CN113651781A - Method for preparing 5-hydroxymethylfurfural from glucose - Google Patents
Method for preparing 5-hydroxymethylfurfural from glucose Download PDFInfo
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- CN113651781A CN113651781A CN202110876311.4A CN202110876311A CN113651781A CN 113651781 A CN113651781 A CN 113651781A CN 202110876311 A CN202110876311 A CN 202110876311A CN 113651781 A CN113651781 A CN 113651781A
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- hydroxymethylfurfural
- glucose
- quaternary ammonium
- ammonium salt
- carboxylic acid
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- 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 119
- 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 43
- 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 55
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000011259 mixed solution Substances 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 230000035484 reaction time Effects 0.000 claims abstract description 15
- 150000001735 carboxylic acids Chemical class 0.000 claims description 47
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims description 36
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 28
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 19
- 229940040102 levulinic acid Drugs 0.000 claims description 18
- 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 14
- 235000019253 formic acid Nutrition 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 25
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 27
- 238000003756 stirring Methods 0.000 description 14
- 238000007086 side reaction Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 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
- 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
- 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
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 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
- 239000012295 chemical reaction liquid Substances 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
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- -1 coatings Substances 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000006317 isomerization 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
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011084 recovery 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
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000000576 coating method Methods 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
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940079593 drug Drugs 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
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent 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
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 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
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, carrying out closed mixing reaction on the glucose and the mixed solution in the S1 to obtain 5-hydroxymethylfurfural; the deep eutectic solvent in the 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 of the invention does not need to add 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-hydroxymethylfurfurral, 5-HMF) is an important biomass-based platform compound, and 5-hydroxymethylfurfural and derivatives thereof are widely applied to industries such as fuels, coatings, medicines, degradable materials and the like. 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 with the existing petroleum industrial system. 5-hydroxymethylfurfural can be produced by dehydration of glucose and fructose. If 5-hydroxymethylfurfural is produced from fructose, the yield is higher than that produced from glucose because the specific furan ring configuration of fructose is easily converted into 5-hydroxymethylfurfural. However, glucose requires isomerization to fructose and then dehydration to 5-hydroxymethylfurfural, and the conversion of glucose to 5-hydroxymethylfurfural is low due to the addition of the isomerization step. However, fructose is much more expensive than glucose, and the preparation of 5-hydroxymethylfurfural from glucose is economically more feasible.
In the prior art, various catalysts are used for preparing 5-hydroxymethylfurfural from glucose in order to improve the yield. For example, chinese patent CN107556271 discloses a method for preparing and separating 5-hydroxymethylfurfural from glucose, which utilizes a deep eutectic solvent formed by glucose and choline chloride as a reaction phase and an organic solvent as an extraction phase to form a bi-directional reaction system, and the yield of the bi-directional reaction system can reach 36.23% at most. However, the method introduces a solid acid catalyst prepared from activated carbon, sulfuric acid and metal salt, the sulfuric acid catalyst can corrode equipment, the carbon deposition of the activated carbon in an acid system is serious and easy to inactivate, and the metal salt has the problem that heavy metal pollutes the environment, so that the problem that the solid acid catalyst needs to be recovered subsequently is also existed.
In order to solve the problem that the catalyst 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, which uses p-toluenesulfonic acid and choline chloride with strong acidity as eutectic solvents, and directly degrades cellulose to obtain 5-hydroxymethylfurfural without adding additional catalyst. However, since this method does not add a catalyst, the yield of 5-hydroxymethylfurfural is only 10.2% at the maximum. Therefore, the yield of 5-hydroxymethylfurfural from glucose is yet to be further improved without using a catalyst.
Disclosure of Invention
The invention aims to solve the technical problems that in the existing method for preparing 5-hydroxymethylfurfural by using glucose, the problem of catalyst recovery can be caused by using a catalyst, and the defect that the yield of 5-hydroxymethylfurfural is low due to the fact that only a deep eutectic solvent is used without using a catalyst are overcome, and the method for preparing 5-hydroxymethylfurfural by using glucose is provided.
