Method for catalyzing selective oxidation of 5-hydroxymethylfurfural by ion-doped birnessite

Abstract

A method for catalyzing selective oxidation of 5-hydroxymethylfurfural by ion-doped birnessite belongs to the field of chemical engineering, and comprises the following steps: adding an ion-doped birnessite type catalyst into a solvent, and catalyzing 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxaldehyde and 2, 5-furandicarboxylic acid in the atmosphere of air or oxygen at the temperature of 25-240 DEG C, wherein the solvent is water, methanol, ethanol, acetonitrile, dichloromethane, N, N-dimethylformamide, N, N-dimethylacetamide and the like. The method is simple, few in by-products and environmentally friendly. By adopting ion-doped birnessite as the catalyst, the method has the advantages of economy, environmental protection, mild conditions, high selectivity, easiness in recovery of the catalyst and the like; the ion-doped birnessite catalyst can efficiently and highly selectively catalyze oxidation of 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxaldehyde, catalytic materials are easy to separate, the production cost is low, and the ion-doped birnessite catalyst has remarkable technical and economic effects and application prospects.

Description

Technical Field

[0001] The invention relates to the chemical industry field, in particular to a method for catalytic selective oxidation of 5-hydroxymethylfurfural by ion-doped manganite Background Art

[0002] Today, the chemical industry remains one of the leading industries for the sustainable development of the global economy. However, most of the chemical industries rely on fossil raw materials, which are unsustainable, and the large amount of carbon emissions they generate has caused irreparable damage to the environment. Against this background, the development and utilization of biomass resources with rich reserves and renewable characteristics have gradually become a current research hotspot. Biomass is an abundant renewable carbon source that can provide valuable intermediates for the production of fuels, chemicals, and biobased plastics.

[0003] 5-Hydroxymethylfurfural (HMF) is an important platform compound with broad application prospects. The preparation of HMF mainly uses the biomass hydrolysis method, whose raw material source is rich and the price is low. It can be further dehydrated from glucose and fructose generated by the hydrolysis of lignocellulose. Due to the presence of aldehyde and hydroxyl groups in the structure of 5-hydroxymethylfurfural, its chemical properties are relatively active, and it can be used as a raw material for many high-value-added plastics and biofuels. For example, HMF can be oxidized to produce high-value-added products such as 2,5-furandicarboxaldehyde (FDC), 2,5-furandicarboxylic acid (FDCA), and levulinic acid (LA). Among them, 2,5-furandicarboxaldehyde, as an important organic chemical intermediate, has very wide applications in many fields, and its commercial price is very expensive. See: Catalysis Communications 57(2014)64–68; Ind.Eng.Chem.Res.53(2014)1313-1319; Chemical Industry and Engineering Progress 9(2011)1937; Applied Catalysis B: Environmental 180(2016)751–757; Food Chemistry 190(2016)481–486; Journal of Catalysis 265(2009)109-116.

[0004] There are many methods for directly oxidizing 5-hydroxymethylfurfural to furandicarboxaldehyde. Among them, scientific researchers have achieved a series of excellent research results in the thermal catalytic reaction system. Commonly used catalyst systems include metal salts, inorganic acids, supported metal catalysts, etc. For the realization of these reaction processes, the catalysts used are generally expensive. For example, gold is loaded onto nanoscale cerium oxide to prepare the catalyst. Therefore, developing an efficient, low-cost, and environmentally friendly catalytic system has important practical significance. Summary of the Invention

[0005] The object of the present invention is to provide a method for catalytic selective oxidation of 5-hydroxymethylfurfural by ion-doped manganite, aiming at the above technical analysis and existing problems. This method has the advantages of simple process, economic environmental protection, good catalytic effect, high product yield, easy separation, mild reaction conditions, low production cost, no safety hazards and environmental friendliness.

