CN114736178B - Method for preparing 5-formyl-2-furancarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural - Google Patents
Method for preparing 5-formyl-2-furancarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural Download PDFInfo
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Abstract
The invention discloses a method for preparing 5-formyl-2-furancarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural. The specific method comprises the following steps: and adding 5-hydroxymethylfurfural, an N-hydroxyphthalimide (NHPI) catalyst and a eutectic solvent (DES) into the Teflon lining, sealing, introducing oxygen for purging, introducing oxygen with a certain pressure after purging for three times, and reacting at a specified temperature to obtain the 5-formyl-2-furancarboxylic acid. The invention couples the organic micromolecular catalyst with the eutectic solvent and is applied to the preparation of FFCA by HMF oxidation, the reaction condition is mild, the operation is simple and convenient, the cost is low, FFCA can be efficiently synthesized (the yield reaches 94 percent), and the invention is an FFCA preparation method under the condition of no alkali and no metal.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a method for preparing 5-formyl-2-furancarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural.
Background
Biomass is a renewable carbon source outside fossil resources, and development and utilization of biomass are important components for realizing sustainable energy, and can provide substitution for chemicals for fossil fuel production. An important pathway for biomass conversion is the conversion of carbohydrates to key platform compounds. Among them, the dehydration product of carbohydrates such as fructose, 5-hydroxymethylfurfural, is widely used, and can be converted into high value-added chemicals through oxidation, hydrogenation, polymerization and ring-opening reactions of its alcohol, aldehyde and furan rings. The 5-Hydroxymethylfurfural (HMF) can be used for synthesizing value-added chemicals such as 5-formyl-2-furancarboxylic acid (FFCA) and the like through oxidation reaction. FFCA is an important biological material and has wide application prospect in the aspects of drug synthesis and chemical intermediate synthesis. Because of the more side reactions and byproducts of the aerobic oxidation process of HMF, the energy barrier for activating oxygen under mild conditions is higher. It is therefore desirable to develop and design catalytic systems that adjust the reaction path by optimizing the catalyst components and reaction medium to achieve higher yields of the desired product.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-efficiency catalytic oxidation system, in particular to a method for preparing 5-formyl-2-furancarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural. The invention relates to a method for catalyzing and oxidizing HMF into FFCA by coupling an organic micromolecular catalyst and a eutectic solvent, which realizes the conversion from HMF to FFCA.
The technical scheme of the invention is as follows:
the method for preparing the 5-formyl-2-furancarboxylic acid by catalytic oxidation of the 5-hydroxymethylfurfural comprises the following steps:
1) Mixing a hydrogen bond donor and a hydrogen bond acceptor according to a molar ratio, heating and stirring at 80-150 ℃ until a uniform and clear liquid is obtained, and obtaining a eutectic solvent (DES);
wherein the hydrogen bond acceptor is tetrabutylammonium chloride and the hydrogen bond donor is PEG2000;
2) Adding 5-hydroxymethylfurfural, a catalyst and a eutectic solvent (DES) into a reaction kettle, sealing, introducing oxygen, purging and evacuating air to enable the reaction kettle to be filled with oxygen, reacting for 6-12h at the temperature of 90-150 ℃ to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid,
wherein the small organic molecule catalyst comprises N-hydroxyphthalimide (NHPI), N-hydroxysuccinimide (NHSI) and N-chloro-phthalimide (NCPI).
Preferably, the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1:0.5 to 3.
Preferably, the synthesis temperature of the eutectic solvent (DES) is 80 ℃.
Preferably, the mass ratio of the 5-hydroxymethylfurfural to the catalyst is 1: the mass ratio of 0.4-4, 5-hydroxymethylfurfural to the eutectic solvent is 1:40 to 240.
Preferably, the pressure of oxygen in the reaction vessel is 1.5MPa.
According to the invention, the HMF is successfully catalyzed and oxidized into FFCA through a NHPI and DES coupling system, and the catalytic activity of the catalyst is improved by utilizing the promotion effect of DES on reactants and the catalyst. Experimental results show that the catalytic cycle of the small organic molecule catalyst and the auxiliary action of DES are necessary in the process of oxidizing HMF into FFCA, under the optimal reaction condition, the HMF conversion rate is 100%, and the FFCA yield reaches 94%.
