CN113651781B - Method for preparing 5-hydroxymethylfurfural from glucose - Google Patents
Method for preparing 5-hydroxymethylfurfural from glucose Download PDFInfo
- Publication number
- CN113651781B CN113651781B CN202110876311.4A CN202110876311A CN113651781B CN 113651781 B CN113651781 B CN 113651781B CN 202110876311 A CN202110876311 A CN 202110876311A CN 113651781 B CN113651781 B CN 113651781B
- Authority
- CN
- China
- Prior art keywords
- hydroxymethylfurfural
- glucose
- preparing
- eutectic solvent
- deep eutectic
- 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.)
- Active
Links
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 120
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 120
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 105
- 239000008103 glucose Substances 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000005496 eutectics Effects 0.000 claims abstract description 64
- 239000002904 solvent Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000011259 mixed solution Substances 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 230000035484 reaction time Effects 0.000 claims abstract description 15
- 150000001735 carboxylic acids Chemical class 0.000 claims description 43
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 26
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical group [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 13
- 235000019253 formic acid Nutrition 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 abstract description 24
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 27
- 238000003756 stirring Methods 0.000 description 23
- 229940040102 levulinic acid Drugs 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000007086 side reaction Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 229930091371 Fructose Natural products 0.000 description 5
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 5
- 239000005715 Fructose Substances 0.000 description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 5
- 238000005352 clarification Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- 229960003237 betaine Drugs 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 235000019743 Choline chloride Nutrition 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 3
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 3
- 229960003178 choline chloride Drugs 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229910052751 metal Chemical class 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000002663 humin Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
Abstract
The invention discloses a method for preparing 5-hydroxymethylfurfural from glucose. The method for preparing 5-hydroxymethylfurfural from glucose comprises the following steps: s1, mixing water and a deep eutectic solvent to obtain a mixed solution; s2, performing airtight mixing reaction on the glucose and the mixed solution in the S1 to obtain 5-hydroxymethylfurfural; wherein the deep eutectic solvent in S1 is a mixture of quaternary ammonium salt and organic carboxylic acid, and the molar ratio of the quaternary ammonium salt to the organic carboxylic acid is 1 (1-10); the mass percentage of water in the mixed solution is 5-80 wt%; the reaction temperature in S2 is 110-170 ℃ and the reaction time is 0.1-6 h. The method does not need to add an extra catalyst, and the highest yield of the 5-hydroxymethylfurfural reaches 36 percent.
Description
Technical Field
The invention relates to the field of biomass catalytic conversion, in particular to a method for preparing 5-hydroxymethylfurfural from glucose.
Background
5-hydroxymethylfurfural (5-HMF) is an important biomass-based platform compound, and 5-hydroxymethylfurfural and derivatives thereof are widely applied to industries such as fuel, paint, medicine and degradable materials. The subsequent production and processing of the 5-hydroxymethylfurfural can be well connected with the existing petroleum industrial system, and is a bridge for connecting biomass energy and the existing petroleum industrial system. 5-hydroxymethylfurfural can be prepared by dehydration of glucose and fructose. If fructose is used as a raw material to prepare 5-hydroxymethylfurfural, the yield will be higher than that of glucose, because the furan ring configuration specific to fructose is easily converted into 5-hydroxymethylfurfural. However, glucose needs to be isomerized to form fructose and then dehydrated to form 5-hydroxymethylfurfural, and the yield of conversion of glucose to 5-hydroxymethylfurfural is low due to the additional isomerization steps. However, the price of fructose is much higher than that of glucose, and compared with glucose, the preparation of 5-hydroxymethylfurfural from glucose as a raw material is economically more feasible.
In the prior art, various catalysts are used for preparing 5-hydroxymethylfurfural from glucose in order to increase the yield. For example, chinese patent CN107556271 discloses a method for preparing and separating 5-hydroxymethylfurfural from glucose, which uses deep eutectic solvent formed by glucose and choline chloride as reaction phase and organic solvent as extraction phase to form a bi-directional reaction system, and the yield can reach 36.23%. However, the method introduces a solid acid catalyst prepared from active carbon, sulfuric acid and metal salt, the sulfuric acid catalyst can corrode equipment, the active carbon is seriously and easily deactivated in an acid system, and the metal salt has the problem of heavy metal pollution to the environment, so that the problem of subsequent need of recycling the solid acid catalyst also exists.
In order to solve the problem that the catalyst also needs to be recovered, chinese patent CN112574143A discloses a method for directly degrading cellulose with high polymerization degree to obtain 5-hydroxymethylfurfural without adding any catalyst, wherein the method uses p-toluenesulfonic acid with strong acidity and choline chloride as eutectic solvents, and does not add additional catalyst to directly degrade cellulose to obtain 5-hydroxymethylfurfural. However, since this method does not add a catalyst, the yield of 5-hydroxymethylfurfural is only 10.2% at maximum. Thus, the yield of 5-hydroxymethylfurfural prepared from glucose remains to be further improved without using a catalyst.