[0006] To achieve the above object, the present invention adopts the following technical scheme:

[0007] A method for catalytic selective oxidation of 5-hydroxymethylfurfural by ion-doped manganite: Using 5-hydroxymethylfurfural as the reaction substrate, adding a solvent, and adding ion-doped manganite as the catalyst. The amount of the catalyst added is between 2.0 and 40.0 mol% of the amount of the reaction substrate; Using air or oxygen at 0.1 - 2 Mpa as the oxidant, heating and stirring, then selectively converting to produce 2,5-furandicarboxaldehyde and 2,5-furandicarboxylic acid.

[0008] The dosage ratio of the 5-hydroxymethylfurfural to the solvent is 0.004 - 0.20 g / mL.

[0009] The solvent is one of acetonitrile, absolute methanol, absolute ethanol, ethyl acetate, diethyl succinate, nitromethane, dichloromethane, cyclohexane, n-hexane, deionized water, distilled water, N,N-dimethylformamide, N,N-dimethylacetamide, acetone, dimethyl sulfoxide, toluene or benzonitrile.

[0010] The amount of the catalyst is between 2.0 and 20.0 mol% of the amount of the reaction substrate.

[0011] The preferred catalyst is Li-doped manganite.

[0012] The reaction time of the reaction system under oxygen or air is 0 - 48 hours.

[0013] The preferred temperature range of the reaction is 25 - 240 °C, and the stirring rate is 0 - 9000 r / min.

[0014] The advantages of the present invention are as follows: This method is simple and easy to operate, with few by-products and environmental friendliness. Using ion-doped manganite as the catalyst has the advantages of economic environmental protection, mild conditions, high selectivity, and easy recovery of the catalyst; The ion-doped manganite catalyst can efficiently and highly selectively catalyze the oxidation of 5-hydroxymethylfurfural to prepare 2,5-furandicarboxaldehyde. The catalytic material is easy to separate, the production cost is low, and it has significant technical and economic effects and good application prospects. Specific embodiments

[0015] The following further illustrates the present invention through examples. In the examples, the Li-doped manganite catalyst is prepared by the precipitation method and stirred at room temperature for 6 h.

[0016] Example 1

[0017] A method for selectively oxidizing 5 - hydroxymethylfurfural by ion - doped birnessite. Using 5 - hydroxymethylfurfural as the substrate and Li - doped birnessite as the catalyst, the selective oxidation of 5 - hydroxymethylfurfural is carried out. The specific method is as follows: Dissolve 0.2 g of 5 - hydroxymethylfurfural in 15 mL of N,N - dimethylformamide, add 0.05 g of Li - doped birnessite, and react at a temperature of 140 °C and a stirring speed of 100 revolutions per minute for 4 hours. Through the high catalytic performance of Li - doped birnessite and its special structural effect, 5 - hydroxymethylfurfural is selectively catalytically oxidized to obtain 2,5 - furandicarboxaldehyde. The reaction results are analyzed by liquid chromatography - mass spectrometry and high - performance liquid chromatography: The conversion rate of 5 - hydroxymethylfurfural is 97.4%, and the selectivity of 2,5 - furandicarboxaldehyde is 99%.

[0018] Example 2

[0019] A method for selectively oxidizing 5 - hydroxymethylfurfural by ion - doped birnessite. Using 5 - hydroxymethylfurfural as the substrate and Li - doped birnessite as the catalyst, the selective oxidation of 5 - hydroxymethylfurfural is carried out. The specific method is as follows: Dissolve 0.2 g of 5 - hydroxymethylfurfural in 15 mL of N,N - dimethylformamide, add 0.05 g of birnessite, and react at a temperature of 140 °C and a stirring speed of 100 revolutions per minute for 4 hours. Through the high catalytic performance of birnessite and its special structural effect, 5 - hydroxymethylfurfural is selectively catalytically oxidized to obtain 2,5 - furandicarboxaldehyde. The reaction results are analyzed by liquid chromatography - mass spectrometry and high - performance liquid chromatography: The conversion rate of 5 - hydroxymethylfurfural is 83.4%, and the selectivity of 2,5 - furandicarboxaldehyde is 87.6%.

