CN112778244B - Method for preparing 5-hydroxymethylfurfural by fructose dehydration - Google Patents
Method for preparing 5-hydroxymethylfurfural by fructose dehydration Download PDFInfo
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- CN112778244B CN112778244B CN202011502050.1A CN202011502050A CN112778244B CN 112778244 B CN112778244 B CN 112778244B CN 202011502050 A CN202011502050 A CN 202011502050A CN 112778244 B CN112778244 B CN 112778244B
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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 60
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000005715 Fructose Substances 0.000 title claims abstract description 39
- 229930091371 Fructose Natural products 0.000 title claims abstract description 39
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000018044 dehydration Effects 0.000 title abstract description 12
- 238000006297 dehydration reaction Methods 0.000 title abstract description 12
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 230000007704 transition Effects 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000002663 humin Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000011521 glass Substances 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- OXMIDRBAFOEOQT-UHFFFAOYSA-N 2,5-dimethyloxolane Chemical compound CC1CCC(C)O1 OXMIDRBAFOEOQT-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- YRLOVQGPXVWPQG-UHFFFAOYSA-N 3-(2-ethoxyethyl)furan-2-carbaldehyde Chemical compound CCOCCC=1C=COC=1C=O YRLOVQGPXVWPQG-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011259 mixed solution Substances 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
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0222—Sulfur-containing compounds comprising sulfonyl groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Saccharide Compounds (AREA)
- Furan Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 5-hydroxymethylfurfural by fructose dehydration. The method comprises the following steps: reacting a mixed reaction system containing fructose and diphenyl sulfoxide and/or a diphenyl sulfoxide derivative, cooling the mixed reaction system to perform phase transition, and separating the 5-hydroxymethylfurfural from a solvent to obtain the 5-hydroxymethylfurfural. In the invention, the diphenyl sulfoxide and/or the diphenyl sulfoxide derivative is/are used as a phase transition solvent with temperature response, is not mutually soluble with water, and is convenient for extracting 5-hydroxymethylfurfural in a system by water after the reaction is finished; compared with the prior art, the solvent used in the invention can realize effective separation of products, and is a preparation method with good potential industrial application prospect; meanwhile, the yield of the 5-hydroxymethylfurfural in the invention can reach 68.4 percent.
Description
Technical Field
The invention belongs to the technical field of biomass energy chemical preparation, particularly relates to a method for preparing 5-hydroxymethylfurfural by fructose dehydration, and particularly relates to a method for preparing 5-hydroxymethylfurfural by a fructose dehydration easily-separated solvent system.
Background
5-Hydroxymethylfurfural (HMF) is an important biomass-based platform compound, and a series of high value-added compounds can be derived by taking the HMF as a raw material, such as 2, 5-furandicarboxylic acid, 2, 5-dimethylfuran, 2, 5-dimethyltetrahydrofuran, ethoxyethylfurfural and the like. Although the preparation of 5-hydroxymethylfurfural has been studied in many ways, most of them are limited to the laboratory scale and are difficult to scale up. One of the main factors hindering the industrial production of 5-hydroxymethylfurfural is the difficulty in separating 5-hydroxymethylfurfural, and the separation of 5-hydroxymethylfurfural from the reaction system often involves complicated and cumbersome steps and requires a large amount of energy consumption. The selection of a proper solvent can simplify the separation step, reduce energy consumption and cost, inhibit the occurrence of side reaction and improve the yield of the 5-hydroxymethylfurfural.
In the ionic liquid, fructose can be efficiently dehydrated and converted to obtain high-yield 5-hydroxymethylfurfural, but the ionic liquid is expensive and the product is difficult to separate; the 5-hydroxymethylfurfural with higher yield can be obtained in an organic solvent such as dimethyl sulfoxide (DMSO), but the separation of the 5-hydroxymethylfurfural is not easy and the energy consumption is overlarge due to the high boiling point of the dimethyl sulfoxide and the good solubility of the 5-hydroxymethylfurfural in the dimethyl sulfoxide.
