CN115772142B - Method for directly preparing 2, 5-diformylfuran by taking fructose as raw material - Google Patents
Method for directly preparing 2, 5-diformylfuran by taking fructose as raw material Download PDFInfo
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- 229930091371 Fructose Natural products 0.000 title claims abstract description 46
- 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 46
- 239000005715 Fructose Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 34
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000002994 raw material Substances 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 238000007885 magnetic separation Methods 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 abstract description 10
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 abstract description 10
- 230000018044 dehydration Effects 0.000 abstract description 9
- 239000000047 product Substances 0.000 abstract description 9
- 239000013067 intermediate product Substances 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000002028 Biomass Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 4
- 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 description 3
- 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 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical group N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for directly preparing 2, 5-diformylfuran by taking fructose as a raw material, which comprises the following steps: takes fructose as raw material and magnetic Fe 3 O 4 @SiO 2 ‑SO 3 H is used as a catalyst, dehydration reaction is carried out in dimethyl sulfoxide solvent by heating, and the obtained reaction liquid and Fe 3 O 4 @SiO 2 ‑SO 3 H utilizes magnetic separation, and adds catalyst Fe into the separated reaction solution 3 BiMo 12 O 42 Oxygen is used as oxidant to perform oxidation reaction under normal pressure and heating condition to prepare the 2, 5-diformylfuran. The raw material fructose can be converted into 2, 5-diformylfuran by a one-pot method, and an intermediate product 5-hydroxymethylfurfural does not need to be separated. The conversion rate of fructose is high, and the yield of the product 2, 5-diformylfuran is high. Dehydration catalyst Fe 3 O 4 @SiO 2 ‑SO 3 H can be conveniently separated from the reaction system through magnetic separation, and can be reused and oxidized with Fe as a catalyst 3 BiMo 12 O 42 Can be reused after being separated from the reaction system.
Description
Field of the art
The invention relates to a method for directly preparing 2, 5-diformylfuran by taking fructose as a raw material.
(II) background art
Modern industry is increasingly dependent on fossil energy. The production of numerous products by using fossil fuel as raw materials is convenient for production and living, and the excessive use of fossil energy source also causes irreversible damage to the environment, thereby bringing about the environmental pollution problems of acid rain, haze, greenhouse effect and the like.
Biomass refers to various organisms synthesized by photosynthesis of plants. The biomass is simply treated to prepare glucose, fructose, starch, cellulose, lignin and other compounds, and the compounds are further deeply processed to obtain various green platform compounds. Compared with the traditional fossil energy, the biomass resource has the advantages of being renewable, large in reserves and environment-friendly. The green platform compound produced by taking biomass as a raw material has very important significance for environmental protection and sustainable development.
The biomass can be hydrolyzed under the acid catalysis to generate six-carbon monosaccharides including glucose and fructose, and the six-carbon monosaccharides are further dehydrated to obtain the 5-hydroxymethylfurfural, which is an important biomass-based platform compound. 2, 5-diformylfuran is one of products obtained by selective oxidation of 5-hydroxymethylfurfural, and is widely used because of a unique symmetrical dialdehyde group structure, and is an important fine chemical intermediate.
Among the processes for producing 5-hydroxymethylfurfural, the process of dehydration and conversion of fructose and glucose, which are six-carbon monosaccharides, into 5-hydroxymethylfurfural is the main stream of research. The traditional preparation method of the 2, 5-diformylfuran is to oxidize 5-hydroxymethylfurfural by using an equivalent oxidizing reagent, such as potassium permanganate, sodium hypochlorite and the like, and the product yield is generally low; in recent years, a large number of homogeneous and heterogeneous catalytic oxidation systems using oxygen or air as an oxidant are developed for the oxidation reaction, but the homogeneous system has the problem that the catalyst is difficult to recover, while part of heterogeneous systems have the problems of low raw material conversion rate, poor product selectivity, easy deactivation of the catalyst and the like.
The preparation of 2, 5-diformylfuran from fructose generally requires two steps, namely, dehydration and conversion of fructose into 5-hydroxymethylfurfural, and selective oxidation of 5-hydroxymethylfurfural to produce 2, 5-diformylfuran. This process necessitates the isolation and purification of the intermediate 5-hydroxymethylfurfural, which increases both the economic and environmental costs.
