CN101367782A - Method for preparing 5-hydroxymethyl furfural by catalyzing glucose with solid ultra-strong acid - Google Patents
Method for preparing 5-hydroxymethyl furfural by catalyzing glucose with solid ultra-strong acid Download PDFInfo
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- CN101367782A CN101367782A CNA2008100462503A CN200810046250A CN101367782A CN 101367782 A CN101367782 A CN 101367782A CN A2008100462503 A CNA2008100462503 A CN A2008100462503A CN 200810046250 A CN200810046250 A CN 200810046250A CN 101367782 A CN101367782 A CN 101367782A
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- 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
Abstract
The present invention relates to a method of preparing 5-methylol furol under the catalysis of solid ultra strong acid. In the method, glucose is used as a raw material, the solid ultra strong acid SO4<2->/Al2O3 or SO4<2->/ZrO<2->Al2O3 is used as a catalyst, dimethyl sulfoxide is used as a reaction medium, and the 5-methylol furol is prepared in a fixed bed reactor. The reaction can be performed under the conditions with normal pressure and with the temperature between 110 DEG C and 150 DEG C. The present invention has the advantages that the reaction conditions are mild, the raw materials are cheap and can be easily acquired, the catalyst can be recycled and repeatedly used, the operation is simple, and the whole process is conducive to the environmental protection.
Description
Technical field:
The present invention relates to a kind of method for preparing 5 hydroxymethyl furfural by catalyzing glucose with solid ultra-strong acid.
Background technology:
5 hydroxymethyl furfural (HMF) is a kind of very important chemical, aspect the synthetic and pesticide producing important use is arranged at medicine, very big application prospect is also being arranged aspect the production of plastics, and in addition, HMF can also substitute exhausted day by day oil and be used to produce gasoline and diesel oil.HMF is called as " giant who is sunk into sleep ".
The industrialized preparing process that does not also have at present HMF.Existing research adopts fructose as raw material usually, but because the fructose price is comparatively expensive, and it is extensive inadequately to originate, therefore prepares HMF by fructose and be difficult to put in the actual industrial production.Glucose is the monose of reserves maximum in the world, and it can be made by starch and Mierocrystalline cellulose direct hydrolysis, is considered to a kind of inexhaustible raw material.Therefore, preparing HMF by glucose has been subjected to people and has more and more paid close attention to.
H.Harry Szmant etc. are at Journal of Chemical Technology and Biotechnology, adopting glucose among 1981 (31) 135-147 is raw material, with the etherate of trifluoroboron is catalyzer, obtained 42% HMF yield 48 hours 100 ℃ of following reaction times, the shortcoming of this method is long reaction time, and etherate of trifluoroboron is a kind of liquid acid catalyst of danger, both can corrosion reaction equipment, be difficult to the partitioning cycle utilization again.
It is raw material that M.Bicker and co-worker thereof propose with glucose in Green Chemistry 2003 (35) 280-284, with the volume ratio is the acetone of 90:10: water is solvent, with sulfuric acid is catalyzer, being reflected at temperature is 180 ℃, pressure is to carry out in 200 supercritical fluids system under the normal atmosphere, and the HMF yield is about 48%.This severe reaction conditions, to the equipment requirements height, and with sulfuric acid as catalyzer to the conversion unit seriously corroded, contaminate environment, catalyzer is difficult to separate with product.
Masaru Watanable seminar is at Carbohydrate Research, and it is raw material that 2005 (340) 1925-1929 propose under hydrothermal condition with glucose, the TiO of Detitanium-ore-type
2Be Preparation of Catalyst HMF, temperature of reaction is 200 ℃, need in autoclave, carry out, and the condition harshness, to the equipment requirements height, the HMF yield only is about 20%.
Haibo Zhao etc. are at Sience, and adopting glucose among 2007 (316) 1597-1600 is raw material, and ionic liquid chloro 1-methyl-3-ethyl imidazol(e) is a reaction medium, CrCl
2Make catalyzer, obtain the HMF yield and be about 70%.But the cost of chloro 1-methyl-3-ethyl imidazol(e) is too high at present, and its application as reaction medium only limits to laboratory study.In addition, catalyzer is difficult to from ionic liquid to separate and continues to recycle, and therefore also can't be applied in the fairly large production.
