.
7. according to claim 6ly prepare the method for 5 hydroxymethyl furfural, it is characterized in that the mass ratio of titanium dioxide and heteropolyacid is 1: 2 in the described catalyzer by fructose.
8. according to claim 1ly prepare the method for 5 hydroxymethyl furfural, it is characterized in that described heteropolyacid is one or more in phospho-molybdic acid, phospho-wolframic acid, silicotungstic acid, the silicomolybdic acid by fructose.
9. according to claim 1ly prepare the method for 5 hydroxymethyl furfural, it is characterized in that described temperature of reaction is 120 ℃～140 ℃ by fructose.
10. according to claim 1ly prepare the method for 5 hydroxymethyl furfural, it is characterized in that the described reaction times is 10min～300min by fructose.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100478058A CN102153527B (en) | 2011-02-28 | 2011-02-28 | Method for preparing 5-hydroxymethylfurfural with fructose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100478058A CN102153527B (en) | 2011-02-28 | 2011-02-28 | Method for preparing 5-hydroxymethylfurfural with fructose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102153527A true CN102153527A (en) | 2011-08-17 |
| CN102153527B CN102153527B (en) | 2013-01-30 |
Family
ID=44435242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100478058A Expired - Fee Related CN102153527B (en) | 2011-02-28 | 2011-02-28 | Method for preparing 5-hydroxymethylfurfural with fructose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102153527B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113326A (en) * | 2013-01-24 | 2013-05-22 | 西北师范大学 | Preparation method of 5-hydroxymethylfurfural |
| CN103694203A (en) * | 2013-12-24 | 2014-04-02 | 华南理工大学 | Method of catalyzing fructose by cellulose base sulfonic acid catalyst to prepare 5-hydroxymethyl furfural |
| CN103788033A (en) * | 2012-11-05 | 2014-05-14 | 中国科学院大连化学物理研究所 | Method for preparing 5-hydroxymethyl furfural through dehydration of fructose |
| CN104072450A (en) * | 2014-07-14 | 2014-10-01 | 南京林业大学 | Novel method for preparing 5-hydroxymethylfurfural and furfural by adopting biomass raw material |
| CN104817524A (en) * | 2015-04-07 | 2015-08-05 | 中南民族大学 | Method for preparing 5-hydroxymethyl furoic acid through catalytic conversion on fructose |
| CN105418561A (en) * | 2015-12-07 | 2016-03-23 | 南京工业大学 | Method for preparing 2,5-furandicarboxylic acid by supported bifunctional catalyst by catalyzing fructose |
| CN106699703A (en) * | 2017-01-06 | 2017-05-24 | 吉林大学 | Method for preparing 5-hydroxymethylfurfural through catalyzing biomass sugar by zirconium phosphate-supported titanium dioxide |
| CN107185510A (en) * | 2016-12-22 | 2017-09-22 | 青岛大学 | It is catalyzed the preparation of the titanate radical nanopipe of fructose dehydration 5 hydroxymethylfurfurals of generation |
| CN109967043A (en) * | 2019-04-01 | 2019-07-05 | 北京化工大学 | A kind of organic-inorganic hybrid material LYZ-PTA of novel adjustable particle size |
| CN111295377A (en) * | 2017-09-28 | 2020-06-16 | Ifp 新能源公司 | Method for producing 5-hydroxymethylfurfural in the presence of an inorganic dehydration catalyst and a chloride source |
| CN113103380A (en) * | 2021-04-13 | 2021-07-13 | 桃江县福丰木业有限公司 | Environment-friendly wood veneer not easy to crack and preparation method thereof |
| CN114426528A (en) * | 2020-09-25 | 2022-05-03 | 中国石油化工股份有限公司 | Method for continuously preparing 5-hydroxymethylfurfural |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289435A (en) * | 2008-06-05 | 2008-10-22 | 大连理工大学 | Process for preparing 5-hydroxymethyl-furfural |