(III) summary of the invention
The technical problem to be solved by the invention is to provide a method for directly preparing 2, 5-diformylfuran with high yield by taking fructose as a raw material.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for directly preparing 2, 5-diformylfuran by taking fructose as a raw material, wherein the chemical formula of the 2, 5-diformylfuran is shown as a formula (I), and the method comprises the following steps: takes fructose as raw material and magnetic Fe 3 O 4 @SiO 2 -SO 3 H is used as a catalyst, dehydration reaction is carried out in dimethyl sulfoxide (DMSO) solvent by heating, and the obtained reaction liquid and Fe 3 O 4 @SiO 2 -SO 3 H utilizes magnetic separation, and adds catalyst Fe into the separated reaction solution 3 BiMo 12 O 42 And (3) taking oxygen as an oxidant, and carrying out oxidation reaction under normal pressure and heating conditions to obtain the 2, 5-diformylfuran shown in the formula (I).
In the invention, the fructose and the catalyst Fe 3 O 4 @SiO 2 -SO 3 The mass ratio of H is 1:0.07-0.17.
In the present invention, the concentration of fructose in dimethyl sulfoxide is 0.05 to 0.3mol/L, preferably 0.1 to 0.3mol/L.
In the invention, the reaction temperature of the fructose for dehydration reaction is 130-150 ℃.
In the invention, the reaction time of the dehydration reaction of the fructose is recommended to be 20-60 min.
In the oxidation reaction, fructose and a catalyst Fe 3 BiMo 12 O 42 The mass ratio of (2) is 1:0.03-0.15, preferably 1:0.05-0.15.
In the present invention, the reaction temperature of the oxidation reaction is 130 to 150 ℃, preferably 140 to 150 ℃.
In the present invention, the reaction time of the oxidation reaction is recommended to be 3 to 10 hours.
Catalyst Fe 3 O 4 @SiO 2 -SO 3 H has magnetism, so that the reaction liquid of dehydration reaction and Fe 3 O 4 @SiO 2 -SO 3 H can be separated by magnetism, typically by adsorbing the catalyst with an external magnet, and then transferring the reaction solution to another reaction vessel.
In the present invention, the catalyst Fe 3 O 4 @SiO 2 -SO 3 H can be reused after magnetic separation; centrifugally separating the reaction liquid of the oxidation reaction, and recovering the catalyst Fe 3 BiMo 12 O 4 Can be repeatedly used.
More specifically, the method of the invention is recommended to be carried out according to the following steps: adding fructose and Fe into a reaction vessel 3 O 4 @SiO 2 -SO 3 H and DMSO, sealing at 130-150 ℃ for dehydration reaction for 20-60 min, and magnetically separating Fe 3 O 4 @SiO 2 -SO 3 H and reaction liquid are separated, fe 3 O 4 @SiO 2 -SO 3 H is available for the next reaction; adding a catalyst Fe into the separated reaction liquid 3 BiMo 12 O 42 Oxidizing at 130-150 deg.c in normal pressure oxygen atmosphere for 3-10 hr to obtain 2, 5-diformylfuran as catalyst Fe 3 BiMo 12 O 42 After centrifugal separation, the mixture can be used for the next reaction; the fructose and the catalyst Fe 3 O 4 @SiO 2 -SO 3 The mass ratio of H is 1:0.07-0.17; the fructose and the catalyst Fe 3 BiMo 12 O 42 The mass ratio of (2) is 1:0.03-0.15.