Disclosure of Invention
The invention aims to overcome the defect and the defect that the existing method for preparing 5-hydroxymethylfurfural by using glucose only uses a deep eutectic solvent without using a catalyst, which can cause low yield of 5-hydroxymethylfurfural, and provides a method for preparing 5-hydroxymethylfurfural by using glucose, wherein the reaction rate is accelerated by adding water into the deep eutectic solvent without using a catalyst, so that the yield of 5-hydroxymethylfurfural can be greatly improved.
The above object of the present invention is achieved by the following technical scheme:
a method for preparing 5-hydroxymethylfurfural from glucose, comprising the steps of:
s1, mixing water and a deep eutectic solvent to obtain a mixed solution;
s2, performing airtight mixing reaction on the glucose and the mixed solution in the S1 to obtain 5-hydroxymethylfurfural;
wherein the deep eutectic solvent in S1 is a mixture of quaternary ammonium salt and organic carboxylic acid, and the molar ratio of the quaternary ammonium salt to the organic carboxylic acid is 1 (1-10);
the mass percentage of water in the mixed solution is 5-80 wt%;
the reaction temperature in S2 is 110-170 ℃ and the reaction time is 0.1-6 h.
It should be noted that S1 and S2 may be performed simultaneously.
The invention selects quaternary ammonium salt and organic carboxylic acid as deep eutectic solvent, which can be used as reaction solvent for preparing 5-hydroxymethyl furfural from glucose, and can also be used as catalyst for catalyzing glucose, wherein the reaction temperature is 110-170 ℃, water exists in the form of hydronium ion at the high temperature in the range, so that proton transfer can be promoted, the reaction rate can be accelerated, side reaction caused by glucose accumulation can be reduced, and the yield of 5-hydroxymethyl furfural can be improved; in addition, the viscosity of the deep eutectic solvent can be reduced by water, so that the problem that mass transfer is difficult and yield is reduced due to the fact that glucose is difficult to mix with the deep eutectic solvent uniformly due to the fact that the viscosity is too high is avoided; in addition, water also serves as a hydrogen bond donor, and the quaternary ammonium salt can form a hydrogen bond with water, so that levulinic acid byproducts generated by hydration reaction of water and 5-hydroxymethylfurfural can be avoided, and the 5-hydroxymethylfurfural can exist stably. The addition of water is excessive, the deep eutectic solvent is insufficient to restrict all water, side reactions can still occur with the product 5-hydroxymethylfurfural, and the yield of 5-hydroxymethylfurfural is reduced, so that the water content in the deep eutectic solvent is strictly controlled to be within the scope of the invention.
In S2, the temperature required for the reaction exceeds 100 ℃, and therefore, it is necessary to perform a closed reaction in a high-pressure reaction vessel, and the pressure actually generated by the closed reaction is determined by various factors such as the temperature and the degree of reaction.
Preferably, the mass percentage of water in the S1 mixed solution is 20-60 wt%. The mass percent of water is in the range, so that the viscosity of a reaction system can be reduced, the reaction rate can be accelerated, the glucose accumulation is prevented from generating side reaction, and the water can be confined by the deep eutectic solvent through a hydrogen bond network, so that the 5-hydroxymethylfurfural can exist stably.
Preferably, the concentration of the glucose solution in S2 is 12.5-100 g/L. The concentration of glucose is too high, glucose can be accumulated to generate side reaction to reduce the yield of 5-hydroxymethylfurfural, and excessive hydrogen protons in the deep eutectic solvent with the concentration of glucose can promote the side reaction to generate to reduce the yield.
Preferably, the concentration of the glucose solution in S2 is 25-50 g/L. The concentration of glucose is within the range, so that glucose accumulation does not generate side reaction, and excessive hydrogen protons in deep eutectic solvent do not promote side reaction to generate excessive reduction of the yield of 5-hydroxymethylfurfural.
Preferably, the molar ratio of the quaternary ammonium salt to the organic carboxylic acid in S1 is 1 (2-3). Part of hydrogen protons in more organic carboxylic acid can form a hydrogen bond network with quaternary ammonium salt, and the other part of hydrogen protons provide an acidic environment, so that glucose is catalyzed to react to generate 5-hydroxymethylfurfural. The content of the organic carboxylic acid is improved, more hydrogen protons can be released to catalyze the dehydration of glucose to generate 5-hydroxymethylfurfural, and the yield of the 5-hydroxymethylfurfural is further improved. However, too high an organic carboxylic acid content, the acid enhancement not only promotes the dehydration of glucose to produce 5-hydroxymethylfurfural, but also promotes the polymerization of 5-hydroxymethylfurfural to produce humins, and increases the selectivity of byproducts, thus reducing the yield of 5-hydroxymethylfurfural.