Disclosure of Invention
The invention mainly aims to provide a method for preparing 5-hydroxymethylfurfural by using a fructose dehydration easily-separated solvent system, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a method for preparing 5-hydroxymethylfurfural by fructose dehydration, which comprises the following steps:
and simultaneously using diphenyl sulfoxide (DPhSO) and/or a diphenyl sulfoxide derivative as a phase transition solvent and a catalyst, reacting a mixed reaction system containing fructose and the diphenyl sulfoxide and/or the diphenyl sulfoxide derivative at 100-160 ℃ for 0.5-11 h, cooling the mixed reaction system to perform phase transition, and separating 5-hydroxymethylfurfural from the solvent to obtain the 5-hydroxymethylfurfural.
Further, the diphenyl sulfoxide and/or the diphenyl sulfoxide derivative act as both a catalyst and a solvent.
Further, the method comprises: and after the reaction is finished, adding water into the mixed reaction system, oscillating and extracting, and then carrying out cooling and liquid separation treatment to obtain the aqueous solution containing the 5-hydroxymethylfurfural.
Further, the method comprises: and after the reaction is finished, cooling the mixed reaction system, adding water for ultrasonic treatment and liquid separation treatment to obtain an aqueous solution containing 5-hydroxymethylfurfural.
Further, the method further comprises: adding H into the solid obtained after the liquid separation treatment 2 O 2 And an alkaline solution of an alkaline substance, followed by thermal oxidation treatment to recover diphenyl sulfoxide and/or a diphenyl sulfoxide derivative.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the diphenyl sulfoxide and/or diphenyl sulfoxide derivative solvent system provided by the invention, the diphenyl sulfoxide and/or diphenyl sulfoxide derivative has a temperature-controlled phase transition property, is solid at normal temperature, has a large distribution coefficient of 5-hydroxymethylfurfural in the diphenyl sulfoxide and/or diphenyl sulfoxide derivative and water, is beneficial to realizing simple separation of products after the reaction is finished, and is a preparation method with good potential industrial application prospect;
(2) according to the diphenyl sulfoxide and/or diphenyl sulfoxide derivative solvent system provided by the invention, fructose dehydration can be catalyzed without adding other catalysts, and the 5-hydroxymethylfurfural has high yield which can reach 68.4%;
(3) according to the diphenyl sulfoxide and/or diphenyl sulfoxide derivative solvent system provided by the invention, the diphenyl sulfoxide and/or diphenyl sulfoxide derivative has good thermal stability and good cycle performance, and can be recycled.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIGS. 1 a-1 b are graphs of the yield and conversion rate of 5-hydroxymethylfurfural prepared by dehydration of fructose in example 1 according to the present invention, respectively;
FIG. 2 is a diagram showing the process of preparing 5-hydroxymethylfurfural by dehydrating fructose in example 1 according to the present invention;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum before and after the reaction of diphenylsulfoxide in example 1 of the present invention;
FIG. 4 is a graph showing the performance test of the recycling of diphenyl sulfoxide in example 5 of the present invention;
FIG. 5 is a photograph showing the reaction before and after the reaction for removing humins by the thermal oxidation method in example 5 of the present invention.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to provide the technical solutions of the present invention, which will be clearly and completely described below. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of an embodiment of the present invention provides a method for preparing 5-hydroxymethylfurfural by dehydration of fructose, which includes:
and simultaneously using diphenyl sulfoxide (DPhSO) and/or a diphenyl sulfoxide derivative as a phase transition solvent and a catalyst, reacting a mixed reaction system containing fructose and the diphenyl sulfoxide and/or the diphenyl sulfoxide derivative at 100-160 ℃ for 0.5-11 h, cooling the mixed reaction system to perform phase transition, and separating 5-hydroxymethylfurfural from the solvent to obtain the 5-hydroxymethylfurfural.
Further, the reaction temperature of the reaction is slightly higher than the melting point of diphenyl sulfoxide and/or diphenyl sulfoxide derivatives.
Furthermore, the mass ratio of the diphenyl sulfoxide and/or the diphenyl sulfoxide derivative to the fructose is 0.05: 1-0.3: 1.
In some more specific embodiments, the method comprises: and after the reaction is finished, adding water into the mixed reaction system, oscillating and extracting, and then carrying out cooling and liquid separation treatment to obtain the aqueous solution containing the 5-hydroxymethylfurfural.
Further, the temperature of the water is 80-90 ℃, the oscillation time is 30-90 s, and the extraction times are 5-8.