In the present invention, the catalyst Fe 3 O 4 @SiO 2 -SO 3 H can be prepared according to the method disclosed in the field, and concretely can be prepared according to the following method:
ferric chloride and ferrous sulfate are dissolved in water according to the mass ratio of 2:1, ammonia water is added under the nitrogen atmosphere, and heating reaction is carried out, thus obtaining Fe 3 O 4 ；
Fe 3 O 4 Dispersing in a mixed solvent of ethanol and water, mixing uniformly by ultrasonic, adjusting the pH of the solution to 10 by ammonia water, adding tetraethoxysilane under the protection of nitrogen, and stirring and reacting in the nitrogen atmosphere to obtain Fe 3 O 4 @SiO 2 ；Fe 3 O 4 The ratio of the amounts of the substances of the tetraethoxysilane is 1:2 to 5;
Fe 3 O 4 @SiO 2 dispersing in a mixed solvent of ethanol and water, adding 3-mercaptopropyl trimethoxy silane, carrying out ultrasonic mixing, heating and refluxing for reaction for 10-20 h, washing the obtained solid with water, and adding ethanol, deionized water and 30wt% of H 2 O 2 Reacting for 10-20 h at room temperature, washing the obtained solid with water, adding 0.1mol/L sulfuric acid solution, stirring for reaction, magnetically separating the solid, washing, and drying to obtain Fe 3 O 4 @SiO 2 -SO 3 H；Fe 3 O 4 @SiO 2 The mass ratio of the 3-mercaptopropyl trimethoxy silane to the water is 1:4-5;
in the present invention, the catalyst Fe 3 BiMo 12 O 48 Preferably prepared by the following method:
slowly pouring the mixed solution of ferric nitrate and bismuth nitrate into vigorously stirred ammonium molybdate (NH) 4 ) 6 Mo 7 O 24 In the solution, stirring for 4-5 h at 70-75 ℃, completely evaporating the reaction solution, drying the obtained solid precipitate at 170-190 ℃ to obtain a catalyst precursor, and calcining the dried catalyst precursor at 650-700 ℃ for 6-8 h in air atmosphere to obtain Fe 3 BiMo 12 O 42 A catalyst;
the ratio of the amounts of the substances of the ferric nitrate, the bismuth nitrate and the ammonium molybdate is 9:3:5.
The synthesis method has the advantages that:
(1) The raw material fructose can be converted into 2, 5-diformylfuran by a one-pot method, and the intermediate product 5-hydroxymethylfurfural does not need to be separated.
(2) The conversion rate of fructose is high, and the yield of the product 2, 5-diformylfuran is high.
(3) Dehydration catalyst Fe 3 O 4 @SiO 2 -SO 3 H can be separated from the reaction system conveniently through magnetic separation, and can not be mixed with byproduct humus of fructose dehydration, and can be reused.
(4) Oxidation catalyst Fe 3 BiMo 12 O 42 Can be reused after being separated from the reaction system.
(IV) detailed description of the invention
The present invention will be further described with reference to the following specific embodiments, but the scope of the present invention is not limited thereto.
Catalyst Fe 3 O 4 @SiO 2 -SO 3 Preparation of H
FeCl is added 3 ·6H 2 O (0.2 mmol,54.00 g)) and FeSO 4 ·7H 2 O (0.1 mmol,27.80 g) was dissolved in 340mL of deionized water and stirred under nitrogen for half an hour, 25% ammonia water (110 mL) was added dropwise, and after the addition was completed, the temperature was raised to 90℃and the reaction was stopped by stirring for 3 hours. Cooling the reaction liquid, adsorbing the solid by using an external magnet, discarding the solution, washing the solid with deionized water for multiple times until the washing liquid is neutral, filtering, and vacuum drying to obtain Fe 3 O 4 。
Fe is added to 3 O 4 (6.95 g,0.03 mol) in a mixed solvent of 45mL of ethanol and 9mL of water, sonicating for 30min, adjusting the pH of the solution to 10 with 25% ammonia water, adding 18mL of ethyl orthosilicate under nitrogen protection, stirring in nitrogen atmosphere for 6h, adsorbing the solid with an external magnet, discarding the solution, washing the solid with ethanol, and vacuum drying to obtain Fe 3 O 4 @SiO 2 。
1.0g of Fe 3 O 4 @SiO 2 Dispersing in a mixed solvent of 45mL ethanol and 9mL water, adding 4g 3-mercaptopropyl trimethoxysilane, performing ultrasonic treatment for 15min, heating and refluxing for 12h, adsorbing the solid with external magnet, discarding the solution, washing the solid with water for three times, adding40mL of ethanol, 40mL of deionized water, and 24mL of 30% H 2 O 2 Reacting at room temperature for 12h, adsorbing the solid with external magnet, discarding the solution, washing the solid with deionized water for three times, adding 90mL of 0.1mol/L sulfuric acid solution, stirring for 3h, adsorbing the solid with external magnet, discarding the solution, washing with deionized water for three times, and vacuum drying to obtain Fe 3 O 4 @SiO 2 -SO 3 H。
Catalyst Fe 3 BiMo 12 O 48 Is prepared from
3.7g (9 mmol) of Fe (NO) 3 ) 3 ·9H 2 O was dissolved in 100mL deionized water and the solution was labeled as solution A. After weighing 7mL of deionized water and 3mL of concentrated nitric acid, mixing, 1.5g (3 mmol) of Bi (NO) was added 3 ) 3 ·5H 2 O, the solution was labeled as solution B. 6.3g (5 mmol) of (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, dissolved in 50mL of deionized water and vigorously stirred, this solution was designated as solution C. After the solution A and the solution B are uniformly mixed, slowly pouring the mixture into a vigorously stirred solution C, stirring the mixture for 4 hours at 70 ℃, almost completely evaporating the reaction solution, and drying the obtained solid precipitate in a vacuum drying oven at 175 ℃ for 8 hours to obtain the catalyst precursor. Then calcining the dried catalyst precursor for 6 hours at 650 ℃ in air atmosphere to obtain Fe 3 BiMo 12 O 42 A catalyst.