Preferably, the reaction temperature in S2 is 130-150 ℃ and the reaction time is 0.5-1.5 h. The reaction temperature in the range can have a faster reaction rate, and the side reaction is not enhanced due to the overhigh temperature. The reaction time is in the range, so that the reaction can be fully carried out, the polymerization of 5-hydroxymethylfurfural can be prevented, and the yield of 5-hydroxymethylfurfural is improved.
Preferably, the quaternary ammonium salt is one or more of triethylbenzyl ammonium chloride, tributylmethyl ammonium chloride or tetramethyl ammonium chloride. The quaternary ammonium salt may also be choline chloride. The chloride ions in the quaternary ammonium salt have strong electronegativity, can form hydrogen bond action with glucose and 5-hydroxymethylfurfural, stabilize the glucose and the 5-hydroxymethylfurfural, reduce side reaction, and further improve yield.
Further preferably, the quaternary ammonium salt is triethylbenzyl ammonium chloride. The triethylbenzyl ammonium chloride has a benzene ring structure and excellent phase transfer capability, can be used as a catalyst for organic reaction, and is beneficial to reducing the melting point and viscosity of deep eutectic solvent and increasing the yield.
Preferably, the organic carboxylic acid is one or more of formic acid, lactic acid, citric acid or levulinic acid. In the organic carboxylic acid selected by the invention, the acidity coefficient is smaller, more hydrogen protons can be released, part of hydrogen protons can form a hydrogen bond network with the quaternary ammonium salt, and the other part of hydrogen protons provide an acidic environment, so that the glucose is catalyzed to react to generate 5-hydroxymethylfurfural.
Further preferably, the organic carboxylic acid is formic acid.
Compared with the prior art, the invention has the beneficial effects that:
the method selects the quaternary ammonium salt and the organic carboxylic acid as deep eutectic solvents, and can be used as a reaction solvent for preparing 5-hydroxymethylfurfural from glucose and can also be used as a catalyst for catalyzing the glucose, so that the method does not need to add an additional catalyst, reduces the step of recovering the catalyst, avoids the negative influence caused by adding catalyst corrosion equipment, is economical, simple and environment-friendly, and the yield of the 5-hydroxymethylfurfural can reach 36% at most under the condition of not adding the additional catalyst.
In addition, the invention adds a proper amount of water into the deep eutectic solvent, which not only can reduce the viscosity of the reaction system, but also can promote proton transfer and accelerate the reaction rate, thereby reducing side reactions caused by glucose accumulation and improving the yield of 5-hydroxymethylfurfural.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
Example 1
The embodiment provides a method for preparing 5-hydroxymethylfurfural from glucose, which comprises the following steps:
s1, mixing water and a deep eutectic solvent to obtain a mixed solution;
s2, performing airtight mixing reaction on the glucose and the mixed solution in the S1 to obtain 5-hydroxymethylfurfural;
the deep eutectic solvent in S1 is a mixture of quaternary ammonium salt and organic carboxylic acid, and the molar ratio of the quaternary ammonium salt to the organic carboxylic acid is 1:2;
the mass percentage of water in the mixed solution is 40wt%;
s2, the reaction temperature is 150 ℃, the reaction time is 1h, and the concentration of the glucose solution is 25g/L;
in S1, the quaternary ammonium salt is triethylbenzyl ammonium chloride, and the organic carboxylic acid is formic acid.
In this example, triethylbenzyl ammonium chloride and formic acid are stirred and mixed until a deep eutectic solvent is obtained by clarification, the mixing temperature can be 50 ℃, and the stirring speed can be 800rpm;
in this example, the mass of water was 16g, the mass of deep eutectic solvent was 24g, the mass of glucose was 1g, and the stirring speed was 600rpm in a high-pressure stirring vessel for stirring and mixing reaction.
Example 2
The embodiment provides a method for preparing 5-hydroxymethylfurfural from glucose, which comprises the following steps:
s1, mixing water and a deep eutectic solvent to obtain a mixed solution;
s2, performing airtight mixing reaction on the glucose and the mixed solution in the S1 to obtain 5-hydroxymethylfurfural;
the deep eutectic solvent in S1 is a mixture of quaternary ammonium salt and organic carboxylic acid, and the molar ratio of the quaternary ammonium salt to the organic carboxylic acid is 1:2;
the mass percentage of water in the mixed solution is 30wt%;
s2, the reaction temperature is 150 ℃, the reaction time is 1h, and the concentration of the glucose solution is 25g/L;
in S1, the quaternary ammonium salt is triethylbenzyl ammonium chloride, and the organic carboxylic acid is levulinic acid.
In this example, triethylbenzyl ammonium chloride and levulinic acid are stirred and mixed until a deep eutectic solvent is obtained by clarification, the mixing temperature can be 25 ℃, and the stirring speed can be 600rpm;
in this example, the mass of water in S2 was 12g, the mass of deep eutectic solvent was 28g, the mass of glucose was 1g, and the stirring speed was 800rpm in a high-pressure stirring vessel.