The beneficial effects of the invention are as follows:
the invention provides a novel catalytic system, namely a coupling system of N-hydroxyphthalimide and a eutectic solvent, which can be effectively applied to the preparation of 5-formyl-2-furancarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural.
The invention provides a method for improving the catalytic performance of a catalyst through interaction of DES and NHPI, and simultaneously, reconstruction of hydrogen bonds between the DES and HMF has a key promotion effect on high conversion rate and high selectivity of the reaction.
In addition, the invention has simple operation of the technological process and mild reaction condition, and is a method for preparing FFCA with low cost and high efficiency under the condition of no alkali and no metal.
The invention provides reference for renewable biomass resource conversion, has important significance for development of novel renewable energy sources, and compared with noble metal catalysts in the prior art, the catalyst used by the invention has higher FFCA selectivity and is more economical.
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1 (reference example, TBAB)
The catalytic oxidation of 5-hydroxymethylfurfural to prepare 5-formyl-2-furancarboxylic acid comprises the following steps:
(1) Mixing PEG2000 and TBAB according to a mole ratio of 1/2, heating and stirring for 1 hour at 80 ℃ to obtain a uniform and clear liquid, namely a eutectic solvent PEG2000/TBAB 1/2;
(2) Adding 0.2mmol of HMF, 20mgNHPI catalyst and 2g of the eutectic solvent (DES) synthesized in the step (1) into a Teflon lining, sealing, purging with oxygen, purging for three times, introducing 1.5MPa of oxygen, and reacting for 6 hours at 130 ℃ to obtain a reaction mixture;
(3) The mixed solution was diluted with water as a solvent, analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, which show that the HMF conversion was 68% and no FFCA was generated.
Example 1 shows that: the eutectic solvent PEG2000/TBAB 1/2 does not allow the catalytic oxidation of 5-hydroxymethylfurfural to produce 5-formyl-2-furancarboxylic acid.
Example 2
The catalytic oxidation of 5-hydroxymethylfurfural to prepare 5-formyl-2-furancarboxylic acid comprises the following steps:
(1) Mixing PEG2000 and tetrabutylammonium chloride (TBAC) according to a molar ratio of 1/2, heating and stirring for 1 hour at 80 ℃ to obtain a uniform and clear liquid, namely, eutectic solvent PEG2000/TBAC 1/2;
(2) Adding 0.2mmol of HMF, 20mg of NHPI catalyst and 2g of DES synthesized in the step (1) into a Teflon lining, sealing, introducing oxygen for purging, introducing 1.5MPa of oxygen after purging for three times, and reacting for 6 hours at 130 ℃ to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid (FFCA);
(3) The mixed solution was diluted with water as a solvent and analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, which show that the HMF conversion was 100% and the FFCA yield was 74%.
Example 2 shows: the eutectic solvent PEG2000/TBAC1/2 can promote the reaction of preparing 5-formyl-2-furancarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural, and the reaction is shown in combination with example 1: although TBAB is close to TBAC in chemical nature, experimental results show that not all low co-solvents coupled with small organic molecule catalysts are capable of achieving catalytic oxidation of 5-hydroxymethylfurfural to 5-formyl-2-furancarboxylic acid.
Examples 5 to 10 described below all use the eutectic solvent (PEG 2000/TBAC) prepared in example 2 as a reaction medium, and examples 3 and 4 below are reference examples without DES addition.
Example 3 (reference example, DES free)
The catalytic oxidation of 5-hydroxymethylfurfural to prepare 5-formyl-2-furancarboxylic acid comprises the following steps:
(1) Adding 0.2mmol of HMF, 20mg of NHPI catalyst and 1.560 g of PEG2000 into a Teflon lining, sealing, introducing oxygen for purging, introducing 1.5MPa of oxygen after purging for three times, and reacting for 6 hours at 130 ℃ to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid (FFCA);
(2) The mixed solution was diluted with water as a solvent and analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, which show that the HMF conversion was 100% and the FFCA yield was only 1%.
Example 4 (reference example, no DES)
The catalytic oxidation of 5-hydroxymethylfurfural to prepare 5-formyl-2-furancarboxylic acid comprises the following steps:
(1) Adding 0.2mmol of HMF, 20mgNHPI catalyst and 0.435g of TBAC into a Teflon lining, sealing, introducing oxygen for purging, introducing 1.5MPa of oxygen after purging for three times, and reacting for 6 hours at 130 ℃ to obtain a reaction mixture;
(2) The mixed solution was diluted with water as a solvent, analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, which show that the HMF conversion was 47% and no FFCA was generated.
Examples 3 and 4 above demonstrate that: without adding DES, only adding organic small molecule catalyst and any component of DES (hydrogen bond donor or hydrogen bond acceptor) has no effect on preparing 5-formyl-2-furancarboxylic acid by catalyzing and oxidizing 5-hydroxymethylfurfural.
Example 5 (reference, no organic small molecule catalyst)
The catalytic oxidation of 5-hydroxymethylfurfural to prepare 5-formyl-2-furancarboxylic acid comprises the following steps:
(1) The eutectic solvent PEG2000/TBAC1/2 was synthesized using the same method as example 2;
(2) Adding 0.2mmol of HMF and 2g of DES synthesized in the step (1) into a Teflon lining, sealing, introducing oxygen for purging, introducing 1.5MPa of oxygen after purging for three times, and reacting for 6 hours at 130 ℃ to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid (FFCA);
(3) The mixed solution was diluted with water as a solvent and analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, which show that the HMF conversion was 100% and the FFCA yield was only 1%.
Example 5 shows that: the addition of DES alone without the addition of small organic molecule catalysts does not allow for the efficient catalytic oxidation of HMF to FFCA. Meanwhile, it is demonstrated in connection with examples 1, 2, 3 and 4 that only small organic molecule catalysts and specific DES (PEG 2000/TBAC) couplings are able to effectively catalyze the oxidation of HMF to FFCA.
Example 6
The catalytic oxidation of 5-hydroxymethylfurfural to prepare 5-formyl-2-furancarboxylic acid comprises the following steps:
(1) The eutectic solvent PEG2000/TBAC1/2 was synthesized using the same method as example 2;
(2) Adding 0.2mmol of HMF, 20mg of NHSI catalyst and 2g of DES synthesized in the step (1) into a Teflon lining, sealing, introducing oxygen for purging, introducing 1.5MPa of oxygen after purging for three times, and reacting for 6 hours at 130 ℃ to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid (FFCA);
(3) The mixed solution was diluted with water as a solvent and analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, which show that the HMF conversion was 81% and the FFCA yield was 21%.
Example 7
The catalytic oxidation of 5-hydroxymethylfurfural to prepare 5-formyl-2-furancarboxylic acid comprises the following steps:
(1) The eutectic solvent PEG2000/TBAC1/2 was synthesized using the same method as example 2;
(2) Adding 0.2mmol of HMF, 20mgNCPI catalyst and 2g of DES synthesized in the step (1) into a Teflon lining, sealing, introducing oxygen for purging, introducing 1.5MPa of oxygen after purging for three times, and reacting for 6 hours at 130 ℃ to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid (FFCA);
(3) The mixed solution was diluted with water as a solvent and analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, which show that the HMF conversion was 98% and the FFCA yield was 17%.
Example 6 and example 7 show that: not all small organic molecule catalysts can be coupled with a low cosolvent to efficiently catalyze and oxidize 5-hydroxymethylfurfural to prepare 5-formyl-2-furancarboxylic acid, and the NHPI catalyst of example 2 has better catalytic effect after coupling.
Example 8
(1) The eutectic solvent PEG2000/TBAC1/2 was synthesized using the same method as example 2;
(2) Adding 0.2mmol of HMF, 20mg of NHPI catalyst and 2g of DES synthesized in the step (1) into a Teflon lining, sealing, introducing oxygen for purging, introducing 1.5MPa of oxygen after purging for three times, and reacting for 8 hours at 130 ℃ to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid (FFCA);
(3) The mixed solution was diluted with water as a solvent and analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, which show that the HMF conversion was 100% and the FFCA yield was 80%.
Example 9
The catalytic oxidation of 5-hydroxymethylfurfural to prepare 5-formyl-2-furancarboxylic acid comprises the following steps:
(1) The eutectic solvent PEG2000/TBAC1/2 was synthesized using the same method as example 2;
(2) Adding 0.2mmol of HMF, 20mg of NHPI catalyst and 2g of DES synthesized in the step (1) into a Teflon lining, sealing, introducing oxygen for purging, introducing 1.5MPa of oxygen after purging for three times, and reacting for 10 hours at 130 ℃ to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid (FFCA);
(3) The mixed solution was diluted with water as a solvent and analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, which show that the HMF conversion was 100% and the FFCA yield was 94%.
Example 10
The catalytic oxidation of 5-hydroxymethylfurfural to prepare 5-formyl-2-furancarboxylic acid comprises the following steps:
(1) The eutectic solvent PEG2000/TBAC1/2 was synthesized using the same method as example 2;
(2) Adding 0.2mmol of HMF, 20mg of NHPI catalyst and 2g of DES synthesized in the step (1) into a Teflon lining, sealing, introducing oxygen for purging, introducing 1.5MPa of oxygen after purging for three times, and reacting for 12h at 130 ℃ to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid (FFCA);
(3) The mixed solution was diluted with water as a solvent and analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, which shows that the HMF conversion was 100% and the FFCA yield was 60%.
Examples 2, 6-10 demonstrate that: the reaction time is preferably 6 to 12 hours, and when the reaction time is less than 6 hours, the reaction is insufficient, and when the reaction time exceeds 12 hours, byproducts are generated.
Example 11
(1) The eutectic solvent PEG2000/TBAC 1/0.5 was synthesized using the same method as example 2;
(2) Adding 0.2mmol of HMF, 20mg of NHPI catalyst and 2g of DES synthesized in the step (1) into a Teflon lining, sealing, introducing oxygen for purging, introducing 1.5MPa of oxygen after purging for three times, and reacting for 10 hours at 130 ℃ to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid (FFCA);
(3) The mixed solution was diluted with water as a solvent and analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, which shows that the HMF conversion was 100% and the FFCA yield was 9%.
Example 12
(1) The eutectic solvent PEG2000/TBAC 1/3 was synthesized using the same method as example 2;
(2) Adding 0.2mmol of HMF, 20mg of NHPI catalyst and 2g of DES synthesized in the step (1) into a Teflon lining, sealing, introducing oxygen for purging, introducing 1.5MPa of oxygen after purging for three times, and reacting for 10 hours at 130 ℃ to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid (FFCA);
(3) The mixed solution was diluted with water as a solvent and analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, which show that the HMF conversion was 100% and the FFCA yield was 36%.
Examples 10, 11, 12 demonstrate: the molar ratio of PEG2000/TBAC in the eutectic solvent has a great influence on preparing 5-formyl-2-furancarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural, the 5-formyl-2-furancarboxylic acid can be prepared by oxidizing 5-hydroxymethylfurfural between PEG2000/TBAC of 1 (0.5-3), and the optimal condition is realized when the PEG2000/TBAC is 1:2.
Example 13
(1) The eutectic solvent PEG2000/TBAC1/2 was synthesized using the same method as example 2;
(2) Adding 0.2mmol of HMF, 10mg of NHPI catalyst and 2g of DES synthesized in the step (1) into a Teflon lining, sealing, introducing oxygen for purging, introducing 1.5MPa of oxygen after purging for three times, and reacting for 10 hours at 130 ℃ to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid (FFCA);
(3) The mixed solution was diluted with water as a solvent and analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, which shows that the HMF conversion was 91% and the FFCA yield was 2%.
Example 14
(1) The eutectic solvent PEG2000/TBAC1/2 was synthesized using the same method as example 2;
(2) Adding 0.2mmol of HMF, 100mgNHPI catalyst and 2g of DES synthesized in the step (1) into a Teflon lining, sealing, introducing oxygen for purging, introducing 1.5MPa of oxygen after purging for three times, and reacting for 10 hours at 130 ℃ to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid (FFCA);
(3) The mixed solution was diluted with water as a solvent and analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, showing that the HMF conversion was 100% and the FFCA yield was 12%.