The above purpose of the invention is realized 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, carrying out closed mixing reaction on the glucose and the mixed solution in the S1 to obtain 5-hydroxymethylfurfural;
the deep eutectic solvent in the 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 method selects quaternary ammonium salt and organic carboxylic acid as deep eutectic solvent, can be used as reaction solvent for preparing 5-hydroxymethylfurfural from glucose, and can also be used as catalyst for catalyzing glucose, the reaction temperature in the method is 110-170 ℃, water exists in the form of hydronium ions at the high temperature in the range, proton transfer can be promoted, the reaction rate is accelerated, so that side reaction caused by accumulation of glucose is reduced, and the yield of 5-hydroxymethylfurfural is improved; in addition, the water can also reduce the viscosity of the deep eutectic solvent, so that the yield reduction caused by mass transfer difficulty due to the difficulty in uniformly mixing the glucose and the deep eutectic solvent caused by overlarge viscosity 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 a levulinic acid byproduct generated by hydration reaction of the water and the 5-hydroxymethylfurfural can be avoided, and the 5-hydroxymethylfurfural can stably exist. The water is added in an excessive amount, the deep eutectic solvent is not enough to confine all water, and the deep eutectic solvent still has side reaction with the product 5-hydroxymethylfurfural, so that the yield of the 5-hydroxymethylfurfural is reduced, and therefore, 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, a closed reaction is required in a high-pressure reactor, and the pressure actually generated by the closed reaction is determined by various factors such as temperature and reaction degree.
Preferably, the mass percent of water in the S1 mixed solution is 20-60 wt%. The mass percentage of the water is in the range, so that the viscosity of a reaction system can be reduced, the reaction rate can be accelerated, the side reaction caused by glucose accumulation can be prevented, and the water can be confined by a 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, the yield of the 5-hydroxymethylfurfural is reduced, and redundant hydrogen protons in the deep eutectic solvent with too low concentration of glucose can promote the generation of the side reaction, and the yield is reduced.
Preferably, the concentration of the glucose solution in S2 is 25-50 g/L. The concentration of the glucose in the range does not cause side reactions due to glucose accumulation, and does not cause excessive reduction of the yield of the 5-hydroxymethylfurfural due to promotion of side reactions by excess hydrogen protons in the deep eutectic solvent.
Preferably, the molar ratio of the quaternary ammonium salt to the organic carboxylic acid in S1 is 1 (2-3). A part of hydrogen protons in more organic carboxylic acids and quaternary ammonium salt can form a hydrogen bond network, and the other part of hydrogen protons provide an acidic environment, so that the glucose is catalyzed to react to generate the 5-hydroxymethylfurfural. The content of the organic carboxylic acid is increased, more hydrogen protons can be released for catalyzing the dehydration of glucose to generate 5-hydroxymethylfurfural, and the yield of the 5-hydroxymethylfurfural is increased. However, if the content of the organic carboxylic acid is too high, the acidity is increased to promote not only the dehydration of glucose to 5-hydroxymethylfurfural but also the polymerization of 5-hydroxymethylfurfural to humins, and the selectivity of byproducts is increased, thereby 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 meanwhile, the side reaction is not enhanced due to overhigh temperature. Within the range, the reaction time can be fully reacted, the 5-hydroxymethylfurfural can be prevented from beginning to polymerize, and the yield of the 5-hydroxymethylfurfural is improved.
Preferably, the quaternary ammonium salt is one or more of triethylbenzylammonium chloride, tributylmethylammonium chloride or tetramethylammonium 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 reactions and improve the yield.
Further preferably, the quaternary ammonium salt is triethylbenzylammonium chloride. The triethyl benzyl ammonium chloride has a benzene ring structure and excellent phase transfer capacity, can be used as a catalyst of organic reaction, is beneficial to reducing the melting point and viscosity of the 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 small, more hydrogen protons can be released, part of the hydrogen protons can form a hydrogen bond network with quaternary ammonium salt, and the other part of the hydrogen protons provide an acidic environment, so that the glucose is catalyzed to react to generate the 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 the deep eutectic solvent, can be used as a reaction solvent for preparing the 5-hydroxymethylfurfural from the glucose, and can also be used as a catalyst for catalyzing the glucose, so that no additional catalyst is needed to be added in the method, the step of recovering the catalyst is reduced, the negative influence caused by the corrosion of equipment due to the addition of the catalyst is avoided, the method is economical, simple, green and environment-friendly, and the yield of the 5-hydroxymethylfurfural can reach 36 percent at most under the condition that no additional catalyst is added.