Summary of the invention:
The object of the present invention is to provide a kind ofly easy to prepare the method for HMF, can not reclaim shortcomings such as repeated use to overcome cost height in the prior art, energy consumption height, conversion unit requirement height and catalyzer by glucose.
The invention main points: normal pressure is reaction down, is raw material with glucose, solid super-strong acid SO
4 2-/ Al
2O
3Perhaps SO
4 2-/ ZrO
2-Al
2O
3Be catalyzer, methyl-sulphoxide is a reaction medium, and wherein the mass ratio of glucose and solvent is 1:4-1:24; Temperature of reaction is 110-150 ℃, and the reaction times is 0.5-8 hours, after reaction finishes with the reaction system water-cooled to room temperature, centrifugation goes out catalyzer.Optimal reaction temperature is 120-140 ℃, and optimum reacting time is 4-6 hours.
Preparation of Catalyst: 1. with Al (NO
3)
39H
2O is mixed with the solution that concentration is 16wt%, dropwise adds 28% ammonia soln to pH=9 under condition of stirring, generates white precipitate, leaves standstill, and suction filtration, washing are to neutral, and drying is ground, and obtains Al (OH)
3Precipitation is 1molL with concentration
-1The dichloroethane solution dipping of chlorsulfonic acid, the pickup of chlorsulfonic acid is 7.5mmol/g, floods 0.5 hour, 110 ℃ were descended dry 12 hours, placed retort furnace then, 550 ℃ of following roastings 4 hours, made catalyst S O
4 2-/ Al
2O
3
2. or with Zr (NO
3)
45H
2O and Al (NO
3)
39H
2O is a raw material, is that 1:9-9:1 is mixed with the solution that concentration is 16wt% according to the Zr/Al mol ratio, dropwise adds 28% ammonia soln to pH=9 under condition of stirring, generate white precipitate, leave standstill, suction filtration, washing are to neutral, drying is ground, and obtains Zr (OH)
4And Al (OH)
3Co-precipitation, be 1molL with concentration
-1The dichloroethane solution dipping of chlorsulfonic acid, the pickup of chlorsulfonic acid is 7.5mmol/g, floods 0.5 hour, 110 ℃ were descended dry 12 hours, placed retort furnace then, 550 ℃ of following roastings 4 hours, made the solid super acid catalyst SO of different Zr/Al mol ratios
4 2-/ ZrO
2-Al
2O
3
Characteristics of the present invention are: 1. be reflected under the gentle condition and carry out normal pressure, low temperature, less energy-consumption.2. solid super-strong acid is a heterogeneous catalyst, is easy to preparation, is easy to separate renewable recycling.3. process no waste discharging, no equipment corrosion, processing step is few, and operational safety has the favorable industrial application prospect.
Embodiment is:
Embodiment 1:
With Al (NO
3)
39H
2O is mixed with the solution that concentration is 16wt%, dropwise adds 28% ammonia soln to pH=9 under condition of stirring, generates white precipitate, leaves standstill, and suction filtration, washing are to neutral, and drying is ground, and obtains Al (OH)
3Precipitation is 1molL with concentration
-1The dichloroethane solution dipping of chlorsulfonic acid, the pickup of chlorsulfonic acid is 7.5mmol/g, floods 0.5 hour, 110 ℃ were descended dry 12 hours, placed retort furnace then, 550 ℃ of following roastings 4 hours, made catalyst S O
4 2-/ Al
2O
3
In a single necked round bottom flask, add 0.09g glucose (0.5mmol) and 1mL methyl-sulphoxide, add 0.018gSO then
4 2-/ Al
2O
3Catalyzer connects prolong and is placed in the oil bath pan, and oil bath pan is warming up to 130 ℃, and constant temperature stirs, and back flow reaction is stopped reaction after 4 hours.To room temperature, centrifugation goes out catalyzer with the reaction system water-cooled.Reaction solution detects with high performance liquid chromatography, records the productive rate 41% of HMF at last.
