CN112851605B - Method for preparing 2, 5-diformylfuran by selective oxidation of 5-hydroxymethylfurfural - Google Patents
Method for preparing 2, 5-diformylfuran by selective oxidation of 5-hydroxymethylfurfural Download PDFInfo
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- CN112851605B CN112851605B CN202110080979.8A CN202110080979A CN112851605B CN 112851605 B CN112851605 B CN 112851605B CN 202110080979 A CN202110080979 A CN 202110080979A CN 112851605 B CN112851605 B CN 112851605B
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- hydroxymethylfurfural
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a method for preparing 2, 5-diformylfuran by selective oxidation of 5-hydroxymethylfurfural, which takes 5-hydroxymethylfurfural as a raw material and a four-component molybdenum-based compound Co9Fe3BiMo12O51The catalyst is prepared by reacting oxygen as oxidant in dimethyl sulfoxide under normal pressure and heating condition for a certain time to obtain 2, 5-diformylfuran, and the catalyst can be reused after centrifugal separation, washing and drying. The invention has high conversion rate of the raw material 5-hydroxymethylfurfural, high yield of the product 2, 5-diformylfuran and high yield of the catalyst Co9Fe3BiMo12O51Can be repeatedly used.
Description
Technical Field
The invention relates to a method for preparing 2, 5-diformylfuran by selective oxidation of 5-hydroxymethylfurfural.
Background
The biomass is used as an initial raw material to prepare various chemicals such as bulk chemicals, special chemicals, intermediates, fine chemicals and the like, and is an important way for biomass resource utilization. To accomplish this utilization of biomass, typically, the biomass is first converted to a platform compound via chemical depolymerization or enzymatic catalysis, and the platform compound is then converted to the corresponding chemical via various chemical processes. The 5-hydroxymethylfurfural can be prepared by dehydrating cellulose, glucose, fructose and other carbohydrates through acid catalysis, and is a very important biomass-based platform compound. The 2, 5-diformylfuran is one of important oxidation products of 5-hydroxymethylfurfural, is widely applied, is mainly used as an antifungal agent, a macrocyclic ligand, a medicine and a monomer of a furyl polymer, and can be used for synthesizing various functional polymers. The oxidation of 5-hydroxymethylfurfural to 2, 5-diformylfuran has been carried out very early, and direct oxidation using stoichiometric amounts of an oxidizing agent was common in the early stages of the study, and it is evident that such a mode of oxidation is environmentally unfriendly. In recent years, a large number of catalytic oxidation systems using oxygen or air as an oxidizing agent have been developed for the reaction, including homogeneous systems and heterogeneous systems. However, the homogeneous system has the problem of difficult catalyst recovery, while the partial heterogeneous system has the problems of low raw material conversion rate, poor product selectivity, easy catalyst deactivation and the like.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing 2, 5-diformylfuran with high yield by taking 5-hydroxymethylfurfural as a raw material and oxygen as a clean oxidant.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing 2, 5-diformylfuran by selective oxidation of 5-hydroxymethylfurfural is characterized by comprising the following steps: the method comprises the following steps: 5-hydroxymethyl furfural shown in formula (II) is used as raw material, and four-component molybdenum-based compound Co is used9Fe3BiMo12O51The catalyst is prepared by reacting oxygen as oxidant in dimethyl sulfoxide (DMSO) under normal pressure and heating for a certain time to obtain 2, 5-diformylfuran shown in formula (I), and the catalyst can be reused after centrifugal separation, washing and drying.
In the invention, the 5-hydroxymethylfurfural and a catalyst Co9Fe3BiMo12O51The mass ratio of (A) to (B) is as follows: 1: 0.8-0.25.
In the invention, the mass usage amount of the dimethyl sulfoxide (DMSO) is 10-50 times of that of the 5-hydroxymethylfurfural.
In the invention, the reaction temperature is 120-140 ℃.
In the invention, the reaction time is 8-12 hours.