[0020] Example 3

[0021] A method for selectively oxidizing 5 - hydroxymethylfurfural by ion - doped birnessite. Using 5 - hydroxymethylfurfural as the substrate and Li - doped birnessite as the catalyst, the selective oxidation of 5 - hydroxymethylfurfural is carried out. The specific method is as follows: Dissolve 0.2 g of 5 - hydroxymethylfurfural in 15 mL of toluene, add 0.05 g of Li - doped birnessite, and react at a temperature of 140 °C and a stirring speed of 100 revolutions per minute for 4 hours. Through the high catalytic performance of Li - doped birnessite and its special structural effect, 5 - hydroxymethylfurfural is selectively catalytically oxidized to obtain 2,5 - furandicarboxaldehyde. The reaction results are analyzed by liquid chromatography - mass spectrometry and high - performance liquid chromatography: The conversion rate of 5 - hydroxymethylfurfural is 82.9%, and the selectivity of 2,5 - furandicarboxaldehyde is 95.1%.

[0022] Example 4

[0023] A method for the selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped birnessite, using 5-hydroxymethylfurfural as the substrate and Li-doped birnessite as the catalyst, for the selective oxidation preparation of 5-hydroxymethylfurfural. The specific method is as follows: Dissolve 0.2 g of 5-hydroxymethylfurfural in 15 mL of water, add 0.05 g of Li-doped birnessite, and react at a temperature of 140 °C and a stirring speed of 100 revolutions per minute for 4 hours. Through the high catalytic performance of Li-doped birnessite and its special structural effect, selectively catalytically oxidize 5-hydroxymethylfurfural to obtain 2,5-furandialdehyde. Analyze the reaction results using a liquid chromatography-mass spectrometry instrument and high-performance liquid chromatography: The conversion rate of 5-hydroxymethylfurfural is 74.8%, and the selectivity of 2,5-furandialdehyde is 94.5%.

[0024] Example 5

[0025] A method for the selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped birnessite, using 5-hydroxymethylfurfural as the substrate and Li-doped birnessite as the catalyst, for the selective oxidation preparation of 5-hydroxymethylfurfural. The specific method is as follows: First, dissolve approximately 0.2 g of 5-hydroxymethylfurfural in 15 mL of acetone, add 0.05 g of Li-doped birnessite, and react at a temperature of 140 °C and a stirring speed of 100 revolutions per minute for 4 hours. Through the high catalytic performance of Li-doped birnessite and its special structural effect, selectively catalytically oxidize 5-hydroxymethylfurfural to obtain 2,5-furandialdehyde. Analyze the reaction results using a liquid chromatography-mass spectrometry instrument and high-performance liquid chromatography: The conversion rate of 5-hydroxymethylfurfural is 33.1%, and the selectivity of 2,5-furandialdehyde is 99%.

[0026] Example 6

[0027] A method for the selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped birnessite, using 5-hydroxymethylfurfural as the substrate and Li-doped birnessite as the catalyst, for the selective oxidation preparation of 5-hydroxymethylfurfural. The specific method is as follows: Dissolve 0.2 g of 5-hydroxymethylfurfural in 15 mL of methanol, add 0.05 g of Li-doped birnessite, and react at a temperature of 140 °C and a stirring speed of 100 revolutions per minute for 4 hours. Through the high catalytic performance of Li-doped birnessite and its special structural effect, selectively catalytically oxidize 5-hydroxymethylfurfural to obtain 2,5-furandialdehyde. Analyze the reaction results using a liquid chromatography-mass spectrometry instrument and high-performance liquid chromatography: The conversion rate of 5-hydroxymethylfurfural is 92.9%, and the selectivity of 2,5-furandialdehyde is 84.9%.