Embodiment 2-6:
With Zr (NO
3)
45H
2O and Al (NO
3) 39H
2O is a raw material, is that 1:9-9:1 is mixed with the solution that concentration is 16wt% according to the Zr/Al mol ratio, dropwise adds 28% ammonia soln to pH=9 under condition of stirring, generate white precipitate, leave standstill, suction filtration, washing are to neutral, drying is ground, and obtains Zr (OH)
4And Al (OH)
3Co-precipitation, be 1molL with concentration
-1The dichloroethane solution dipping of chlorsulfonic acid, the pickup of chlorsulfonic acid is 7.5mmol/g, floods 0.5 hour, 110 ℃ were descended dry 12 hours, placed retort furnace then, 550 ℃ of following roastings 4 hours, made the solid super acid catalyst SO of different Zr/Al mol ratios
4 2-/ ZrO
2-Al
2O
3, the Zr/Al mol ratio sees Table 1.
In five single necked round bottom flask, add 0.09g glucose (0.5mmol), the 1mL methyl-sulphoxide adds the SO of the different Zr/Al mol ratios that 0.018g prepares as stated above then respectively
4 2-/ ZrO
2-Al
2O
3Catalyzer connects prolong and is placed in the oil bath pan, and oil bath pan is warming up to 130 ℃, and constant temperature stirs, and back flow reaction is stopped reaction after 4 hours.To room temperature, centrifugation goes out catalyzer with the reaction system water-cooled.Reaction solution detects with high performance liquid chromatography, and the result who is obtained by different catalysts is set forth in the table 1.
Table 1
| The embodiment sequence number | Catalyst S O 4 2-/ZrO 2-Al 2O 3The zirconium al mole ratio | The productive rate % of HMF |
| 2 | Zr：Al＝9：1 | 27 |
| 3 | Zr：Al＝7：3 | 41 |
| 4 | Zr：Al＝5：5 | 47 |
| 5 | Zr：Al＝3：7 | 43 |
| 6 | Zr：Al＝1：9 | 37 |
Embodiment 7-8:
In two single necked round bottom flask, add 0.045g (0.25mmol) and 0.18g glucose (1mmol) respectively, the 1mL methyl-sulphoxide, adding 0.018g then is the SO of 5:5 according to the Zr/Al mol ratio that embodiment 4 prepares
4 2-/ ZrO
2-Al
2O
3Catalyzer places four oil bath pans respectively after connecting prolong, and the oil bath pan temperature is risen to 130 ℃ respectively, and constant temperature stirs, and back flow reaction is stopped reaction after 4 hours.To room temperature, centrifugation goes out catalyzer with the reaction system water-cooled.Reaction solution detects with high performance liquid chromatography, and the result that the different amount of adding glucose responses are obtained is set forth in the table 2.
Table 2
| The embodiment sequence number | Glucose quality (g) | The productive rate % of HMF |
| 7 | 0.045 | 45 |
| 8 | 0.27 | 44 |
Embodiment 9-12:
In four single necked round bottom flask, add 0.09g glucose (0.5mmol), the 1mL methyl-sulphoxide, adding 0.018g then is the SO of 5:5 according to the Zr/Al mol ratio that embodiment 4 prepares
4 2-/ ZrO
2-Al
2O
3Catalyzer places four oil bath pans respectively after connecting prolong, and the oil bath pan temperature is risen to 110 ℃, 120 ℃, 140 ℃, 150 ℃ respectively, and constant temperature stirs, and back flow reaction is stopped reaction after 4 hours.To room temperature, centrifugation goes out catalyzer with the reaction system water-cooled.Reaction solution detects with high performance liquid chromatography, and the result that reaction obtains under the differing temps is set forth in the table 3.
Table 3
| The embodiment sequence number | Temperature (℃) | The productive rate % of HMF |
| 9 | 110 | 34 |
| 10 | 120 | 45 |
| 11 | 140 | 42 |
| 12 | 150 | 37 |
Embodiment 13-16:
In four single necked round bottom flask, add 0.09g glucose (0.5mmol), the 1mL methyl-sulphoxide, adding 0.018g then is the SO of 5:5 according to the Zr/Al mol ratio that embodiment 4 prepares
4 2-/ ZrO
2-Al
2O
3Catalyzer places four oil bath pans respectively after connecting prolong, and oil bath pan is warming up to 130 ℃, and constant temperature stirs, respectively back flow reaction stopped reaction after 0.5,2,6,8 hours.To room temperature, centrifugation goes out catalyzer with the reaction system water-cooled.Reaction solution detects with high performance liquid chromatography, and the result that reaction obtains under the differential responses time is set forth in the table 4.