Example 3
The embodiment provides a method for preparing 5-hydroxymethylfurfural from glucose, which comprises the following steps:
s1, mixing water and a deep eutectic solvent to obtain a mixed solution;
s2, performing airtight mixing reaction on the glucose and the mixed solution in the S1 to obtain 5-hydroxymethylfurfural;
the deep eutectic solvent in S1 is a mixture of quaternary ammonium salt and organic carboxylic acid, and the molar ratio of the quaternary ammonium salt to the organic carboxylic acid is 1:2;
the mass percentage of water in the mixed solution is 30wt%;
s2, the reaction temperature is 150 ℃, the reaction time is 1h, and the concentration of the glucose solution is 25g/L;
in S1, the quaternary ammonium salt is tributyl methyl ammonium chloride, and the organic carboxylic acid is formic acid.
In this example, tributyl methyl ammonium chloride and formic acid are mixed until the mixture is clarified to obtain deep eutectic solvent, the mixing temperature can be 45 ℃, and the stirring speed can be 600rpm;
in this example, the mass of water in S2 was 12g, the mass of deep eutectic solvent was 28g, the mass of glucose was 1g, and the stirring speed was 200rpm in a high-pressure stirring vessel.
Example 4
The embodiment provides a method for preparing 5-hydroxymethylfurfural from glucose, which comprises the following steps:
s1, mixing water and a deep eutectic solvent to obtain a mixed solution;
s2, performing airtight mixing reaction on the glucose and the mixed solution in the S1 to obtain 5-hydroxymethylfurfural;
the deep eutectic solvent in S1 is a mixture of quaternary ammonium salt and organic carboxylic acid, and the molar ratio of the quaternary ammonium salt to the organic carboxylic acid is 1:2;
the mass percentage of water in the mixed solution is 40wt%;
the reaction temperature in S2 is 130 ℃, the reaction time is 0.5h, and the concentration of glucose solution is 50g/L;
in S1, the quaternary ammonium salt is triethylbenzyl ammonium chloride, and the organic carboxylic acid is lactic acid.
In this example, triethylbenzyl ammonium chloride and lactic acid were mixed with stirring until a clear deep eutectic solvent was obtained, the mixing temperature could be 25 ℃, and the stirring speed could be 800rpm;
in this example, the mass of water in S2 was 16g, the mass of deep eutectic solvent was 24g, the mass of glucose was 2g, and the stirring speed was 600rpm in a high-pressure stirring vessel.
Example 5
The embodiment provides a method for preparing 5-hydroxymethylfurfural from glucose, which comprises the following steps:
s1, mixing water and a deep eutectic solvent to obtain a mixed solution;
s2, performing airtight mixing reaction on the glucose and the mixed solution in the S1 to obtain 5-hydroxymethylfurfural;
the deep eutectic solvent in S1 is a mixture of quaternary ammonium salt and organic carboxylic acid, and the molar ratio of the quaternary ammonium salt to the organic carboxylic acid is 1:2;
the mass percentage of water in the mixed solution is 40wt%;
the reaction temperature in S2 is 150 ℃, the reaction time is 1.5h, and the concentration of glucose solution is 25g/L;
in S1, the quaternary ammonium salt is triethylbenzyl ammonium chloride, and the organic carboxylic acid is citric acid.
In this example, triethylbenzyl ammonium chloride and citric acid were mixed until a deep eutectic solvent was obtained by clarification, the mixing temperature could be 50 ℃, and the stirring speed could be 800rpm;
in this example, the mass of water in S2 was 16g, the mass of deep eutectic solvent was 24g, the mass of glucose was 1g, and the stirring speed was 600rpm in a high-pressure stirring vessel.
Example 6
The embodiment provides a method for preparing 5-hydroxymethylfurfural from glucose, which comprises the following steps:
s1, mixing water and a deep eutectic solvent to obtain a mixed solution;
s2, performing airtight mixing reaction on the glucose and the mixed solution in the S1 to obtain 5-hydroxymethylfurfural;
the deep eutectic solvent in S1 is a mixture of quaternary ammonium salt and organic carboxylic acid, and the molar ratio of the quaternary ammonium salt to the organic carboxylic acid is 1:2;
the mass percentage of water in the mixed solution is 40wt%;
s2, the reaction temperature is 150 ℃, the reaction time is 1h, and the concentration of the glucose solution is 25g/L;
in S1, the quaternary ammonium salt is tetramethyl ammonium chloride, and the organic carboxylic acid is levulinic acid.
In this example, tetramethylammonium chloride and levulinic acid are mixed until a deep eutectic solvent is obtained by clarification, the mixing temperature can be 50 ℃, and the stirring speed can be 800rpm;
in this example, the mass of water in S2 was 16g, the mass of deep eutectic solvent was 24g, the mass of glucose was 1g, and the stirring speed was 600rpm in a high-pressure stirring vessel.