Example 1
To a 15 mL-sealed tube equipped with a magnetic stirrer, fructose (180 mg,1 mmol) and Fe were added 3 O 4 @SiO 2 -SO 3 H (15 mg) and 6mL DMSO, sealing, dehydrating at 140deg.C for 30min, cooling, and adsorbing magneton and Fe with external magnet 3 O 4 @SiO 2 -SO 3 H，Fe 3 O 4 @SiO 2 -SO 3 H can be reused, and the reaction solution is transferred to another branch which is filled with 10mg Fe 3 BiMo 12 O 42 In the tube sealing of (2), the air in the tube is replaced by oxygen, the bottle mouth is closed by a rubber plug, and then an oxygen balloon is inserted, and the process is carried out at 140 DEG COxidizing for 5h to obtain 2, 5-diformylfuran, fe 3 BiMo 12 O 42 Can be reused after centrifugal separation. The conversion of fructose was found to be 100% by liquid chromatography and the yield of 2, 5-diformylfuran was found to be 85% by gas chromatography. The conversion rate of fructose is detected by adopting a high performance liquid chromatography external standard method, and the yield of the product 2, 5-diformylfuran is detected by adopting a gas chromatography internal standard method.
Example 2
The reaction procedure was as in example 1 except that the dehydration temperature was changed to 130℃and the dehydration time was changed to 60min, the oxidation reaction was changed to 150℃and the oxidation time was changed to 3h, the fructose conversion was 98% and the yield of 2, 5-diformylfuran was 82%.
Example 3
The reaction procedure was as in example 1 except that the dehydration temperature was changed to 150℃and the dehydration time was changed to 20 minutes, the oxidation reaction was changed to 130℃and the oxidation time was changed to 10 hours, the conversion of fructose was 100%, and the yield of 2, 5-diformylfuran was 75%.
Example 4
The reaction procedure is as in example 1, except that Fe 3 O 4 @SiO 2 -SO 3 H is 30mg, fe 3 BiMo 12 O 42 The amount was changed to 25mg, the fructose conversion was 100%, and the yield of the product 2, 5-diformylfuran was 87%.
Example 5
The reaction procedure is as in example 1, except that Fe 3 BiMo 12 O 42 The dosage is changed to 6mg, the oxidation reaction time is changed to 9h, the fructose conversion rate is 100%, and the yield of the product 2, 5-diformylfuran is 80%.
Example 6
The catalyst Fe in example 1 3 O 4 @SiO 2 -SO 3 H and Fe 3 BiMo 12 O 42 The procedure used was repeated for the preparation of 2, 5-diformylfuran from fructose as in example 1. Recovered three times, and the obtained reaction results are shown in the table1 is shown as follows:
TABLE 1 recovery of catalyst Fe 3 O 4 @SiO 2 -SO 3 H and Fe 3 BiMo 12 O 42 Reaction for preparing 2, 5-diformylfuran from fructose
The recovered catalyst has no influence on the fructose conversion rate and the yield of 2, 5-diformylfuran, and the catalytic activity of the recovered catalyst is basically unchanged.