Further, the temperature of the water is less than the melting point of the diphenyl sulfoxide and/or the diphenyl sulfoxide derivative.
In some more specific embodiments, the method comprises: and after the reaction is finished, cooling the mixed reaction system, adding water for ultrasonic treatment and liquid separation treatment to obtain an aqueous solution containing 5-hydroxymethylfurfural.
Further, the ultrasonic treatment time is 20-60 min.
Further, the diphenyl sulfoxide derivative includes diphenyl sulfoxide substituted with a functional group on a benzene ring, and is not limited thereto.
Further, the functional group includes any one or a combination of two or more of a sulfonic acid group, a hydroxyl group, and a carboxyl group, and is not limited thereto.
In some more specific embodiments, the method further comprises: adding H into the solid obtained after the liquid separation treatment 2 O 2 And an alkaline solution of an alkaline substance, followed by thermal oxidation treatment to recover diphenyl sulfoxide and/or a diphenyl sulfoxide derivative.
Further, the thermal oxidation treatment is at least used for removing humins in the solid.
Further, the humins are byproducts in the process of preparing 5-hydroxymethylfurfural by dehydrating fructose.
Further, the alkaline substance includes sodium hydroxide, and is not limited thereto.
Further, the concentration of alkaline substances in the alkali solution is 0.5-2 mol/L.
Further, H in the alkali solution 2 O 2 The concentration of (b) is 10-30 wt%.
Further, H in the alkali solution 2 O 2 The concentration of (B) is 30 wt%.
Further, the conditions of the thermal oxidation treatment include: the reaction temperature is 50-70 ℃, and the reaction time is 2-10 min.
In some more specific embodiments, the method for preparing 5-hydroxymethylfurfural by dehydrating fructose specifically comprises:
(1) adding fructose and diphenyl sulfoxide into a sealed glass bottle or a high-pressure reaction kettle according to a certain proportion, heating in an oil bath kettle or an oven, and reacting for a period of time at a given temperature to convert the fructose into a product 5-hydroxymethylfurfural;
(2) taking out the reacted mixture, adding hot water for oscillation extraction, cooling and standing to obtain an upper 5-hydroxymethylfurfural aqueous solution and a lower diphenyl sulfoxide solid, or transferring the cooled reaction phase into a volumetric flask, and ultrasonically dissolving 5-hydroxymethylfurfural in the reaction phase into water;
(3) by thermal oxidation, adding H 2 O 2 And an alkaline solution of sodium hydroxide, and then removing humins generated by the reaction in the diphenyl sulfoxide solid.
Preferably, in the step (1), the mass ratio of the diphenyl sulfoxide to the fructose is 0.05: 1-0.3: 1, the dosage of the diphenyl sulfoxide is 1-30 g, the heating temperature is 100-160 ℃, and the heating time is 0.5-11 h.
Preferably, the temperature of hot water in the step (2) is 80-90 ℃, the oscillation time is 30-90 s, the extraction times are 5-8 times, the using amount of the water in ultrasonic dissolution is 10-50 mL, and the ultrasonic time is 20-60 min.
Preferably, in step (3), H is contained in the alkali solution 2 O 2 The concentration of the alkali solution is 30wt%, the concentration of the sodium hydroxide solution is 1mol/L, the adding amount of the alkali solution is 2-10 mL, the heating temperature is 50-70 ℃, and the reaction time is 2-10 min.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples below were obtained from conventional biochemicals unless otherwise specified.
Example 1
50mg of fructose and 1.0g of diphenyl sulfoxide are added into a sealed glass bottle, then the glass bottle is placed into a preheated oven, the reaction temperature is respectively (100 ℃, 120 ℃, 140 ℃ and 160 ℃), then sampling is carried out at certain time intervals, and the reaction is stopped after 11 hours of reaction. Adding 2mL of water into the taken glass bottle, oscillating for 30s, extracting 5-hydroxymethylfurfural in the reaction solution into an aqueous solution, standing, cooling, separating to obtain an aqueous solution, repeatedly extracting for 6 times, analyzing, and recovering the diphenyl sulfoxide. The fructose conversion rate and the yield of the 5-hydroxymethylfurfural are qualitatively and quantitatively analyzed by adopting a high performance liquid chromatography.