Table 4
| The embodiment sequence number | Time (hour) | The productive rate % of HMF |
| 13 | 0.5 | 26 |
| 14 | 2 | 42 |
| 15 | 6 | 50 |
| 16 | 8 | 47 |
Claims (3)
1. the method by catalyzing glucose with solid ultra-strong acid preparation 5-hydroxymethylfurfural is a raw material with glucose, and normal pressure reaction down is characterized in that with solid super-strong acid SO
4 2-/ Al
2O
3Perhaps SO
4 2-/ ZrO
2-Al
2O
3Be catalyzer, methyl-sulphoxide is a reaction medium, and wherein the mass ratio of glucose and methyl-sulphoxide is 1:4-1:24, and temperature of reaction is 110-150 ℃, and the reaction times is 0.5-8 hours.
2. method according to claim 1 is characterized in that temperature of reaction is 120-140 ℃.
3. method according to claim 1 is characterized in that the reaction times is 4-6 hours.
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|---|---|---|---|
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|---|---|---|---|
| CN2008100462503A CN101367782B (en) | 2008-10-09 | 2008-10-09 | Method for preparing 5-hydroxymethyl furfural by catalyzing glucose with solid ultra-strong acid |
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| Publication Number | Publication Date |
|---|---|
| CN101367782A true CN101367782A (en) | 2009-02-18 |
| CN101367782B CN101367782B (en) | 2012-04-25 |
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|---|---|---|---|
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829593A (en) * | 2010-04-13 | 2010-09-15 | 中国地质大学（武汉） | Preparation method of titanium dioxide persulfate-loaded mordenite solid superacid catalyst |
| CN101935312A (en) * | 2010-08-18 | 2011-01-05 | 四川大学 | Method for preparing 5-hydroxymethylfurfural by catalyzing starch by heterogeneous catalysts |
| CN101613331B (en) * | 2009-07-23 | 2011-09-14 | 四川大学 | Method for preparing 5-acetoxymethyl furfural with carbohydrate |
| CN103012335A (en) * | 2012-11-30 | 2013-04-03 | 中国科学院广州能源研究所 | Method for co-producing furfural and 5-hydroxymethylfurfural by using lignocellulose-containing biomass |
| CN103214438A (en) * | 2013-01-21 | 2013-07-24 | 塔里木大学 | Method for preparing 5-hydroxymethylfurfural with grape as raw mateiral |
| 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 |
| CN104383904A (en) * | 2014-12-04 | 2015-03-04 | 江南大学 | Method for preparing 5-hydroxymethylfurfural from mesoporous self-assembly sulfonated nano-zirconia catalytic fructose |
| US9012664B2 (en) | 2011-12-28 | 2015-04-21 | E I Du Pont De Nemours And Company | Process for the production of furfural |
| US9024047B2 (en) | 2010-12-21 | 2015-05-05 | E I Du Pont De Nemours And Company | Methods for furfural production from branched non-fermentable sugars in stillage or syrup |
| US9181211B2 (en) | 2011-12-28 | 2015-11-10 | E I Du Pont De Nemours And Company | Process for the production of furfural |
| US9181210B2 (en) | 2011-12-28 | 2015-11-10 | E I Du Pont De Nemours And Company | Processes for making furfurals |
| US9181209B2 (en) | 2011-12-28 | 2015-11-10 | E I Du Pont De Nemours And Company | Process for the production of furfural |
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| CN109550491A (en) * | 2018-11-07 | 2019-04-02 | 山东科技大学 | Prepare ZrO2The method of catalyst |
| CN112246240A (en) * | 2020-10-15 | 2021-01-22 | 江苏金聚合金材料有限公司 | Preparation and application of dimethyl carbonate catalyst |
| CN112830907A (en) * | 2019-12-20 | 2021-05-25 | 中国科学院宁波材料技术与工程研究所 | Method for preparing 5-hydroxymethylfurfural |
| CN114733570A (en) * | 2022-04-26 | 2022-07-12 | 南京林业大学 | Solid catalyst with sodium carboxymethylcellulose as matrix, preparation method and application thereof |