In addition, the proper amount of water is added into the deep eutectic solvent, so that the viscosity of a reaction system can be reduced, proton transfer can be promoted, the reaction rate is accelerated, side reactions caused by glucose accumulation are reduced, and the yield of the 5-hydroxymethylfurfural is improved.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
This example provides 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, carrying out closed 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 percent of water in the mixed solution is 40 wt%;
in the S2, the reaction temperature is 150 ℃, the reaction time is 1h, and the concentration of the glucose solution is 25 g/L;
in S1, the quaternary ammonium salt is triethyl benzyl ammonium chloride, and the organic carboxylic acid is formic acid.
In the embodiment, triethyl benzyl ammonium chloride and formic acid are stirred and mixed until the mixture is clarified to obtain the deep eutectic solvent, wherein the mixing temperature can be 50 ℃, and the stirring speed can be 800 rpm;
in this example, the mass of water was 16g, the mass of deep eutectic solvent was 24g, and the mass of glucose was 1g, and the reaction was stirred and mixed in a high-pressure stirred tank at a stirring speed of 600 rpm.
Example 2
This example provides 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, carrying out closed 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 percent of water in the mixed solution is 30 wt%;
in the S2, the reaction temperature is 150 ℃, the reaction time is 1h, and the concentration of the glucose solution is 25 g/L;
in S1, the quaternary ammonium salt is triethyl benzyl ammonium chloride, and the organic carboxylic acid is levulinic acid.
In the embodiment, triethyl benzyl ammonium chloride and levulinic acid are stirred and mixed until the mixture is clarified to obtain the deep eutectic solvent, the mixing temperature can be 25 ℃, and the stirring speed can be 600 rpm;
in this example, the mass of water in S2 was 12g, the mass of deep eutectic solvent was 28g, and the mass of glucose was 1g, and the reaction was stirred and mixed in a high-pressure stirred tank at a stirring speed of 800 rpm.
Example 3
This example provides 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, carrying out closed 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 percent of water in the mixed solution is 30 wt%;
in the S2, the reaction temperature is 150 ℃, the reaction time is 1h, and the concentration of the glucose solution is 25 g/L;
in S1, the quaternary ammonium salt is tributyl methyl ammonium chloride, and the organic carboxylic acid is formic acid.
In the embodiment, tributylmethylammonium chloride and formic acid are stirred and mixed until the mixture is clarified to obtain the deep eutectic solvent, wherein the mixing temperature can be 45 ℃, and the stirring speed can be 600 rpm;
in this example, the mass of water in S2 was 12g, the mass of deep eutectic solvent was 28g, and the mass of glucose was 1g, and the reaction was stirred and mixed in a high-pressure stirred tank at a stirring speed of 200 rpm.
Example 4
This example provides 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, carrying out closed 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 percent of water in the mixed solution is 40 wt%;
in the S2, the reaction temperature is 130 ℃, the reaction time is 0.5h, and the concentration of the glucose solution is 50 g/L;
in S1, the quaternary ammonium salt is triethyl benzyl ammonium chloride, and the organic carboxylic acid is lactic acid.
In the embodiment, triethyl benzyl ammonium chloride and lactic acid are stirred and mixed until the mixture is clarified to obtain the deep eutectic solvent, wherein the mixing temperature can be 25 ℃, and the stirring speed can be 800 rpm;
in this example, the mass of water in S2 was 16g, the mass of deep eutectic solvent was 24g, and the mass of glucose was 2g, and the reaction was stirred and mixed in a high-pressure stirred tank at a stirring speed of 600 rpm.
Example 5
This example provides 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, carrying out closed 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 percent of water in the mixed solution is 40 wt%;
in the S2, the reaction temperature is 150 ℃, the reaction time is 1.5h, and the concentration of the glucose solution is 25 g/L;
in S1, the quaternary ammonium salt is triethyl benzyl ammonium chloride, and the organic carboxylic acid is citric acid.