And (3) performance characterization: FIG. 1a and FIG. 1b show the yield and conversion rate of 5-hydroxymethylfurfural prepared by dehydration of fructose in this example, respectively; FIG. 2 is a picture of a reaction process; FIG. 3 shows NMR hydrogen spectra before and after the reaction of diphenyl sulfoxide in the practice of the present invention.
As can be seen from fig. 1 and 2: fructose can be dehydrated in a diphenyl sulfoxide system to generate 5-hydroxymethylfurfural, the yield and the conversion rate are high, and the 5-hydroxymethylfurfural is easy to separate from the diphenyl sulfoxide after the reaction is finished.
Example 2: influence of fructose concentration on catalytic performance in preparation of 5-hydroxymethylfurfural by fructose dehydration
50mg, 100mg, 200mg and 300mg of fructose and 1.0g of diphenyl sulfoxide are respectively added into a sealed glass bottle, then the sealed glass bottle is placed into an oven preheated to 120 ℃, then sampling is carried out at certain time intervals, and the reaction is stopped after 11 hours of reaction. Adding 2mL of water with the temperature of 80 ℃ into the taken glass bottle, oscillating for 30s, extracting 5-hydroxymethylfurfural in the reaction solution into the aqueous solution, standing, cooling, taking the aqueous solution, repeating the operation for 6 times, analyzing, and recovering the diphenyl sulfoxide. The fructose conversion rate and the yield of the 5-hydroxymethylfurfural are qualitatively and quantitatively analyzed by adopting a high performance liquid chromatography.
Example 3: 5-hydroxymethylfurfural prepared by dissolving fructose and dehydrating by ultrasonic method
The reaction of fructose and diphenyl sulfoxide is the same as that in example 1, after the reaction is completed, the system is cooled in an ice bath, the reactant is transferred to a volumetric flask, water is added to a constant volume, circulating water is used for ultrasonic treatment for 30min, a 5-hydroxymethylfurfural aqueous solution is obtained by filtration, and diphenyl sulfoxide is recovered. The fructose conversion rate and the yield of the 5-hydroxymethylfurfural are qualitatively and quantitatively analyzed by adopting a high performance liquid chromatography.
Example 4: post-treatment of reacted diphenylsulfoxide and six-cycle experiment
To the reacted system of example 1, H was added 2 O 2 (30 wt%) and sodium hydroxide (1mol/L) in water (2mL) at 50 deg.C for 2min to remove impurities such as humins generated by reaction in diphenyl sulfoxide, washing the treated diphenyl sulfoxide with water for three times and vacuum drying at 50 deg.C, and making into final productThen, the operation of the catalytic reaction in example 1 was repeated 6 times with respect to the dried diphenylsulfoxide, and the catalytic cycle stability of diphenylsulfoxide was measured.
And (3) performance characterization: FIG. 4 is a graph showing the performance test of the recycling of diphenylsulfoxide in example 5 of the present invention; FIG. 5 is a photograph showing the reaction before and after the reaction for removing humins by the thermal oxidation method in example 5 of the present invention.
As can be seen from fig. 4 and 5: the structure is stable before and after the regeneration of the diphenyl sulfoxide, and the good recycling performance is achieved.
Comparative example 1
50mg of fructose and 1mL of dimethyl sulfoxide are added into a sealed glass bottle, then the bottle is placed into a preheated oven, the reaction temperature is 120 ℃, and the reaction is stopped after 11 hours of reaction. And adding a mixed solution of ethyl acetate and water into the system after the reaction is finished to obtain a layered solution, extracting the 5-hydroxymethylfurfural into the ethyl acetate, removing water, and separating the 5-hydroxymethylfurfural from the ethyl acetate by using a reduced pressure distillation technology. In the experiment, a large amount of ethyl acetate solution is needed, the operation is complex, the separation is difficult, and the dimethyl sulfoxide is also mixed in water and is difficult to recycle.