Example 7
This example provides a method for preparing 5-hydroxymethylfurfural from glucose, unlike example 1, in which the deep eutectic solvent in S1 is a mixture of a quaternary ammonium salt and an organic carboxylic acid in a molar ratio of 1:3, a step of; in S1, the quaternary ammonium salt is triethylbenzyl ammonium chloride, and the organic carboxylic acid is formic acid.
The remainder is the same as in example 1 and will not be described again here.
Example 8
This example provides a method for preparing 5-hydroxymethylfurfural from glucose, unlike example 1, in which the deep eutectic solvent in S1 is a mixture of a quaternary ammonium salt and an organic carboxylic acid in a molar ratio of 1:10; in S1, the quaternary ammonium salt is triethylbenzyl ammonium chloride, and the organic carboxylic acid is formic acid.
The remainder is the same as in example 1 and will not be described again here.
Example 9
This example provides a process for preparing 5-hydroxymethylfurfural from glucose, differing from example 1 in that the concentration of the glucose solution in S2 is 12.5g/L.
The mass of water in S2 is 16g, the mass of deep eutectic solvent is 24g, and the mass of glucose is 0.5g.
The remainder is the same as in example 1 and will not be described again here.
Example 10
This example provides a process for preparing 5-hydroxymethylfurfural from glucose, unlike example 1, in which the concentration of the glucose solution in S2 is 100g/L.
The mass of water in S2 is 16g, the mass of deep eutectic solvent is 24g, and the mass of glucose is 4g.
The remainder is the same as in example 1 and will not be described again here.
Example 11
This example provides a process for preparing 5-hydroxymethylfurfural from glucose, differing from example 1 in that the mass percentage of water in the S1 mixed solution is 20wt%;
the remainder is the same as in example 1 and will not be described again here.
Example 12
This example provides a process for preparing 5-hydroxymethylfurfural from glucose, differing from example 1 in that the mass percentage of water in the S1 mixed solution is 60wt%;
the remainder is the same as in example 1 and will not be described again here.
Example 13
This example provides a process for preparing 5-hydroxymethylfurfural from glucose, differing from example 1 in that the mass percentage of water in the S1 mixed solution is 5wt%;
the remainder is the same as in example 1 and will not be described again here.
Example 14
This example provides a process for preparing 5-hydroxymethylfurfural from glucose, differing from example 1 in that the mass percentage of water in the S1 mixed solution is 80wt%;
the remainder is the same as in example 1 and will not be described again here.
Example 15
This example provides a method for preparing 5-hydroxymethylfurfural from glucose, unlike example 1, in which the deep eutectic solvent in S1 is a mixture of a quaternary ammonium salt and an organic carboxylic acid in a molar ratio of 1:1, a step of; in S1, the quaternary ammonium salt is triethylbenzyl ammonium chloride, and the organic carboxylic acid is formic acid.
The remainder is the same as in example 1 and will not be described again here.
Example 16
This example provides a process for preparing 5-hydroxymethylfurfural from glucose, differing from example 1 in that the reaction temperature in S2 is 110 ℃ and the reaction time is 6h.
The remainder is the same as in example 1 and will not be described again here.
Example 17
This example provides a process for preparing 5-hydroxymethylfurfural from glucose, differing from example 1 in that the reaction temperature in S2 was 170 ℃ and the reaction time was 0.1h.
The remainder is the same as in example 1 and will not be described again here.
Example 18
This example provides a process for preparing 5-hydroxymethylfurfural from glucose, unlike example 1, in which the concentration of the glucose solution in S2 is 200g/L.
The mass of the water in S2 is 16g, the mass of the deep eutectic solvent is 24g, the mass of the glucose is 8g,
the remainder is the same as in example 1 and will not be described again here.
Comparative example 1
This comparative example provides a process for the preparation of 5-hydroxymethylfurfural from glucose, except that, unlike example 1, 0.05g of aluminum chloride hexahydrate was also added as a catalyst.
The remainder is the same as in example 1 and will not be described again here.
Comparative example 2
This comparative example provides a method for preparing 5-hydroxymethylfurfural from glucose, unlike example 1, in which the deep eutectic solvent in S1 is tetramethylammonium chloride and ethanol.
The remainder is the same as in example 1 and will not be described again here.
Comparative example 3
This comparative example provides a process for preparing 5-hydroxymethylfurfural from glucose comprising the steps of:
s1, preparing a deep eutectic solvent;
s2, carrying out airtight mixing reaction on glucose and deep eutectic solvent to obtain 5-hydroxymethylfurfural;
the deep eutectic solvent in S1 is a mixture of quaternary ammonium salt and organic carboxylic acid, and the molar ratio of the quaternary ammonium salt to the organic carboxylic acid is 1:10;
s2, the reaction temperature is 150 ℃, the reaction time is 1h, and the concentration of the glucose solution is 25g/L;
in S1, the quaternary ammonium salt is triethylbenzyl ammonium chloride, and the organic carboxylic acid is formic acid.