-
2011
- 2011-02-28 CN CN2011100478058A patent/CN102153527B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289435A (en) * | 2008-06-05 | 2008-10-22 | 大连理工大学 | Process for preparing 5-hydroxymethyl-furfural |
Non-Patent Citations (1)
| Title |
|---|
| 《J.Am.Chem.Soc.》 20090121 Joseph B.Binder and Ronald T.Raines Simple Chemical Transformation of Lignocellulosic Biomass into Furans for Fuels and Chemicals 1979-1985 1-10 第131卷, 第5期 * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788033B (en) * | 2012-11-05 | 2016-04-06 | 中国科学院大连化学物理研究所 | A kind of fructose Dehydration is for the method for 5 hydroxymethyl furfural |
| CN103788033A (en) * | 2012-11-05 | 2014-05-14 | 中国科学院大连化学物理研究所 | Method for preparing 5-hydroxymethyl furfural through dehydration of fructose |
| CN103113326A (en) * | 2013-01-24 | 2013-05-22 | 西北师范大学 | Preparation method of 5-hydroxymethylfurfural |
| CN103113326B (en) * | 2013-01-24 | 2016-04-13 | 西北师范大学 | A kind of preparation method of 5 hydroxymethyl furfural |
| CN103694203A (en) * | 2013-12-24 | 2014-04-02 | 华南理工大学 | Method of catalyzing fructose by cellulose base sulfonic acid catalyst to prepare 5-hydroxymethyl furfural |
| CN103694203B (en) * | 2013-12-24 | 2015-04-22 | 华南理工大学 | Method of catalyzing fructose by cellulose base sulfonic acid catalyst to prepare 5-hydroxymethyl furfural |
| CN104072450A (en) * | 2014-07-14 | 2014-10-01 | 南京林业大学 | Novel method for preparing 5-hydroxymethylfurfural and furfural by adopting biomass raw material |
| CN104072450B (en) * | 2014-07-14 | 2016-03-02 | 南京林业大学 | Biomass material prepares the novel method of 5 hydroxymethyl furfural and furfural |
| CN104817524B (en) * | 2015-04-07 | 2017-03-08 | 中南民族大学 | A kind of method that catalyzed conversion fructose prepares 5 methylol furancarboxylic acids |
| CN104817524A (en) * | 2015-04-07 | 2015-08-05 | 中南民族大学 | Method for preparing 5-hydroxymethyl furoic acid through catalytic conversion on fructose |
| CN105418561A (en) * | 2015-12-07 | 2016-03-23 | 南京工业大学 | Method for preparing 2,5-furandicarboxylic acid by supported bifunctional catalyst by catalyzing fructose |
| CN105418561B (en) * | 2015-12-07 | 2018-03-30 | 南京工业大学 | A kind of method that support type bifunctional catalyst catalysis fructose prepares 2,5 furandicarboxylic acids |
| CN107185510A (en) * | 2016-12-22 | 2017-09-22 | 青岛大学 | It is catalyzed the preparation of the titanate radical nanopipe of fructose dehydration 5 hydroxymethylfurfurals of generation |
| CN106699703A (en) * | 2017-01-06 | 2017-05-24 | 吉林大学 | Method for preparing 5-hydroxymethylfurfural through catalyzing biomass sugar by zirconium phosphate-supported titanium dioxide |
| CN106699703B (en) * | 2017-01-06 | 2020-09-29 | 吉林大学 | Method for preparing 5-hydroxymethylfurfural by catalyzing biomass sugar with zirconium phosphate loaded titanium dioxide |
| CN111295377A (en) * | 2017-09-28 | 2020-06-16 | Ifp 新能源公司 | Method for producing 5-hydroxymethylfurfural in the presence of an inorganic dehydration catalyst and a chloride source |
| CN109967043A (en) * | 2019-04-01 | 2019-07-05 | 北京化工大学 | A kind of organic-inorganic hybrid material LYZ-PTA of novel adjustable particle size |
| CN114426528A (en) * | 2020-09-25 | 2022-05-03 | 中国石油化工股份有限公司 | Method for continuously preparing 5-hydroxymethylfurfural |
| CN114426528B (en) * | 2020-09-25 | 2024-02-09 | 中国石油化工股份有限公司 | Method for continuously preparing 5-hydroxymethylfurfural |