Example 5
Adding 0.1g of fructose and 1.0g of diphenyl sulfoxide into a sealed glass bottle, then placing the sealed glass bottle into a preheated oven, reacting at the temperature of 120 ℃ for 11 hours, stopping the reaction, adding 2mL of 90 ℃ water into the glass bottle, oscillating for 90s, extracting 5-hydroxymethylfurfural in a reaction solution into an aqueous solution, standing, cooling, separating the solution to obtain the aqueous solution, and repeatedly extracting for 6 times for analysis;
adding H to the solid phase 2 O 2 Heating in water bath at 50 deg.C for 2min to remove impurities such as humin generated in diphenyl sulfoxide, washing treated diphenyl sulfoxide with water for three times, vacuum drying at 50 deg.C, and recovering dried diphenyl sulfoxide.
Example 6
Adding 0.3g of fructose and 1.0g of diphenyl sulfoxide into a sealed glass bottle, then placing the sealed glass bottle into a preheated oven, wherein the reaction temperature is 160 ℃, the reaction is stopped after 0.5h of reaction, after the reaction is finished, cooling the system in an ice bath, transferring the reactant into a volumetric flask, adding water to fix the volume, carrying out ultrasonic treatment on circulating water for 20min, and filtering to obtain a 5-hydroxymethylfurfural aqueous solution;
adding H to the solid phase 2 O 2 Heating in water bath at 60 deg.C for 5min to remove impurities such as humin generated in diphenyl sulfoxide, washing treated diphenyl sulfoxide with water for three times, vacuum drying at 50 deg.C, and recovering dried diphenyl sulfoxide.
Example 7
Adding 0.3g of fructose and 1.0g of diphenyl sulfoxide into a sealed glass bottle, then placing the sealed glass bottle into a preheated oven, wherein the reaction temperature is 160 ℃, the reaction is stopped after 0.5h of reaction, after the reaction is finished, cooling a system in an ice bath, transferring a reactant into a volumetric flask, adding water to fix the volume, carrying out ultrasonic treatment on circulating water for 10min, and filtering to obtain a 5-hydroxymethylfurfural aqueous solution;
adding H to the solid phase 2 O 2 (30 wt%) and sodium hydroxide (1mol/L) in water (2mL) at 50 ℃ for 10min to remove impurities such as humins generated in the reaction in the diphenyl sulfoxide, washing the treated diphenyl sulfoxide with water three times, vacuum-drying at 50 ℃, and then recovering the dried diphenyl sulfoxide.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered illustrative in all respects and not restrictive, the scope of the invention being defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
Although the present invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (9)
1. A method for preparing 5-hydroxymethylfurfural by dehydrating fructose is characterized by comprising the following steps:
simultaneously using diphenyl sulfoxide as a phase transition solvent and a catalyst, and reacting a mixed reaction system containing fructose and diphenyl sulfoxide at 100-160 ℃ for 0.5-11 h;
after the reaction is finished, adding water into the mixed reaction system, oscillating and extracting, and then carrying out cooling and liquid separation treatment to obtain an aqueous solution containing 5-hydroxymethylfurfural; or after the reaction is finished, cooling the mixed reaction system, adding water for ultrasonic treatment and liquid separation treatment to obtain an aqueous solution containing 5-hydroxymethylfurfural.
2. The method of claim 1, wherein: the mass ratio of the diphenyl sulfoxide to the fructose is 0.05: 1-0.3: 1.
3. The method of claim 1, wherein: the temperature of water used in the water adding oscillation extraction is 80-90 ℃, the oscillation time is 30-90 s, and the extraction times are 5-8.
4. The method of claim 1, wherein: the ultrasonic treatment time is 10-30 min.
5. The method of claim 1, further comprising: adding H into the solid obtained after the liquid separation treatment 2 O 2 And an alkaline solution of an alkaline substance, and then performing thermal oxidation treatment to recover the diphenyl sulfoxide.
6. The method of claim 5, wherein: the thermal oxidation treatment is at least used for removing humins in the solid.
7. The method of claim 5, wherein: the alkaline substance is sodium hydroxide; the concentration of alkaline substances in the alkaline solution is 0.5-2 mol/L.
8. The method of claim 5, wherein: h in the alkali solution 2 O 2 The concentration of (A) is 10-30 wt%.
9. The method according to claim 6, characterized in that the conditions of the thermal oxidation treatment comprise: the reaction temperature is 50-70 ℃, and the reaction time is 2-10 min.
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