In this comparative example, triethylbenzyl ammonium chloride and formic acid were mixed until a deep eutectic solvent was obtained by clarification at 50℃with a stirring speed of 800rpm;
in this comparative example, the mass of the deep eutectic solvent in S2 was 40g, the mass of glucose was 1g, and the mixture was stirred in a high-pressure stirring vessel at a stirring speed of 600rpm.
Comparative example 4
This comparative example provides a method for preparing 5-hydroxymethylfurfural from glucose, unlike example 1, in which the hydrogen bond acceptor of the deep eutectic solvent in S1 is betaine.
The remainder is the same as in example 1 and will not be described again here.
Result detection
(1) The 5-hydroxymethylfurfural yields of examples 1 to 18 and comparative examples 1 to 4 were tested as follows:
taking the reaction liquids obtained by the reactions of examples 1-18 and comparative examples 1-4, testing the concentration of 5-hydroxymethylfurfural by using a high performance liquid chromatograph of the model LC-20AT/SPD-M20, simultaneously measuring the volume of the reaction liquid, and calculating the yield of 5-hydroxymethylfurfural.
The yield of 5-hydroxymethylfurfural was calculated according to the following formula:
hydroxymethylfurfural yield (%) = [ (5-hydroxymethylfurfural concentration: (volume of reaction solution/126.11 g/mol)/(glucose mass/180.16 g/mol) ]: 100
The detection results are shown in the following table 1.
(2) The viscosity of the mixed solution of example 1 and the deep eutectic solvent of comparative example 3 were measured with a viscosity tester.
(3) The concentrations of levulinic acid in example 1, example 12 and comparative example 3 were measured by high performance liquid chromatography.
Table 1: yield of 5-hydroxymethylfurfural prepared in examples 1 to 18 and comparative examples 1 to 4
| Sequence number | Yield of 5-hydroxymethylfurfural (%) |
| Example 1 | 36 |
| Example 2 | 32 |
| Example 3 | 28 |
| Example 4 | 30 |
| Example 5 | 28 |
| Example 6 | 34 |
| Example 7 | 32 |
| Example 8 | 12 |
| Example 9 | 25 |
| Example 10 | 27 |
| Example 11 | 36 |
| Example 12 | 35 |
| Example 13 | 31 |
| Example 14 | 34 |
| Example 15 | 31 |
| Example 16 | 19 |
| Example 17 | 17 |
| Example 18 | 12 |
| Comparative example 1 | 24 |
| Comparative example 2 | 0 |
| Comparative example 3 | 10 |
| Comparative example 4 | 10 |
The viscosity of the mixed solution in step S1 of example 8 was 15cp, the viscosity of the deep eutectic solvent in step S1 of comparative example 3 was 40cp, the yield of 5-hydroxymethylfurfural obtained in example 8 was 12%, and the yield of 5-hydroxymethylfurfural obtained in comparative example 3 was 10%, indicating that not only the viscosity was decreased but also the yield of 5-hydroxymethylfurfural was increased after the addition of water. The viscosity of the deep eutectic solvent can be reduced by water, so that the problem that mass transfer is difficult and yield is reduced due to the fact that glucose is difficult to mix with the deep eutectic solvent uniformly due to excessive viscosity is avoided; in addition, water is also used as a hydrogen bond donor, and the quaternary ammonium salt can form a hydrogen bond with water, so that levulinic acid byproducts generated by hydration reaction of water and 5-hydroxymethylfurfural can be avoided, the 5-hydroxymethylfurfural can exist stably, and the yield of the 5-hydroxymethylfurfural is further improved.
In comparative example 3, the concentration of the byproduct levulinic acid was 0g/L, and the yield of 5-hydroxymethylfurfural was 10%; in example 1, the mass percentage of water in the S1 mixed solution is 40%, the concentration of the byproduct levulinic acid is 0.76g/L, and the yield of 5-hydroxymethylfurfural is 36%; in test example 12, the mass percentage of water in the S1 mixed solution is 60%, the concentration of the byproduct levulinic acid is 1.13g/L, and the yield of 5-hydroxymethylfurfural is 35%; in example 14, the mass percentage of water in the S1 mixed solution was 80%, the concentration of the byproduct levulinic acid was 0.45g/L, and the yield of 5-hydroxymethylfurfural was 34%.