In the embodiment, triethyl benzyl ammonium chloride and citric acid are mixed until clarification to obtain the deep eutectic solvent, the mixing temperature can be 50 ℃, and the stirring speed can be 800 rpm;
in this example, the mass of water in S2 was 16g, the mass of deep eutectic solvent was 24g, and the mass of glucose was 1g, and the reaction was stirred and mixed in a high-pressure stirred tank at a stirring speed of 600 rpm.
Example 6
This example provides 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, carrying out closed 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 percent of water in the mixed solution is 40 wt%;
in the S2, the reaction temperature is 150 ℃, the reaction time is 1h, and the concentration of the glucose solution is 25 g/L;
in S1, the quaternary ammonium salt is tetramethylammonium chloride, and the organic carboxylic acid is levulinic acid.
In the embodiment, tetramethylammonium chloride and levulinic acid are mixed until the mixture is clarified to obtain the deep eutectic solvent, the mixing temperature can be 50 ℃, and the stirring speed can be 800 rpm;
in this example, the mass of water in S2 was 16g, the mass of deep eutectic solvent was 24g, and the mass of glucose was 1g, and the reaction was stirred and mixed in a high-pressure stirred tank at a stirring speed of 600 rpm.
Example 7
This example provides a process for preparing 5-hydroxymethylfurfural from glucose, differing from example 1 in that the deep eutectic solvent in S1 is a mixture of a quaternary ammonium salt and an organic carboxylic acid, the molar ratio of the quaternary ammonium salt to the organic carboxylic acid being 1: 3; in S1, the quaternary ammonium salt is triethyl benzyl ammonium chloride, and the organic carboxylic acid is formic acid.
The rest is the same as embodiment 1, and the description is omitted here.
Example 8
This example provides a process for preparing 5-hydroxymethylfurfural from glucose, differing from example 1 in that the deep eutectic solvent in S1 is a mixture of a quaternary ammonium salt and an organic carboxylic acid, the molar ratio of the quaternary ammonium salt to the organic carboxylic acid being 1: 10; in S1, the quaternary ammonium salt is triethyl benzyl ammonium chloride, and the organic carboxylic acid is formic acid.
The rest is the same as embodiment 1, and the description is omitted here.
Example 9
This example provides a process for producing 5-hydroxymethylfurfural from glucose, differing from example 1 in that the concentration of the glucose solution in S2 was 12.5 g/L.
The mass of water in S2 was 16g, the mass of deep eutectic solvent was 24g, and the mass of glucose was 0.5 g.
The rest is the same as embodiment 1, and the description is omitted here.
Example 10
This example provides a process for producing 5-hydroxymethylfurfural from glucose, differing from example 1 in that the concentration of the glucose solution in S2 is 100 g/L.
The mass of water in S2 was 16g, the mass of deep eutectic solvent was 24g, and the mass of glucose was 4 g.
The rest is the same as embodiment 1, and the description is omitted here.
Example 11
This example provides a method for preparing 5-hydroxymethylfurfural from glucose, which is different from example 1 in that the mass percentage of water in the S1 mixed solution is 20 wt%;
the rest is the same as embodiment 1, and the description is omitted here.
Example 12
This example provides a method for preparing 5-hydroxymethylfurfural from glucose, which is different from example 1 in that the mass percentage of water in the S1 mixed solution is 60 wt%;
the rest is the same as embodiment 1, and the description is omitted here.
Example 13
This example provides a method for preparing 5-hydroxymethylfurfural from glucose, which is different from example 1 in that the mass percentage of water in the S1 mixed solution is 5 wt%;
the rest is the same as embodiment 1, and the description is omitted here.
Example 14
This example provides a method for preparing 5-hydroxymethylfurfural from glucose, which is different from example 1 in that the mass percentage of water in the S1 mixed solution is 80 wt%;
the rest is the same as embodiment 1, and the description is omitted here.