Claims (9)
1. A method for directly preparing 2, 5-diformylfuran by taking fructose as a raw material is characterized in that the chemical formula of the 2, 5-diformylfuran is shown as a formula (I), and the method is as follows: takes fructose as raw material and magnetic Fe 3 O 4 @SiO 2 -SO 3 H is used as a catalyst, dehydration reaction is carried out in dimethyl sulfoxide solvent by heating, and the obtained reaction liquid and Fe 3 O 4 @SiO 2 -SO 3 H utilizes magnetic separation, and adds catalyst Fe into the separated reaction solution 3 BiMo 12 O 42 Oxidizing reaction under normal pressure and heating condition by taking oxygen as oxidant to obtain 2, 5-diformylfuran shown in formula (I);
catalyst Fe 3 O 4 @SiO 2 -SO 3 H is prepared by the following method:
ferric chloride and ferrous sulfate are dissolved in water according to the mass ratio of 2:1, ammonia water is added under the nitrogen atmosphere, and heating reaction is carried out, thus obtaining Fe 3 O 4 ；
Fe 3 O 4 Dispersing in a mixed solvent of ethanol and water, mixing with ultrasound, adjusting pH to 10 with ammonia water, adding ethyl orthosilicate under nitrogen protection, and stirring in nitrogen atmosphereMixing and reacting to obtain Fe 3 O 4 @SiO 2 ；Fe 3 O 4 The ratio of the amounts of the substances of the tetraethoxysilane is 1:2 to 5;
Fe 3 O 4 @SiO 2 dispersing in a mixed solvent of ethanol and water, adding 3-mercaptopropyl trimethoxy silane, carrying out ultrasonic mixing, heating and refluxing for reaction for 10-20 h, washing the obtained solid with water, and adding ethanol, deionized water and 30wt% of H 2 O 2 Reacting for 10-20 h at room temperature, washing the obtained solid with water, adding 0.1mol/L sulfuric acid solution, stirring for reaction, magnetically separating the solid, washing, and drying to obtain Fe 3 O 4 @SiO 2 -SO 3 H；Fe 3 O 4 @SiO 2 The mass ratio of the 3-mercaptopropyl trimethoxy silane to the water is 1:4-5;
the catalyst Fe 3 BiMo 12 O 48 The preparation method comprises the following steps:
slowly pouring the mixed solution of ferric nitrate and bismuth nitrate into vigorously stirred ammonium molybdate (NH) 4 ) 6 Mo 7 O 24 In the solution, stirring for 4-5 h at 70-75 ℃, completely evaporating the reaction solution, drying the obtained solid precipitate at 170-190 ℃ to obtain a catalyst precursor, and calcining the dried catalyst precursor at 650-700 ℃ for 6-8 h in air atmosphere to obtain Fe 3 BiMo 12 O 42 A catalyst; the ratio of the amounts of the substances of the ferric nitrate, the bismuth nitrate and the ammonium molybdate is 9:3:5.
2. The method according to claim 1, wherein the fructose and the catalyst Fe 3 O 4 @SiO 2 -SO 3 The mass ratio of H is 1:0.07-0.17.
3. The method according to claim 1, wherein fructose and a catalyst Fe are used in the oxidation reaction 3 BiMo 12 O 42 The mass ratio of (2) is 1:0.03-0.15.
4. The method according to claim 1, wherein the concentration of fructose in dimethyl sulfoxide is 0.05-0.3 mol/L.
5. The method according to claim 1, wherein the fructose is subjected to a dehydration reaction at a reaction temperature of 130 ℃ to 150 ℃.
6. The method according to claim 1, wherein the fructose is dehydrated for a reaction time of 20 to 60 minutes.
7. The method of claim 1, wherein the oxidation reaction is carried out at a temperature of 130 ℃ to 150 ℃.
8. The method according to claim 1, wherein the reaction time of the oxidation reaction is 3 to 10 hours.
9. The method of claim 1, wherein the method is performed according to the steps of: adding fructose and Fe into a reaction vessel 3 O 4 @SiO 2 -SO 3 H and DMSO, sealing at 130-150 ℃ for dehydration reaction for 20-60 min, and magnetically separating Fe 3 O 4 @SiO 2 -SO 3 H and reaction liquid are separated, fe 3 O 4 @SiO 2 -SO 3 H is available for the next reaction; adding a catalyst Fe into the separated reaction liquid 3 BiMo 12 O 42 Oxidizing at 130-150 deg.c in normal pressure oxygen atmosphere for 3-10 hr to obtain 2, 5-diformylfuran as catalyst Fe 3 BiMo 12 O 42 After centrifugal separation, the mixture can be used for the next reaction; the fructose and the catalyst Fe 3 O 4 @SiO 2 -SO 3 The mass ratio of H is 1:0.07-0.17; the fructose and the catalyst Fe 3 BiMo 12 O 42 The mass ratio of (2) is 1:0.03-0.15.
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