In the present invention, catalyst Co9Fe3BiMo12O51After centrifugal separation, washing with water and ethanol in sequence, and drying to obtain the final product for the next reaction.
The reaction liquid is analyzed by gas chromatography, and the conversion rate of the raw material 5-hydroxymethylfurfural and the yield of the product 2, 5-diformylfuran are determined by an external standard method.
More specifically, the method of the present invention is recommended to be performed according to the following steps: adding 5-hydroxymethylfurfural and Co into a reaction vessel9Fe3BiMo12O51Reacting with DMSO in normal pressure oxygen atmosphere at 120-140 deg.C for 8-12 hr to obtain 2, 5-diformylfuran, and reactingThe liquid is analyzed by gas chromatography, and the catalyst can be repeatedly used after centrifugal separation, washing and drying; the 5-hydroxymethylfurfural and a catalyst Co9Fe3BiMo12O51The mass ratio of (A) to (B) is as follows: 1: 0.8-0.25; the mass usage amount of the DMSO is 10-50 times of that of 5-hydroxymethylfurfural.
The synthesis method has the advantages that the conversion rate of the raw material 5-hydroxymethylfurfural is high, the yield of the product 2, 5-diformylfuran is high, and the catalyst Co is used9Fe3BiMo12O51Can be repeatedly used.
Detailed Description
The present invention is further illustrated by the following specific embodiments, but the scope of the invention is not limited thereto.
Catalyst Co9Fe3BiMo12O51Preparation of
7.9g of Co (NO)3)2·6H2O (27mmol) and 3.7g Fe (NO)3)3·9H2O (9mmol) was dissolved in 100mL of distilled water (labeled as solution A). 1.5g of Bi (NO)3)3·5H2O (3mmol) was dissolved in 7mL of distilled water and acidified with 3mL of concentrated nitric acid (labeled as solution B). Then, solution B was added to solution A, and the resulting mixed solution was added dropwise to a solution containing 6.4g of (NH) under vigorous stirring4)6Mo7O24·4H2O (5mmol) in 50mL of water. In the coprecipitation step, 25% ammonia water is dripped to control the pH value of the mixed solution to be between 1 and 2, and the mixed solution is vigorously stirred for 4 hours at the temperature of 70 ℃ to evaporate all the solvent, so that the obtained solid precipitate is the catalyst precursor. Drying the catalyst precursor at 175 ℃ for 8h, and then calcining the dried catalyst precursor in a tubular furnace for 6h under the air atmosphere, wherein the calcining temperature is 650 ℃, and the heating rate is 3 ℃/min. Collecting the catalyst after the tube furnace is naturally cooled and grinding the catalyst into powder to obtain Co9Fe3BiMo12O51A catalyst.
Example 1
In a 15mL pack equipped with a magnetic stirrerIn the tube, 5-hydroxymethylfurfural (1mmol) and Co were added9Fe3BiMo12O51(0.025g), replacing the air in the tube with oxygen, sealing the opening of the tube with a rubber plug, inserting an oxygen balloon, injecting 3mL of DMSO into the sealed tube, reacting at 130 ℃ for 10 hours to obtain 2, 5-diformylfuran, and analyzing the reaction liquid by gas chromatography, wherein the conversion rate of 5-hydroxymethylfurfural is 99% and the yield of the product 2, 5-diformylfuran is 98%.
Example 2
The reaction procedure was as in example 1, except that Co9Fe3BiMo12O51The dosage is changed to 0.01g, the conversion rate of 5-hydroxymethylfurfural is 93%, and the yield of the product 2, 5-diformylfuran is 92%.
Example 3
The reaction procedure was as in example 1, except that Co9Fe3BiMo12O51The dosage is changed to 0.02g, the conversion rate of the 5-hydroxymethylfurfural is 96 percent, and the yield of the product 2, 5-diformylfuran is 95 percent.
Example 4
The reaction procedure was the same as in example 1, except that the reaction temperature was changed to 120 ℃, the conversion of 5-hydroxymethylfurfural was 50%, and the yield of the product 2, 5-diformylfuran was 49%.