[0028] Example 7

[0029] A method for the selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped birnessite, using 5-hydroxymethylfurfural as the substrate and Li-doped birnessite as the catalyst, for the selective oxidation of 5-hydroxymethylfurfural. The specific method is as follows: Dissolve 0.2 g of 5-hydroxymethylfurfural in 15 mL of ethanol, add 0.05 g of Li-doped birnessite, and react at a temperature of 140 °C and a stirring speed of 100 revolutions per minute for 2 hours. Through the high catalytic performance of Li-doped birnessite and its special structural effect, selectively catalytically oxidize 5-hydroxymethylfurfural to obtain 2,5-furandialdehyde. Analyze the reaction results by liquid chromatography-mass spectrometry and high-performance liquid chromatography: The conversion rate of 5-hydroxymethylfurfural is 79.4%, and the selectivity of 2,5-furandialdehyde in the product is 88.9%.

[0030] Example 8

[0031] A method for the selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped birnessite, using 5-hydroxymethylfurfural as the substrate and Li-doped birnessite as the catalyst, for the selective oxidation of 5-hydroxymethylfurfural. The specific method is as follows: Dissolve 0.2 g of 5-hydroxymethylfurfural in 15 mL of N,N-dimethylformamide, add 0.05 g of Li-doped birnessite, and react at a temperature of 120 °C and a stirring speed of 100 revolutions per minute for 4 hours. Through the high catalytic performance of Li-doped birnessite and its special structural effect, selectively catalytically oxidize 5-hydroxymethylfurfural to obtain 2,5-furandialdehyde. Analyze the reaction results by liquid chromatography-mass spectrometry and high-performance liquid chromatography: The conversion rate of 5-hydroxymethylfurfural is 85.9%, and the selectivity of 2,5-furandialdehyde is 95.1%.

[0032] Example 9

[0033] A method for the selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped birnessite, using 5-hydroxymethylfurfural as the substrate and Li-doped birnessite as the catalyst, for the selective oxidation of 5-hydroxymethylfurfural. The specific method is as follows: Dissolve 0.2 g of 5-hydroxymethylfurfural in 15 mL of N,N-dimethylformamide, add 0.05 g of Li-doped birnessite, and react at a temperature of 140 °C and a stirring speed of 100 revolutions per minute for 2 hours. Through the high catalytic performance of Li-doped birnessite and its special structural effect, selectively catalytically oxidize 5-hydroxymethylfurfural to obtain 2,5-furandialdehyde. Analyze the reaction results by liquid chromatography-mass spectrometry and high-performance liquid chromatography: The conversion rate of 5-hydroxymethylfurfural is 63.7%, and the selectivity of 2,5-furandialdehyde is 96.2%.

[0034] Example 10

[0035] A method for the selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped birnessite, using 5-hydroxymethylfurfural as a substrate and Li-doped birnessite as a catalyst, for the selective oxidation preparation of 5-hydroxymethylfurfural. The specific method is as follows: Dissolve 0.5 g of 5-hydroxymethylfurfural in 15 mL of N,N-dimethylformamide, add 0.10 g of Li-doped birnessite, and react at a temperature of 140 °C and a stirring speed of 100 revolutions per minute for 6 hours. Through the high catalytic performance of Li-doped birnessite and its special structural effect, selectively catalytically oxidize 5-hydroxymethylfurfural to obtain 2,5-furandicarboxaldehyde. Use liquid chromatography-mass spectrometry and high performance liquid chromatography to analyze the reaction results: The conversion rate of 5-hydroxymethylfurfural is 90.7%, and the selectivity of 2,5-furandicarboxaldehyde is 99%.

[0036] Example 11

[0037] A method for the selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped birnessite, using 5-hydroxymethylfurfural as a substrate and Li-doped birnessite as a catalyst, for the selective oxidation preparation of 5-hydroxymethylfurfural. The specific method is as follows: Dissolve 1.0 g of 5-hydroxymethylfurfural in 15 mL of N,N-dimethylformamide, add 0.30 g of Li-doped birnessite, and react at a temperature of 140 °C and a stirring speed of 100 revolutions per minute for 7 hours. Through the high catalytic performance of Li-doped birnessite and its special structural effect, selectively catalytically oxidize 5-hydroxymethylfurfural to obtain 2,5-furandicarboxaldehyde. Use liquid chromatography-mass spectrometry and high performance liquid chromatography to analyze the reaction results: The conversion rate of 5-hydroxymethylfurfural is 85.3%, and the selectivity of 2,5-furandicarboxaldehyde is 99%.