Example 15
This example provides a process for preparing 5-hydroxymethylfurfural from glucose, differing from example 1 in that the deep eutectic solvent in S1 is a mixture of a quaternary ammonium salt and an organic carboxylic acid, the molar ratio of the quaternary ammonium salt to the organic carboxylic acid being 1: 1; in S1, the quaternary ammonium salt is triethyl benzyl ammonium chloride, and the organic carboxylic acid is formic acid.
The rest is the same as embodiment 1, and the description is omitted 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 6 hours.
The rest is the same as embodiment 1, and the description is omitted 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 0.1 h.
The rest is the same as embodiment 1, and the description is omitted here.
Example 18
This example provides a process for producing 5-hydroxymethylfurfural from glucose, differing from example 1 in that the concentration of the glucose solution in S2 was 200 g/L.
S2, the mass of water is 16g, the mass of deep eutectic solvent is 24g, the mass of glucose is 8g,
the rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
This comparative example provides a process for preparing 5-hydroxymethylfurfural from glucose, which differs from example 1 by the addition of 0.05g of aluminum chloride hexahydrate as catalyst.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 2
This comparative example provides a method for preparing 5-hydroxymethylfurfural from glucose, and differs from example 1 in that the deep eutectic solvent in S1 is tetramethylammonium chloride and ethanol.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 3
The present comparative example provides a process for preparing 5-hydroxymethylfurfural from glucose, comprising the steps of:
s1, preparing a deep eutectic solvent;
s2, carrying out closed mixing reaction on glucose and a 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;
in the S2, the reaction temperature is 150 ℃, the reaction time is 1h, and the concentration of the glucose solution is 25 g/L;
in S1, the quaternary ammonium salt is triethyl benzyl ammonium chloride, and the organic carboxylic acid is formic acid.
In the comparative example, triethyl benzyl ammonium chloride and formic acid were mixed until clarified to obtain a deep eutectic solvent, the mixing temperature was 50 ℃, and the stirring speed was 800 rpm;
in this comparative example, the mass of the deep eutectic solvent in S2 was 40g, and the mass of glucose was 1g, and the reaction was stirred and mixed in a high-pressure stirred tank at a stirring speed of 600 rpm.
Comparative example 4
This comparative example provides a method for preparing 5-hydroxymethylfurfural from glucose, differing from example 1 in that the hydrogen bond acceptor of the deep eutectic solvent in S1 is betaine.
The rest is the same as embodiment 1, and the description is omitted here.
Result detection
(1) The 5-hydroxymethylfurfural yields of examples 1 to 18 and comparative examples 1 to 4 were tested by the following specific method:
taking reaction liquid obtained by the reaction of the examples 1 to 18 and the comparative examples 1 to 4, testing the concentration of the 5-hydroxymethylfurfural by using a high performance liquid chromatograph model LC-20AT/SPD-M20, measuring the volume of the reaction liquid, and calculating the yield of the 5-hydroxymethylfurfural.
The yield of 5-hydroxymethylfurfural was calculated according to the following formula:
hydroxymethylfurfural yield (%) - (5-hydroxymethylfurfural concentration · reaction liquid volume/126.11 g/mol)/(glucose mass/180.16 g/mol) ]. 100
The results of the measurements are shown in Table 1 below.
(2) The viscosity of the mixed solution of example 1 and the deep eutectic solvent of comparative example 3 was measured using a viscosity tester.
(3) The concentration of levulinic acid in example 1, example 12 and comparative example 3 was tested by high performance liquid chromatography.
Table 1: yields of 5-hydroxymethylfurfural prepared in examples 1 to 18 and comparative examples 1 to 4
| Serial number | 5-hydroxymethylfurfural yield (%) |
| 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%, which indicates that not only the viscosity decreased but also the yield of 5-hydroxymethylfurfural increased after the addition of water. The reason is that the water can reduce the viscosity of the deep eutectic solvent, and the reduction of yield caused by mass transfer difficulty due to the difficulty in uniformly mixing the glucose and the deep eutectic solvent caused by overlarge viscosity 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 a levulinic acid byproduct generated by hydration reaction of the water and the 5-hydroxymethylfurfural can be avoided, the 5-hydroxymethylfurfural can stably exist, and the yield of the 5-hydroxymethylfurfural is improved.