| CN113103380A (en) * | 2021-04-13 | 2021-07-13 | 桃江县福丰木业有限公司 | Environment-friendly wood veneer not easy to crack and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102153527B (en) | 2013-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102153527B (en) | Method for preparing 5-hydroxymethylfurfural with fructose | |
| Li et al. | High conversion of glucose to 5-hydroxymethylfurfural using hydrochloric acid as a catalyst and sodium chloride as a promoter in a water/γ-valerolactone system | |
| Zhuo et al. | Hydrolysis of cellulose catalyzed by novel acidic ionic liquids | |
| Xia et al. | High yield synthesis of 5-hydroxymethylfurfural from cellulose using FePO4 as the catalyst | |
| CN104072450B (en) | Biomass material prepares the novel method of 5 hydroxymethyl furfural and furfural | |
| Dutta et al. | Direct conversion of cellulose and lignocellulosic biomass into chemicals and biofuel with metal chloride catalysts | |
| CN103242270B (en) | A kind of from biomass-making the method for Furnan products | |
| CN101812039B (en) | Method for generating 5-hydroxymethylfurfural by using ionic liquid catalysis | |
| CN104250237B (en) | Method for preparing 5-hydroxymethylfurfural through catalyzing fructose conversion by solid catalyst | |
| CN103172599B (en) | Method for catalyzing carbohydrate to prepare 5-(hydroxymethyl) furfural (5-HMF) and levulinic acid (LA) | |
| CN104829560A (en) | Method of synthesizing 5-hydroxymethyl furfural | |
| CN103910903A (en) | Application of molybdenum-based catalyst to prepare organic chemicals from lignin | |
| CN104277020B (en) | Aqueous catalysis 5 hydroxymethyl furfural prepares the method for 2,5-furandicarboxylic acid | |
| CN106824226A (en) | A kind of preparation method and its usage of carbon-based solid acid | |
| Shi et al. | Multiple-SO3H functionalized ionic liquid as efficient catalyst for direct conversion of carbohydrate biomass into levulinic acid | |
| CN104894298A (en) | Method used for degrading lignocellulose with solid acid catalyst | |
| CN112608289A (en) | Method for efficiently preparing 5-hydroxymethylfurfural by catalyzing bio-based fructose through organic solvent-ionic liquid composite system | |
| Islam et al. | Microwave-assisted catalytic conversion of chitin to 5-hydroxymethylfurfural using polyoxometalate as catalyst | |
| CN106699703B (en) | Method for preparing 5-hydroxymethylfurfural by catalyzing biomass sugar with zirconium phosphate loaded titanium dioxide | |
| CN103626633A (en) | Method for promoting solid catalyst to depolymerize cellulose | |
| Huang et al. | Conversion of carbohydrates into furfural and 5-hydroxymethylfurfural using furfuryl alcohol resin-based solid acid as catalyst | |
| CN105521802A (en) | Visible light responding silver phosphate composite photocatalyst and preparation and application thereof | |
| CN102850303B (en) | New application and using method of mesoporous solid acid catalyst | |
| CN103508985B (en) | Produce the method for furfural and/or 5 hydroxymethyl furfural taking red algae living beings as raw material | |
| CN102321489B (en) | Method for catalyzing and liquefying agricultural wastes by using ion liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191231 Address after: 314416 No.318, Nanjie Road, Yuanhua Town, Haining City, Jiaxing City, Zhejiang Province Patentee after: Haining Yuanhua Town Industrial Investment Co., Ltd Address before: 321004 No. 688 Yingbin Road, Zhejiang, Jinhua Patentee before: Zhejiang Normal University |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130130 Termination date: 20200228 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |