CN115785037A - Green synthesis method for preparing 2, 5-furandicarboxylic acid by catalyzing tandem oxidation of 5-hydroxymethylfurfural - Google Patents

Green synthesis method for preparing 2, 5-furandicarboxylic acid by catalyzing tandem oxidation of 5-hydroxymethylfurfural Download PDF

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CN115785037A
CN115785037A CN202211504571.XA CN202211504571A CN115785037A CN 115785037 A CN115785037 A CN 115785037A CN 202211504571 A CN202211504571 A CN 202211504571A CN 115785037 A CN115785037 A CN 115785037A
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汤骏
陈俊宝
胡晓龙
李鹏
刘志强
马勤城
王滢
张战玉
柯清平
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Anhui University of Technology AHUT
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Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a green synthesis method for preparing 2, 5-furandicarboxylic acid by catalyzing 5-hydroxymethylfurfural through tandem oxidation, which comprises the steps of adding HMF, a reaction medium, TBHP and C @ CoMn into a reaction vessel, and stirring for oxidation reaction to obtain FDCA; c @ CoMn is used as a catalyst, porous carbon on the outer layer of the catalyst contains basic sites rich in pyridine nitrogen, pyrrole nitrogen and graphite nitrogen to promote HMF to form an easily oxidized gem-diol intermediate, and meanwhile, the bimetallic catalyst has rich oxygen vacancies and Mn 3+ Can activate TBHP to form high-activity superoxide radical. The invention overcomes the problems of low selectivity of the HMF oxidation process and environmental pollution caused by the use of alkaline reagents, realizes the efficient and high-selectivity conversion of HMF into FDCA in a mild environment by the Lewis alkaline site regulation and control effect of C @ CoMn and the promotion of the generation of superoxide radical beneficial to the oxidation reaction by manganese active species, and has the advantages of industrial productionAnd the application prospect is improved.

Description

Green synthesis method for preparing 2, 5-furandicarboxylic acid by catalyzing tandem oxidation of 5-hydroxymethylfurfural
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a green synthesis method for preparing 2, 5-furandicarboxylic acid by catalyzing the tandem oxidation of 5-hydroxymethylfurfural.
Background
With the increasing consumption of fossil energy and the global warming problem brought by greenhouse effect, the development and utilization of sustainable energy are greatly promoted. If abundant biomass resources in the nature can be converted into chemicals with high added values by developing a novel catalytic reaction technology, the current energy and environment crisis can be relieved. 5-Hydroxymethylfurfural (HMF) is a widely used compound, obtainable by hydrolysis of cellulose. HMF can be used for synthesizing high value-added chemicals such as 2, 5-furandicarbaldehyde (DFF), 2, 5-furandicarboxylic acid (FDCA), 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), maleic Acid (MA) and the like through catalytic oxidation. Among them, FDCA is considered as the most market potential key monomer, and is an important monomer for producing the green polymer polyethylene-2, 5-furandicarboxylate. Therefore, the method for preparing FDCA by using 5-Hydroxymethylfurfural (HMF) as a platform compound through multi-step oxidation by using a green catalytic technology has important significance for developing a green chemical route synthesized by bio-based chemicals to replace the traditional petrochemical products.
To develop an environmentally friendly epoxidation technology, green molecular oxygen (O) is used 2 ) Hydrogen peroxide (H) 2 O 2 ) And tert-butyl hydroperoxide (TBHP) are of critical importance as oxidizing agents. Compared with O 2 Activation requires noble metals, or photosensitizers, etc., H 2 O 2 And TBHP can be passed throughMolecular sieves, transition metals, carbon materials and the like are used as catalysts to realize the conversion of HMF. H 2 O 2 And TBHP as an oxidant has the disadvantage of lower selectivity for FDCA. This is because H 2 O 2 And TBHP can simultaneously form superoxide radical (HO) in the activation process 2 (-) and hydroxyl radical (. OH), which easily causes side reaction and reduces reaction selectivity. To increase the selectivity of FDCA, a base (e.g., naHCO) is additionally added to the reaction solution 3 Etc.) to facilitate conversion of HMF to FDCA. However, the addition of alkali brings inconvenience to the subsequent separation and purification and also causes environmental pollution. The oxidation of HMF can also be catalyzed with the solid base catalytic sites of the material itself without additional addition of base. Compared with transition metal catalyst, the non-metal catalyst has lower cost and environment-friendly treatment and recovery process. Non-metallic catalysts based on carbon and nitrogen exhibit excellent performance in catalytic oxidation reactions for HMF. For example, nitrogen-doped carbon materials have the advantages of simple preparation process, low cost, good catalytic performance and the like. Doping of the N atoms can form porous carbon containing pyridine nitrogen, pyrrole nitrogen, and graphite nitrogen basic sites due to the formation of these basic sites. Meanwhile, the N site can activate TBHP to form superoxide radical HO 2 Promoting the efficient and high-selectivity conversion of HMF into FDCA.
Therefore, there is a need to provide a new green synthesis method for the preparation of 2, 5-furandicarboxylic acid, which enables efficient and highly selective conversion of HMF.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a green synthesis method for preparing 2, 5-furandicarboxylic acid by catalyzing the tandem oxidation of 5-hydroxymethylfurfural, which can realize the efficient and high-selectivity conversion of HMF.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a green synthesis method for preparing 2, 5-furandicarboxylic acid by catalyzing series oxidation of 5-hydroxymethylfurfural is characterized by adding HMF, a reaction medium, TBHP and C @ CoMn into a reaction vessel, and stirring for oxidation reaction to obtain FDCA.
Further, the preparation method of the C @ CoMn comprises the following steps:
1) Dissolving polyoxyethylene polyoxypropylene ether and dopamine hydrochloride in a water-ethanol mixed solution according to a ratio, and adding manganese salt and cobalt salt under a stirring condition to obtain a solution;
2) Adding ammonia water into the solution A, and stirring for reaction to obtain a catalyst precursor;
3) Calcining the obtained catalyst precursor in an air atmosphere at 330-370 ℃ for 2-6 h to obtain the C @ CoMn.
Further, in the step 1), the mol ratio of the polyoxyethylene polyoxypropylene ether to the dopamine hydrochloride to the manganese salt to the cobalt salt is 1: 60-65: 50 to 55:60 to 65 portions;
the manganese salt is manganese nitrate tetrahydrate, manganese acetate dihydrate, manganese sulfate monohydrate or manganese carbonate;
the cobalt salt is cobalt nitrate tetrahydrate, cobalt carbonate, cobalt sulfate or cobalt acetate;
and mixing water and ethanol in the water-ethanol mixed solution in any proportion.
Further, in the step 2), the mass fraction of the ammonia water is 25-28%, and the proportion relationship between the ammonia water and the polyoxyethylene polyoxypropylene ether is 3-5 ml/g.
Further, in the step 3), the calcining temperature is 350 ℃ and the calcining time is 4 hours.
Furthermore, the concentration of the added C @ CoMn is 30-35 g/L.
Further, the concentration of the added HMF is 0.15-0.2 mol/L.
Further, the molar amount of the TBHP is 3-6 times that of the HMF.
Further, the reaction medium is any one of toluene, acetonitrile, tetrahydrofuran and 1, 4-dioxane.
Furthermore, the reaction temperature is controlled to be 60-75 ℃, and the reaction time is controlled to be 5-7 h.
The invention has the beneficial effects that:
1. the invention provides aA green synthesis method for preparing 2, 5-furandicarboxylic acid by catalyzing 5-hydroxymethylfurfural through tandem oxidation is characterized in that HMF, a reaction medium, an oxidant TBHP and a catalyst C @ CoMn are added into a reaction tube and uniformly mixed, and oxidation reaction is carried out to obtain FDCA. The invention takes C @ CoMn as a catalyst, porous carbon on the outer layer of the catalyst contains abundant pyridine nitrogen, pyrrole nitrogen and graphite nitrogen basic sites to promote HMF to form an easily oxidized gem-diol intermediate, and meanwhile, the bimetallic catalyst has abundant oxygen vacancies and Mn 3+ Can activate TBHP to form high-activity superoxide radical, realizes the efficient and high-selectivity conversion of HMF into FDCA in a mild environment, and has industrial application prospect.
2. The catalytic reaction system adopted by the invention is simple and easy to operate, does not need to additionally add an alkaline reagent to improve the selectivity of the product, and can realize the efficient conversion of HMF at a lower temperature. The catalyst has simple preparation conditions and green reaction process, and avoids the problem of environmental pollution caused by the use of an alkaline reagent.
Of course, it is not necessary for any product to achieve all of the above advantages at the same time in the practice of the invention.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an XRD spectrum of a C @ CoMn catalyst;
FIG. 2 is an O1s XPS spectrum of a C @ CoMn catalyst;
FIG. 3 is the formation of HO from TBHP activated by C @ CoMn 2 An EPR map of;
FIG. 4 is a schematic representation of FDCA prepared 1 H NMR spectrum;
FIG. 5 is a schematic diagram of the oxidation reaction of HMF.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
The invention takes dopamine hydrochloride as a nitrogen source and a carbon source, adds cobalt and manganese ions, and prepares the precursor of the coated bimetallic catalyst by a polymerization method in one step. And (3) calcining at high temperature to obtain the carbon-coated bimetallic catalyst C @ CoMn. TBHP is used as an oxidant, and a stable, cheap and environment-friendly carbon-based catalyst is used for efficiently converting HMF into FDCA without the participation of an alkaline auxiliary agent. The process is a green and pollution-free chemical process, and meets the strategic target of green sustainable development promoted by the state.
In the present invention, the HMF oxidation reaction is shown in fig. 5. After the HMF oxidation reaction is completed, the present invention preferably centrifuges the obtained reaction solution, recovers the catalyst, and evaporates the obtained oil phase liquid to obtain FDCA. The process of centrifugation, evaporation and filtration is not particularly limited and may be performed according to a process well known in the art.
The invention takes C @ CoMn as a catalyst, porous carbon on the outer layer of the catalyst contains abundant pyridine nitrogen, pyrrole nitrogen and graphite nitrogen basic sites to promote HMF to form an easily oxidized gem-diol intermediate, and meanwhile, the bimetallic catalyst has abundant oxygen vacancies and Mn 3+ Can activate TBHP to form high-activity superoxide radical, and realize the high-efficiency and high-selectivity conversion of HMF into FDCA under a mild environment.
The related specific embodiments of the invention are as follows:
in the following examples, the preparation of C @ CoMn is: 1g of polyoxyethylene polyoxypropylene ether (molecular weight 12600) and 1g of dopamine hydrochloride were dissolved in 100mL of a water-ethanol (volume ratio 1. Adding 4mL of ammonia water (mass fraction: 26%) into the solution, and stirring for reaction for 24h to obtain a catalyst precursor. And placing the obtained catalyst precursor in a muffle furnace, and calcining for 4 hours at the temperature of 350 ℃ in the air atmosphere to obtain the C @ CoMn catalyst.
XRD results of C @ CoMn catalyst are shown in FIG. 1, O1s XPS results of C @ CoMn catalyst are shown in FIG. 2, and C @ CoMn activates TBHP to form HO 2 The results of (a) are shown in FIG. 3.
Example 1
5-hydroxymethylfurfural HMF (0.5 mmol), acetonitrile (5 mL), oxidant TBHP (2.5 mmol) and catalyst C @ CoMn (0.1 g) were added to the reaction tube. The reaction temperature is 70 ℃, and the stirring reaction is carried out for 5 hours at 800 rpm. After the reaction is finished, separating and purifying to obtain the target product FDCA. HMF conversion was >99.9% with selectivity 94%.