-
2008
- 2008-10-09 CN CN2008100462503A patent/CN101367782B/en not_active Expired - Fee Related
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|---|---|---|---|---|
| CN101613331B (en) * | 2009-07-23 | 2011-09-14 | 四川大学 | Method for preparing 5-acetoxymethyl furfural with carbohydrate |
| CN101829593B (en) * | 2010-04-13 | 2011-08-31 | 中国地质大学（武汉） | Preparation method of titanium dioxide persulfate-loaded mordenite solid superacid catalyst |
| CN101829593A (en) * | 2010-04-13 | 2010-09-15 | 中国地质大学（武汉） | Preparation method of titanium dioxide persulfate-loaded mordenite solid superacid catalyst |
| CN101935312A (en) * | 2010-08-18 | 2011-01-05 | 四川大学 | Method for preparing 5-hydroxymethylfurfural by catalyzing starch by heterogeneous catalysts |
| CN101935312B (en) * | 2010-08-18 | 2012-07-04 | 四川大学 | Method for preparing 5-hydroxymethylfurfural by catalyzing starch by heterogeneous catalysts |
| US9024047B2 (en) | 2010-12-21 | 2015-05-05 | E I Du Pont De Nemours And Company | Methods for furfural production from branched non-fermentable sugars in stillage or syrup |
| US9181209B2 (en) | 2011-12-28 | 2015-11-10 | E I Du Pont De Nemours And Company | Process for the production of furfural |
| US9181210B2 (en) | 2011-12-28 | 2015-11-10 | E I Du Pont De Nemours And Company | Processes for making furfurals |
| US9012664B2 (en) | 2011-12-28 | 2015-04-21 | E I Du Pont De Nemours And Company | Process for the production of furfural |
| US9181211B2 (en) | 2011-12-28 | 2015-11-10 | E I Du Pont De Nemours And Company | Process for the production of furfural |
| CN103012335A (en) * | 2012-11-30 | 2013-04-03 | 中国科学院广州能源研究所 | Method for co-producing furfural and 5-hydroxymethylfurfural by using lignocellulose-containing biomass |
| CN103012335B (en) * | 2012-11-30 | 2015-03-11 | 中国科学院广州能源研究所 | Method for co-producing furfural and 5-hydroxymethylfurfural by using lignocellulose-containing biomass |
| CN103214438A (en) * | 2013-01-21 | 2013-07-24 | 塔里木大学 | Method for preparing 5-hydroxymethylfurfural with grape as raw mateiral |
| 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 |
| 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 |
| CN104383904A (en) * | 2014-12-04 | 2015-03-04 | 江南大学 | Method for preparing 5-hydroxymethylfurfural from mesoporous self-assembly sulfonated nano-zirconia catalytic fructose |
| CN106984333A (en) * | 2017-05-26 | 2017-07-28 | 湖南大学 | The preparation method of the loaded catalyst regenerated for carbon dioxide enriched amine aqueous solution |
| CN106984333B (en) * | 2017-05-26 | 2019-11-05 | 湖南大学 | Preparation method for the carbon dioxide enriched regenerated loaded catalyst of amine aqueous solution |
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| CN109550491A (en) * | 2018-11-07 | 2019-04-02 | 山东科技大学 | Prepare ZrO2The method of catalyst |
| CN112830907A (en) * | 2019-12-20 | 2021-05-25 | 中国科学院宁波材料技术与工程研究所 | Method for preparing 5-hydroxymethylfurfural |
| CN112246240A (en) * | 2020-10-15 | 2021-01-22 | 江苏金聚合金材料有限公司 | Preparation and application of dimethyl carbonate catalyst |
| CN112246240B (en) * | 2020-10-15 | 2023-06-16 | 江苏金聚合金材料有限公司 | Preparation and application of dimethyl carbonate catalyst |
| CN114733570A (en) * | 2022-04-26 | 2022-07-12 | 南京林业大学 | Solid catalyst with sodium carboxymethylcellulose as matrix, preparation method and application thereof |
| CN114733570B (en) * | 2022-04-26 | 2023-08-15 | 南京林业大学 | Solid catalyst with sodium carboxymethyl cellulose as matrix, preparation method and application thereof |
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