Example 5
The reaction procedure was the same as in example 1, except that the reaction temperature was changed to 140 ℃, the conversion of 5-hydroxymethylfurfural was 99%, and the yield of the product 2, 5-diformylfuran was 98%.
Example 6
The reaction solution in example 1 was centrifuged, and the obtained catalyst Co was recovered9Fe3BiMo12O51Washed with water and ethanol respectively, and repeatedly used in the reaction of selectively oxidizing 5-hydroxymethylfurfural into 2, 5-diformylfuran after being dried, and the using method is the same as that of example 1. Recovered three times, the reaction results obtained are shown in table 1:
TABLE 1 catalyst Co recovery9Fe3BiMo12O51For oxidation reaction of 5-hydroxymethylfurfural
Claims (6)
1. A method for preparing 2, 5-diformylfuran by selective oxidation of 5-hydroxymethylfurfural is characterized by comprising the following steps: the method comprises the following steps: 5-hydroxymethyl furfural shown in formula (II) is used as raw material, and four-component molybdenum-based compound Co is used9Fe3BiMo12O51Taking oxygen as an oxidant, reacting in dimethyl sulfoxide under the conditions of normal pressure and heating to the reaction temperature of 130-140 ℃ for a certain time to obtain 2, 5-diformylfuran shown as a formula (I), and performing centrifugal separation, washing and drying on the catalyst for reuse;
the catalyst is prepared by the following method:
7.9g of Co (NO)3)2·6H2O and 3.7g Fe (NO)3)3·9H2Dissolving O in 100mL of distilled water, and marking as a solution A; 1.5g of Bi (NO)3)3·5H2Dissolving O in 7mL of distilled water, acidifying with 3mL of concentrated nitric acid, and marking as a solution B; then, solution B was added to solution A, and the resulting mixed solution was added dropwise to a solution containing 6.4g of (NH) under vigorous stirring4)6Mo7O24·4H250mL of an aqueous solution of O; in the coprecipitation step, 25% ammonia water is dripped to control the pH value of the mixed solution to be 1-2, the mixed solution is stirred vigorously for 4 hours at 70 ℃ to evaporate all the solvent, and the obtained solid precipitate is a catalyst precursor; drying the catalyst precursor at 175 ℃ for 8h, and then calcining the dried catalyst precursor in a tubular furnace for 6h under the air atmosphere, wherein the calcining temperature is 650 ℃, and the heating rate is 3 ℃/min; collecting the catalyst after the tube furnace is naturally cooled and grinding the catalyst into powder to obtain Co9Fe3BiMo12O51A catalyst.
2. The process according to claim 1, wherein the selective oxidation of 5-hydroxymethylfurfural to 2, 5-diformylfuran is carried out by: the 5-hydroxymethylfurfural and a catalyst Co9Fe3BiMo12O51The mass ratio of (A) to (B) is as follows: 1: 0.8-0.25.
3. The process according to claim 1, wherein the selective oxidation of 5-hydroxymethylfurfural to 2, 5-diformylfuran is carried out by: the mass amount of the dimethyl sulfoxide is 10-50 times of that of the 5-hydroxymethylfurfural.
4. The process according to claim 1, wherein the selective oxidation of 5-hydroxymethylfurfural to 2, 5-diformylfuran is carried out by: the reaction time is 8-12 hours.
5. The process according to claim 1, wherein the selective oxidation of 5-hydroxymethylfurfural to 2, 5-diformylfuran is carried out by: catalyst Co9Fe3BiMo12O51After centrifugal separation, washing with water and ethanol in sequence, and drying to obtain the final product for the next reaction.
6. The process according to claim 1, wherein the selective oxidation of 5-hydroxymethylfurfural to 2, 5-diformylfuran is carried out by: the reaction liquid is analyzed by gas chromatography, and the conversion rate of the raw material 5-hydroxymethylfurfural and the yield of the product 2, 5-diformylfuran are determined by an external standard method.
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