Preparation of the resulting FDCA 1 H NMR is shown in FIG. 4:
1 H NMR(400MHz,CDCl 3 )δ7.54,7.28,7.16,7.02,5.60,4.22,4.18,2.38,2.30,2.28,1.56,1.45,1.39,1.36,1.31,1.28,1.05,0.90,0.88,0.87,0.17,0.02,-0.13。
example 2
5-hydroxymethylfurfural HMF (0.5 mmol), acetonitrile (4.5 mL), oxidant TBHP (3.2 mmol), and catalyst C @ CoMn (0.12 g) were added to the reaction tube. The reaction temperature was 70 ℃ and the reaction was stirred at 800rpm for 5 hours. After the reaction is finished, separating and purifying to obtain the target product FDCA. HMF conversion was >99.9% with selectivity 89%.
Example 3
5-hydroxymethylfurfural HMF (0.5 mmol), acetonitrile (5.5 mL), oxidant TBHP (2 mmol) and catalyst C @ CoMn (0.06 g) were added to the reaction tube. The reaction temperature is 70 ℃, and the stirring reaction is carried out for 5 hours at 800 rpm. After the reaction is finished, separating and purifying to obtain the target product FDCA. HMF conversion was 90% and selectivity was 87%.
Example 4
5-hydroxymethylfurfural HMF (0.5 mmol), acetonitrile (5 mL), oxidant TBHP (2.5 mmol) and catalyst C @ CoMn (0.1 g) were added to the reaction tube. The reaction temperature was 60 ℃ and the reaction was stirred at 800rpm for 5 hours. After the reaction is finished, separating and purifying to obtain the target product FDCA. HMF conversion was 90% and selectivity was 90%.
Example 5
5-hydroxymethylfurfural HMF (0.5 mmol), acetonitrile (5 mL), oxidant TBHP (2.5 mmol) and catalyst C @ CoMn (0.1 g) were added to the reaction tube. The reaction temperature is 75 ℃, and the stirring reaction is carried out for 5 hours at 800 rpm. After the reaction is finished, separating and purifying to obtain the target product FDCA. HMF conversion was 90% and selectivity was 85%.
Example 6
5-hydroxymethylfurfural HMF (0.5 mmol), acetonitrile (5 mL), oxidant TBHP (2.5 mmol) and catalyst C @ CoMn (0.1 g) were added to the reaction tube. The reaction temperature was 70 ℃ and the reaction was stirred at 500rpm for 5 hours. After the reaction is finished, separating and purifying to obtain the target product FDCA. HMF conversion was 88.2% with a selectivity of 91%.
Example 7
5-hydroxymethylfurfural HMF (0.5 mmol), acetonitrile (5 mL), oxidant TBHP (2.5 mmol) and catalyst C @ CoMn (0.1 g) were added to the reaction tube. The reaction temperature was 70 ℃ and the reaction was stirred at 1200rpm for 5 hours. After the reaction is finished, separating and purifying to obtain the target product FDCA. HMF conversion was 98% with a selectivity of 91.5%.
Example 8
5-hydroxymethylfurfural HMF (0.5 mmol), acetonitrile (5 mL), oxidant TBHP (2.5 mmol) and catalyst C @ CoMn (0.1 g) were added to the reaction tube. The reaction temperature is 70 ℃, and the stirring reaction is carried out for 3 hours at 800 rpm. After the reaction is finished, separating and purifying to obtain the target product FDCA. HMF conversion was 65% and selectivity was 80%.
Example 9
5-hydroxymethylfurfural HMF (0.5 mmol), acetonitrile (5 mL), oxidant TBHP (2.5 mmol) and catalyst C @ CoMn (0.1 g) were added to the reaction tube. The reaction temperature was 70 ℃ and the reaction was stirred at 800rpm for 6 hours. After the reaction is finished, separating and purifying to obtain the target product FDCA. HMF conversion was >99.9% with selectivity 92%.
Example 10
5-hydroxymethylfurfural HMF (0.5 mmol), toluene (5 mL), oxidant TBHP (2.5 mmol), and catalyst C @ CoMn (0.1 g) were added to the reaction tube. The reaction temperature was 70 ℃ and the reaction was stirred at 800rpm for 6 hours. After the reaction is finished, separating and purifying to obtain the target product FDCA. HMF conversion was 90% and selectivity was 86%.
Example 11
5-hydroxymethylfurfural HMF (0.5 mmol), tetrahydrofuran (5 mL), oxidant TBHP (2.5 mmol) and catalyst C @ CoMn (0.1 g) were added to the reaction tube. The reaction temperature was 70 ℃ and the reaction was stirred at 800rpm for 6 hours. After the reaction is finished, separating and purifying to obtain the target product FDCA. HMF conversion was 90.9% with selectivity 83%.
Example 12
5-hydroxymethylfurfural HMF (0.5 mmol), 1, 4-dioxane (5 mL), oxidant TBHP (2.5 mmol), and catalyst C @ CoMn (0.1 g) were added to the reaction tube. The reaction temperature was 70 ℃ and the reaction was stirred at 800rpm for 6 hours. After the reaction is finished, separating and purifying to obtain the target product FDCA. HMF conversion was 95% and selectivity was 80%.
The invention overcomes the problems of low selectivity of the HMF oxidation process and environmental pollution caused by the use of an alkaline reagent, and realizes the efficient and high-selectivity conversion of HMF into FDCA in a mild environment by the Lewis alkaline site regulation and control effect of C @ CoMn and the promotion of the generation of superoxide radical beneficial to the oxidation reaction by manganese active species, thereby having industrial application prospect.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (10)

1. A green synthesis method for preparing 2, 5-furandicarboxylic acid by catalyzing 5-hydroxymethylfurfural through tandem oxidation is characterized in that HMF, a reaction medium, TBHP and C @ CoMn are added into a reaction container, and are stirred to perform oxidation reaction, so that FDCA is obtained.
2. The green synthesis method according to claim 1, wherein the preparation method of C @ CoMn comprises the following steps:
1) Dissolving polyoxyethylene polyoxypropylene ether and dopamine hydrochloride in a water-ethanol mixed solution according to a ratio, and adding manganese salt and cobalt salt under a stirring condition to obtain a solution;
2) Adding ammonia water into the solution A, and stirring for reaction to obtain a catalyst precursor;
3) Calcining the obtained catalyst precursor in an air atmosphere at 330-370 ℃ for 2-6 h to obtain the C @ CoMn.
3. The green synthesis method according to claim 2, wherein in the step 1), the molar ratio of the polyoxyethylene polyoxypropylene ether to the dopamine hydrochloride to the manganese salt to the cobalt salt is 1: 60-65: 50 to 55:60 to 65 portions;
the manganese salt is manganese nitrate tetrahydrate, manganese acetate dihydrate, manganese sulfate monohydrate or manganese carbonate monohydrate;
the cobalt salt is cobalt nitrate tetrahydrate, cobalt carbonate, cobalt sulfate or cobalt acetate;
and mixing water and ethanol in the water-ethanol mixed solution in any proportion.
4. The green synthesis method according to claim 2, wherein in the step 2), the mass fraction of the ammonia water is 25-28%, and the volume of the ammonia water and the molar weight ratio of the polyoxyethylene polyoxypropylene ether are 6-10 ml/mol.
5. The green synthesis method according to claim 2, wherein in step 3), the calcination temperature is 350 ℃ and the calcination time is 4 hours.
6. The green synthesis method according to claim 1, wherein the concentration of C @ CoMn after addition is 30-35 g/L.
7. A green synthesis method according to claim 1, characterized in that the concentration of HMF after addition is 0.15-0.2 mol/L.
8. The green synthesis method according to claim 1, wherein the molar amount of TBHP is 3-6 times that of HMF.
9. The green synthesis method according to claim 1, wherein the reaction medium is any one of toluene, acetonitrile, tetrahydrofuran and 1, 4-dioxane.
10. The green synthesis method according to claim 1, wherein the reaction temperature is controlled to be 60-75 ℃, and the reaction time is controlled to be 5-7 h.
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