In comparative example 3, the concentration of the by-product 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 was 40%, the concentration of the by-product levulinic acid was 0.76g/L, and the yield of 5-hydroxymethylfurfural was 36%; in test example 12, the mass percentage of water in the S1 mixed solution was 60%, the concentration of the by-product levulinic acid was 1.13g/L, and the yield of 5-hydroxymethylfurfural was 35%; in example 14, the mass percentage of water in the S1 mixed solution was 80%, the concentration of the by-product levulinic acid was 0.45g/L, and the yield of 5-hydroxymethylfurfural was 34%.
As can be seen from comparative example 3, example 1, example 12 and example 14, the yield of 5-hydroxymethylfurfural reached only 10% without addition of water, although levulinic acid was not 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 much higher than that in example 1, indicating that the concentration of 5-hydroxymethylfurfural produced in example 12 was high, but a large portion of 5-hydroxymethylfurfural was converted into levulinic acid. Example 14, in which the content of water was twice that of example 1, showed that the yield of 5-hydroxymethylfurfural and the concentration of levulinic acid as a by-product were lower than those of example 1, indicating that an excessively high water content decreased the concentration of 5-hydroxymethylfurfural and decreased the concentration of levulinic acid produced as a by-product from 5-hydroxymethylfurfural.
As can be seen from example 1 and comparative example 1, the yield of 5-hydroxymethylfurfural was 24% after adding aluminum chloride hexahydrate as a catalyst to the system, however, the yield of 5-hydroxymethylfurfural reached 36% at the maximum without adding the catalyst according to the present invention. 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 after the addition of aluminum chloride hexahydrate.
From example 1 and comparative example 2, it can be seen that the yield of 5-hydroxymethylfurfural after formic acid was changed to ethanol was 0, because triethylbenzylammonium chloride and ethanol form a deep eutectic solvent with no catalytic effect, and ethanol does not provide an acidic catalytic environment and therefore cannot catalyze glucose to form 5-hydroxymethylfurfural.
From example 1 and comparative example 4, it can be seen that the yield of 5-hydroxymethylfurfural is low, only 10%, when the quaternary ammonium salt is betaine, because betaine is zwitterion and does not belong to quaternary ammonium salt, and betaine does not contain chloride ions, and chloride ions have strong electronegativity and can form hydrogen bonding with glucose and 5-hydroxymethylfurfural, stabilize glucose and 5-hydroxymethylfurfural, reduce side reactions and improve yield.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A method for preparing 5-hydroxymethylfurfural from glucose is characterized by comprising the following steps:
s1, mixing water and a deep eutectic solvent to obtain a mixed solution;
s2, carrying out closed mixing reaction on the glucose and the mixed solution in the S1 to obtain 5-hydroxymethylfurfural;
the deep eutectic solvent in the 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.
2. The method for preparing 5-hydroxymethylfurfural from glucose as claimed in claim 1, wherein the mass percentage of water in the S1 mixed solution is 20 to 60 wt%.
3. The method for producing 5-hydroxymethylfurfural from glucose as claimed in claim 1 or 2, wherein the concentration of the glucose solution in S2 is 12.5 to 100 g/L.
4. The method for preparing 5-hydroxymethylfurfural from glucose as claimed in claim 3, wherein the concentration of the glucose solution in S2 is 25 to 50 g/L.
5. The method for preparing 5-hydroxymethylfurfural from glucose as claimed in claim 1, wherein the molar ratio of the quaternary ammonium salt to the organic carboxylic acid in S1 is 1 (2-3).
6. The method for preparing 5-hydroxymethylfurfural from glucose as claimed in claim 1, wherein the reaction temperature in S2 is 130 ℃ to 150 ℃ and the reaction time is 0.5 to 1.5 hours.
7. The method of claim 1, wherein the quaternary ammonium salt is one or more of triethylbenzylammonium chloride, tributylmethylammonium chloride, or tetramethylammonium chloride.
8. The method of claim 7, wherein the quaternary ammonium salt is triethylbenzylammonium chloride.
9. The method of claim 1, wherein the organic carboxylic acid is one or more of formic acid, lactic acid, citric acid, or levulinic acid.
10. The method of claim 9, wherein the organic carboxylic acid is formic acid.
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