It can be seen from comparative example 3, example 1, example 12 and example 14 that the yield of 5-hydroxymethylfurfural can only reach 10% without the addition of water, although no levulinic acid is produced as a by-product. Although the yield of 5-hydroxymethylfurfural in example 12 was lower than that in example 1, the concentration of levulinic acid in example 12 was significantly higher than that in example 1, indicating that the concentration of 5-hydroxymethylfurfural produced in example 12 was high, but a larger portion of 5-hydroxymethylfurfural was converted to acetopropylene. The water content of example 14 was twice that of example 1, and the yield of 5-hydroxymethylfurfural and the concentration of levulinic acid as a by-product were lower than those of example 1, indicating that too high a water content would decrease the concentration of 5-hydroxymethylfurfural and the concentration of levulinic acid generated by side reaction of 5-hydroxymethylfurfural would also decrease.
It can be seen from example 1 and comparative example 1 that the yield of 5-hydroxymethylfurfural was 24% after adding aluminum chloride hexahydrate as a catalyst to the system, but the present invention did not add a catalyst, and the yield of 5-hydroxymethylfurfural was up to 36%. According to the invention, no additional catalyst is added, quaternary ammonium salt and carboxylic acid are selected as deep eutectic solvents, and glucose can be catalyzed to generate 5-hydroxymethylfurfural. Moreover, comparative example 1 has a problem of catalyst recovery in the subsequent step after addition of aluminum chloride hexahydrate.
As can be seen from example 1 and comparative example 2, after the formic acid was changed to ethanol, the yield of 5-hydroxymethylfurfural was 0 because the deep eutectic solvent formed by triethylbenzyl ammonium chloride and ethanol did not have a catalytic effect, and ethanol did not provide an acidic catalytic environment, and thus, glucose was not catalyzed to form 5-hydroxymethylfurfural.
As can be seen from example 1 and comparative example 4, when the quaternary ammonium salt is betaine, the yield of 5-hydroxymethylfurfural is lower, and is only 10%, because betaine is a zwitterionic and not a quaternary ammonium salt, and the betaine contains no chloride ions, so that the chloride ions have strong electronegativity, can form hydrogen bonding with glucose and 5-hydroxymethylfurfural, stabilize glucose and 5-hydroxymethylfurfural, reduce side reactions, and improve yield.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (5)
1. A method for preparing 5-hydroxymethylfurfural from glucose, comprising the steps of:
s1, mixing water and a deep eutectic solvent to obtain a mixed solution;
s2, performing airtight mixing reaction on the glucose and the mixed solution in the S1 to obtain 5-hydroxymethylfurfural;
wherein the deep eutectic solvent in S1 is a mixture of quaternary ammonium salt and organic carboxylic acid, and the molar ratio of the quaternary ammonium salt to the organic carboxylic acid is 1 (1-10);
the mass percentage of water in the mixed solution is 5-80 wt%;
the reaction temperature in S2 is 110-170 ℃ and the reaction time is 0.1-6 h;
the quaternary ammonium salt is triethylbenzyl ammonium chloride;
the organic carboxylic acid is formic acid;
the concentration of the glucose solution in the S2 is 12.5-100 g/L.
2. The method for preparing 5-hydroxymethylfurfural from glucose according to claim 1, wherein the mass percentage of water in the S1 mixed solution is 20 to 60wt%.
3. The method for preparing 5-hydroxymethylfurfural from glucose according to claim 1, wherein the concentration of the glucose solution in S2 is 25 to 50g/L.
4. The method for preparing 5-hydroxymethylfurfural from glucose according to claim 1, wherein the molar ratio of quaternary ammonium salt to organic carboxylic acid in S1 is 1 (2 to 3).
5. The method for preparing 5-hydroxymethylfurfural from glucose according to claim 1, wherein the reaction temperature in S2 is 130 ℃ to 150 ℃ and the reaction time is 0.5 to 1.5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110876311.4A CN113651781B (en) | 2021-07-31 | 2021-07-31 | Method for preparing 5-hydroxymethylfurfural from glucose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110876311.4A CN113651781B (en) | 2021-07-31 | 2021-07-31 | Method for preparing 5-hydroxymethylfurfural from glucose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113651781A CN113651781A (en) | 2021-11-16 |
| CN113651781B true CN113651781B (en) | 2024-01-19 |
Family
ID=78479064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110876311.4A Active CN113651781B (en) | 2021-07-31 | 2021-07-31 | Method for preparing 5-hydroxymethylfurfural from glucose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113651781B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116178316A (en) * | 2021-11-29 | 2023-05-30 | 中国科学院宁波材料技术与工程研究所 | Method for preparing 5-hydroxymethyl-2-furaldehyde by using fructose |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087372A (en) * | 2019-12-26 | 2020-05-01 | 长春工业大学 | Method for preparing 5-HMF by catalyzing fructose dehydration through low eutectic solvent |