Examples 13 and 14 show that: the dosage of the catalyst in the reaction system has great influence on preparing 5-formyl-2-furancarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural, and the oxidation of 5-hydroxymethylfurfural can be realized to prepare 5-formyl-2-furancarboxylic acid between HMF and NHPI with the mass ratio of 1 (0.4-4).
Example 15
(1) The eutectic solvent PEG2000/TBAC1/2 was synthesized using the same method as example 2;
(2) Adding 0.2mmol of HMF, 20mg of NHPI catalyst and 1g of DES synthesized in the step (1) into a Teflon lining, sealing, introducing oxygen for purging, introducing 1.5MPa of oxygen after purging for three times, and reacting for 10 hours at 130 ℃ to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid (FFCA);
(3) The mixed solution was diluted with water as a solvent and analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, which show that the HMF conversion was 98% and the FFCA yield was 34%.
Example 16
(1) The eutectic solvent PEG2000/TBAC1/2 was synthesized using the same method as example 2;
(2) Adding 0.2mmol of HMF, 20mg of NHPI catalyst and 6g of DES synthesized in the step (1) into a Teflon lining, sealing, introducing oxygen for purging, introducing 1.5MPa of oxygen after purging for three times, and reacting for 10 hours at 130 ℃ to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid (FFCA);
(3) The mixed solution was diluted with water as a solvent and analyzed by a high performance liquid chromatograph, and the product type was identified by using a standard solution, and the results are shown in table 1, showing that the HMF conversion was 100% and the FFCA yield was 1%.
Examples 15 and 16 show that: the usage amount of the eutectic solvent in the reaction system has a great influence on preparing 5-formyl-2-furancarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural, and the 5-formyl-2-furancarboxylic acid can be prepared by oxidizing 5-hydroxymethylfurfural between HMF and DES (DES) in a mass ratio of 1 (40-240).
TABLE 1 reaction results of the preparation of FFCA by catalytic oxidation of HMF of examples 1-10
The detailed description demonstrates in part the feasibility of a eutectic solvent (PEG 2000/TBAC 1/2) and small organic molecule catalyst coupling system for use in catalyzing the oxidation of HMF to FFCA, and the introduction of different DES components or different NHPI analogs can alter product distribution, but with lower effect on both conversion and FFCA selectivity than described in example 8. Examples 8-16 illustrate that under optimal reaction conditions: 130 ℃, 10h, 2g of eutectic solvent (PEG 2000/TBAC 1/2), 0.2mmol HMF, 20mg NHPI, as in example 9, the HMF conversion can reach 100% and FFCA yield reaches 94%. Further, the lengthy reaction time resulted in partial conversion of FFCA to FDCA, which was manifested as a drop in FFCA yield to 60% (example 10).
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (3)
1. The method for preparing 5-formyl-2-furancarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural is characterized by comprising the following steps:
1) Mixing a hydrogen bond donor and a hydrogen bond acceptor according to a molar ratio of 80-150 o Heating and stirring under the condition of C until a uniform and clear liquid is obtained, thus obtaining the eutectic solvent;
wherein the hydrogen bond acceptor is tetrabutylammonium chloride and the hydrogen bond donor is PEG2000; the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1: 0.5-3;
2) Adding 5-hydroxymethylfurfural, an organic micromolecular catalyst and a eutectic solvent into a reaction kettle, sealing, and introducing oxygen to purge and empty air to ensure that the reaction kettle is filled with oxygen at 90-150 o C, reacting for 6-12h at the temperature to obtain a reaction mixture containing 5-formyl-2-furancarboxylic acid,
wherein the organic micromolecular catalyst is N-hydroxyphthalimide, N-hydroxysuccinimide and N-chloro-phthalimide; the mass ratio of the 5-hydroxymethylfurfural to the organic small molecule catalyst is 1: 0.4-4, wherein the mass ratio of the 5-hydroxymethylfurfural to the eutectic solvent is 1: 40-240.
2. The method according to claim 1, wherein the eutectic solvent has a synthesis temperature of 80 o C。
3. The method according to claim 1, wherein the pressure of oxygen in the reaction vessel is 1.5MPa.
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