[0038] Example 12

[0039] A method for the selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped birnessite, using 5-hydroxymethylfurfural as a substrate and Li-doped birnessite as a catalyst, for the selective oxidation preparation of 5-hydroxymethylfurfural. The specific method is as follows: Dissolve 0.2 g of 5-hydroxymethylfurfural in 15 mL of water (deionized water and distilled water), add 0.05 g of Li-doped birnessite, and react at a temperature of 140 °C and a stirring speed of 100 revolutions per minute for 8 hours. Through the high catalytic performance of Li-doped birnessite and its special structural effect, selectively catalytically oxidize 5-hydroxymethylfurfural to obtain 2,5-furandicarboxaldehyde. Use liquid chromatography-mass spectrometry and high performance liquid chromatography to analyze the reaction results: The conversion rate of 5-hydroxymethylfurfural is 96.4%, and the selectivity of 2,5-furandicarboxylic acid is 67.9%.

[0040] Example 13

[0041] A method for selectively oxidizing 5-hydroxymethylfurfural by ion-doped birnessite, using 5-hydroxymethylfurfural as a substrate and Li-doped birnessite as a catalyst for the selective oxidation preparation of 5-hydroxymethylfurfural. The specific method is as follows: Dissolve 0.2 g of 5-hydroxymethylfurfural in 15 mL of water (deionized water and distilled water), add 0.05 g of Li-doped birnessite, and react at a temperature of 120 °C and a stirring speed of 100 revolutions per minute for 10 hours. Through the high catalytic performance of Li-doped birnessite and its special structural effect, selectively catalytically oxidize 5-hydroxymethylfurfural to obtain 2,5-furandicarboxaldehyde. Analyze the reaction results by liquid chromatography-mass spectrometry and high-performance liquid chromatography: The conversion rate of 5-hydroxymethylfurfural is 98.3%, and the selectivity of 2,5-furandicarboxylic acid is 61.4%.

Claims

1. A method for selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped manganite, characterized in that: 5-Hydroxymethylfurfural is used as a reaction substrate, a solvent is added, and ion-doped manganite is added as a catalyst, wherein the amount of the added catalyst is between 2.0 and 40.0 mol% of the amount of the reaction substrate; 0.1-2Mpa air or oxygen is used as an oxidant, and heating and stirring are performed to selectively convert and generate 2,5-furandicarboxaldehyde and 2,5-furandicarboxylic acid.

2. The method for selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped manganite as claimed in claim 1, characterized in that: The dosage ratio of the 5-hydroxymethylfurfural to the solvent is 0.004-0.20 g / mL.

3. The method for selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped manganite as claimed in claim 1, characterized in that: The solvent is one of acetonitrile, anhydrous methanol, anhydrous ethanol, ethyl acetate, diethyl succinate, nitromethane, dichloromethane, cyclohexane, n-hexane, deionized water, distilled water, N,N-dimethylformamide, N,N-dimethylacetamide, acetone, dimethyl sulfoxide, toluene or benzonitrile.

4. The method for selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped manganite as claimed in claim 1, characterized in that: The amount of the catalyst is between 2.0 and 20.0 mol% of the amount of the reaction substrate.

5. The method for selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped manganite as claimed in claim 1 is characterized in that: The catalyst is preferably Li-doped manganite.

6. The method for selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped manganite as claimed in claim 1, characterized in that: The reaction time of the reaction system under oxygen or air is 0 to 48 hours.

7. The method for selective oxidation of 5-hydroxymethylfurfural catalyzed by ion-doped manganite as claimed in claim 1, characterized in that: The reaction temperature range is preferably 25-240° C., and the stirring rate is 0-9000 r / min.