| CN112424179A (en) * | 2018-07-13 | 2021-02-26 | 诺瓦蒙特股份公司 | Method for producing and separating 5-hydroxymethylfurfural by using quaternary ammonium salt |
| CN112608289A (en) * | 2020-12-21 | 2021-04-06 | 中国科学院广州能源研究所 | Method for efficiently preparing 5-hydroxymethylfurfural by catalyzing bio-based fructose through organic solvent-ionic liquid composite system |
| CN112812081A (en) * | 2021-01-15 | 2021-05-18 | 中国科学院广州能源研究所 | Method for selectively preparing 5-hydroxymethylfurfural by catalyzing carbohydrate in water-ionic liquid mixed system |
-
2021
- 2021-07-31 CN CN202110876311.4A patent/CN113651781B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112424179A (en) * | 2018-07-13 | 2021-02-26 | 诺瓦蒙特股份公司 | Method for producing and separating 5-hydroxymethylfurfural by using quaternary ammonium salt |
| CN111087372A (en) * | 2019-12-26 | 2020-05-01 | 长春工业大学 | Method for preparing 5-HMF by catalyzing fructose dehydration through low eutectic solvent |
| CN112608289A (en) * | 2020-12-21 | 2021-04-06 | 中国科学院广州能源研究所 | Method for efficiently preparing 5-hydroxymethylfurfural by catalyzing bio-based fructose through organic solvent-ionic liquid composite system |
| CN112812081A (en) * | 2021-01-15 | 2021-05-18 | 中国科学院广州能源研究所 | Method for selectively preparing 5-hydroxymethylfurfural by catalyzing carbohydrate in water-ionic liquid mixed system |
Non-Patent Citations (2)
| Title |
|---|
| "Insights into the Play of Novel Brønsted Acid-Based Deep Eutectic Solvents for the Conversion of Glucose into 5‑Hydroxymethylfurfural without Additional Catalysts";Shunhui Tao, et al.,;《 Ind. Eng. Chem. Res. 》;第61卷;第11645−11654页 * |
| "低共熔溶剂体系中葡萄糖高效转化制备5-羟甲基糠醛的研究";陶顺辉;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》(第01期);第B016-587页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113651781A (en) | 2021-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| He et al. | Production of levoglucosenone and 5-hydroxymethylfurfural from cellulose in polar aprotic solvent–water mixtures | |
| Zuo et al. | An effective pathway for converting carbohydrates to biofuel 5-ethoxymethylfurfural via 5-hydroxymethylfurfural with deep eutectic solvents (DESs) | |
| Hu et al. | Upgrading biomass-derived furans via acid-catalysis/hydrogenation: the remarkable difference between water and methanol as the solvent | |
| Agirrezabal-Telleria et al. | Furfural production from xylose+ glucose feedings and simultaneous N 2-stripping | |
| CN103797004B (en) | For the preparation of the method for furfural | |
| CN101812039B (en) | Method for generating 5-hydroxymethylfurfural by using ionic liquid catalysis | |
| US10428039B2 (en) | Process for preparing furan-2,5-dicarboxylic acid | |
| CN110183403B (en) | Method for converting fructose into 5-hydroxymethylfurfural by using ionic liquid as catalyst | |
| CN101811066A (en) | Catalyst for synthesizing 5-hydroxymethylfurfural by hexose dehydration and method for synthesizing 5-hydroxymethylfurfural | |
| CN113651781B (en) | Method for preparing 5-hydroxymethylfurfural from glucose | |
| US20180319759A1 (en) | A process for preparing a mixture comprising 5-(hydroxymethyl) furfural and specific hmf esters | |
| CN112608289A (en) | Method for efficiently preparing 5-hydroxymethylfurfural by catalyzing bio-based fructose through organic solvent-ionic liquid composite system | |
| CN113402485A (en) | Method for preparing 5-hydroxymethylfurfural by converting cellulose in composite molten salt hydrate | |
| WO2023226181A1 (en) | Method for preparing 2,5-furandicarboxylic acid by using furfural | |
| CN111995602A (en) | Method for synthesizing 5-hydroxymethylfurfural by utilizing acidic resin to catalyze fructose | |
| Zhang et al. | Conversion of bio-carbohydrates to 5-hydroxymethylfurfural in three-component deep eutectic solvent | |
| Song et al. | Sugar dehydration to 5-hydroxymethylfurfural in mixtures of water/[Bmim] Cl catalyzed by iron sulfate | |
| CN109280039B (en) | Method for preparing 5-hydroxymethylfurfural based on cellulose conversion | |
| CN107722030A (en) | A kind of method for preparing dissident's sugar alcohol | |
| CN108047021B (en) | Preparation method of levulinic acid | |
| CN107141206B (en) | Method for preparing acrolein by catalytic conversion of glycerol | |
| CN107540520B (en) | Method for preparing pyromellitic acid or trimellitic acid from pinacol | |
| Galkin et al. | A catalytic system for the selective conversion of cellulose to 5-hydroxymethylfurfural under mild conditions | |
| CN112812081A (en) | Method for selectively preparing 5-hydroxymethylfurfural by catalyzing carbohydrate in water-ionic liquid mixed system | |
| CN111531119B (en) | Fructose modified furan resin for casting and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |