CN106565647A - Method for preparing 2, 5-furandicarboxylic acid by conducting catalytic oxidation on 5-hydroxymethylfurfural - Google Patents

Abstract

The invention relates to a method for preparing 2,5-furandicarboxylic acid (FDCA) by catalytically oxidizing a biomass derivative——5-hydroxymethylfurfural (HMF), and belongs to the field of synthesizing renewable chemicals from biomass and derivatives . The method comprises: using non-noble metal cerium-based composite oxide as a catalyst and oxygen or air as an oxidant to effectively catalyze and oxidize 5-hydroxymethylfurfural to synthesize 2,5-furandicarboxylic acid. The method is simple in operation, mild in conditions, and the yield of 2,5-furandicarboxylic acid can reach up to 86.7%. The catalyst is easy to separate and recover, has good reusability, and has good industrial application prospects.

Description

A method for preparing 2,5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural

technical field

The invention relates to a method for preparing 2, 5-furandicarboxylic acid (FDCA), which belongs to the field of synthesis of renewable chemicals from biomass and derivatives. More specifically, it relates to a method for preparing 2,5-furandicarboxylic acid by oxidation of 5-hydroxymethylfurfural.

Background technique

2,5-Furandicarboxylic acid (FDCA), as a furan compound that can be prepared from biomass, was identified as one of the 12 "platform compounds" by the US Department of Energy in 2004. It has a furan ring and two carboxyl groups, and is expected to replace petroleum-based monomer terephthalic acid in the polyester industry to synthesize green degradable plastics; it can also replace phthalic acid to synthesize green non-toxic plasticizers. Introducing the utilization of biomass into the polyester industry can reduce the dependence of the polyester industry on petroleum energy and reduce environmental pollution. In addition, starting from 2, 5-furandicarboxylic acid, derivatives with bactericidal and anesthetic functions such as succinic acid, dichlorofurandicarboxylic acid and dimethyl furandicarboxylate can also be synthesized.

At present, 2, 5-furandicarboxylic acid is mainly prepared by oxidation of 5-hydroxymethylfurfural (HMF), which generally requires the addition of catalysts, and catalysts are divided into heterogeneous catalysts and homogeneous catalysts. Homogeneous catalysts are mainly transition metal salts such as Co and Mn. For example, ^Grushin ’s research group used cobalt salts to catalyze the oxidation of HMF. The initial concentration of HMF is about 8%. The catalytic reaction was carried out for 3 hours, and the yield of FDCA was 60% (W. Partenheimer, VV Grushin, Adv. Synth. Catal., 2001, 343:102-111). In its patent (patent number: 201010516208.0), Canon Corporation of Japan prepared high-purity FDCA by reacting HMF with an oxidizing agent in an organic acid solvent in the presence of bromine and metal catalysts. These homogeneous catalytic reaction systems have disadvantages such as low yield, difficult separation of metal salts, and serious environmental pollution of bromine. In contrast, the heterogeneous catalytic method has the advantages of high selectivity, environmental protection, and easy separation of products. For HMF oxidation, there are mainly two categories of noble metal catalysts and non-noble metal catalysts. Noble metal catalysts include Pt, Au, Pd, etc. For example, Miao Zhenzhen et al. used the noble metal Au supported by CeBi composite oxide as a catalyst to catalyze the oxidation of HMF. At room temperature, the efficient conversion of HMF can be achieved (Zhenzhen Miao, Yibo Zhang, Catal. Sci. Technol., 2015, 5:1314-1322). Han Xuewang et al. used carbon-magnesia as the basic carrier to support the precious metal Pt, and achieved excellent results under alkali-free conditions, and the FDCA yield could reach 95% (Xuewang Han, Liang Geng, Green Chemistry, 2015,14: 4-17 ). In their patent (Patent No.: 201210390203.7), Ma Hong et al. use noble metals (Au, Ag, Pd, Pt, Ru) to load on the basic carrier to catalyze the oxidation of HMF, and the selectivity can reach 99%. In their patent (patent number: 201010228459), Lin Lu et al. used Pt, Au, Pd supported C or CuO-Ag ₂ O as a catalyst to catalyze the oxidation of HMF in alkaline solution to prepare FDCA, and obtained a higher yield of FDCA. Although these noble metal catalysts have good catalytic selectivity and high stability, the noble metals are expensive and not suitable for large-scale industrial production. However, the existing non _- noble metal heterogeneous catalysts generally have the problems of low selectivity and poor stability under the condition _of oxygen or air. With butanol as the oxidant, the FDCA yield can reach 68.6%, but if oxygen is used as the oxidant, the FDCA yield is only 4.2% (Shuguo Wang, Zehui Zhang, ACS Sustainable Chem. Eng., 2015, 3: 406-412). The porphyrin cobalt catalyst supported by chloromethyl resin can also obtain higher FDCA yield under the condition of tert-butanol peroxide as oxidant, but the FDCA yield is very low when oxygen is used as oxidant (Langchang Gao, Kejian Deng , Zehui Zhang, Chemical Engineering Journal, 2015, 270: 444-449). Therefore, it is urgent to find a stable and efficient non-precious metal catalyst for the oxidation of HMF to FDCA by oxygen or air.

Compared with the existing reports, the present invention uses non-noble metal cerium-based composite oxide as the catalyst, which has the following advantages: (1) The reaction conditions are mild, the conversion rate of HMF is high, and the yield of FDCA can reach 86.7%. (2) Using non-precious metals as active components, the catalyst cost is low. (3) The catalyst prepared and used in the present invention has good reusability. The method for synthesizing 2,5-furandicarboxylic acid provided by the present invention is innovative and has strong application value.

Contents of the invention

Aiming at the shortcomings of the prior art, the present invention proposes a FDCA preparation method with mild reaction conditions, low cost and high yield.

In order to achieve the above object, the concrete technical scheme of the present invention is as follows:

Mix an aqueous solution containing 5-hydroxymethylfurfural (HMF) with a non-precious metal cerium-based composite oxide catalyst, react with oxygen in the presence of a basic additive to prepare 2, 5-furandicarboxylic acid (FDCA), and filter the reaction mixture The catalyst is separated from the liquid, and the obtained filtrate is acidified to precipitate crystals, which are 2, 5-furandicarboxylic acid (FDCA). The catalyst can be recycled after being washed and dried.

The non-noble metal cerium-based composite oxide contains one or two of cerium and manganese, iron, cobalt, copper, titanium, zirconium, zinc, chromium, vanadium, nickel, wherein the mass percentage of cerium oxide is 1% -90%, preferably 10%-50%.

The non-noble metal cerium-based composite oxide can be prepared by hydrothermal method, sol-gel method, co-precipitation method and other methods. Co-precipitation method: weigh cerium nitrate and another metal salt, and add deionized water to dissolve. Under the condition of water bath, the alkali solution was added dropwise to the mixed solution. After the dropwise addition is completed, the precipitate is obtained by filtering and washing, dried and then ground and calcined to obtain the non-noble metal cerium-based composite oxide. Hydrothermal method: Weigh cerium nitrate and another metal salt, and add deionized water to dissolve to obtain a mixed solution. Ammonia water was added dropwise until the precipitation was complete. After continuous stirring, it was transferred to a stainless steel autoclave lined with polytetrafluoroethylene, and crystallized to obtain a solid. Grinding and calcining after drying to obtain non-noble metal cerium-based composite oxides. Sol-gel method: Weigh cerium nitrate and another metal salt, and add deionized water and citric acid to dissolve them completely. The mixed solution was evaporated to a transparent gel under magnetic stirring at 80°C, and dried overnight. Grinding and calcining after drying to obtain non-noble metal cerium-based composite oxides.

The HMF can be pure HMF, or HMF obtained by dehydration of six-carbon sugar.

The oxidizing agent is molecular oxygen or air, and the reaction pressure is 0.1MPa-6.0MPa, preferably 0.5-3.0MPa.

The alkaline additives include alkalis such as sodium hydroxide, potassium hydroxide, and calcium hydroxide, organic bases such as urea, pyridine, triethylamine, and ethylenediamine, and inorganic bases such as sodium carbonate, potassium carbonate, potassium bicarbonate, and sodium bicarbonate. One or more types of salt.

The molar ratio of the basic additive to HMF is 0-20, preferably 0.5-8.0.

The mass ratio of the cerium-based composite oxide to HMF is 0.1-50, preferably 0.5-10.

The reaction temperature is 10-200°C, preferably 70-150°C;

The reaction time is 1-48 hours, preferably 6-12 hours.

The invention has mild reaction conditions, high conversion rate of HMF, high FDCA yield and selectivity; non-noble metal is used as the catalyst active component, the cost is low, and the catalyst has good reusability.

The reaction solution was analyzed by high performance liquid chromatography, the chromatographic column was AminexHPX-87H (Biorad), the mobile phase was 0.004mol/L sulfuric acid aqueous solution, the temperature of the chromatographic column was constant at 55°C, the detector was an ultraviolet detector, and the signal at the wavelength of 260nm was collected .

Quantitative analysis of products was carried out by external standard method. Prepare standard solutions with different concentrations of the above-mentioned standard samples of each product, measure their liquid chromatography peak areas, and make a standard curve with the relationship between concentration and peak area.

Description of drawings

Accompanying drawing 1 is the XRD spectrogram of the cerium-chromium composite oxide catalyst prepared in Example 1 (the mass percentage of cerium oxide is 50%).

Accompanying drawing 2 is the (mass percentage composition of cerium oxide is 20%) H-TPR spectrogram of the cerium-manganese composite oxide catalyst prepared in embodiment 2

Accompanying drawing 3 is the cycle stability diagram of the cerium-iron composite oxide catalyst (the mass percentage of cerium oxide is 20%) used in the reaction of preparing FDCA by oxidation of 5-HMF in Example 10.

detailed description

In order to facilitate the understanding of the present invention, the present invention enumerates the following examples, but the examples are only used to help understand the present invention, and should not be regarded as specific limitations to the present invention.

Example 1

Put 600mg of cerium-chromium composite oxide catalyst prepared by co-precipitation method (the mass percentage of cerium oxide is 50%), 10mL of 0.05mol/L HMF aqueous solution, 0.424g of sodium carbonate, into a stainless steel autoclave, and fill it with 3MPa oxygen As an oxygen source, it was reacted at 150° C. for 12 hours while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion rate and product yield. The conversion rate of HMF was 97.7%, and the yield of FDCA was 86.7%.

Example 2

Put 100mg of cerium-manganese composite oxide catalyst prepared by hydrothermal method (the mass percentage of cerium oxide is 30%), 10mL of 0.05mol/L HMF aqueous solution, 0.08g of sodium hydroxide, into a stainless steel autoclave, and fill it with a 2MPa Oxygen was used as an oxygen source, and the reaction was carried out at 110° C. for 8 hours while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion rate and product yield. The conversion rate of HMF was 98.5%, and the yield of FDCA was 81.8%.

Example 3

Add 30mg of cerium-iron composite oxide catalyst prepared by sol-gel method (the mass percentage of cerium oxide is 10%), 10mL of 0.05mol/L HMF aqueous solution, 0.015g of ethylenediamine, into a stainless steel autoclave, and fill it with 0.5 MPa oxygen was used as an oxygen source, and the reaction was carried out at 70° C. for 6 hours while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion rate and product yield. The conversion rate of HMF was 98.6%, and the yield of FDCA was 84.8%.

Example 4

Put 100mg of cerium-copper composite oxide catalyst prepared by co-precipitation method (the mass percentage of cerium oxide is 50%), 10mL of 0.05mol/L HMF aqueous solution, 0.106g of sodium carbonate, into a stainless steel autoclave, and fill it with 1MPa oxygen As an oxygen source, it was reacted at 110° C. for 10 hours while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion rate and product yield. The conversion rate of HMF was 84.5%, and the yield of FDCA was 27.0%.

Example 5

Put 200mg of cerium-manganese composite oxide catalyst prepared by hydrothermal method (the mass percentage of cerium oxide is 60%), 10mL of 0.05mol/L HMF aqueous solution, 0.212g of sodium carbonate, into a stainless steel autoclave, and fill it with 5MPa oxygen As an oxygen source, the reaction was performed at 90° C. for 10 hours while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion rate and product yield. The conversion rate of HMF was 99.3%, and the yield of FDCA was 40.1%.

Example 6

Put 1.0 g of cerium-chromium composite oxide catalyst prepared by co-precipitation method (the mass percentage of cerium oxide is 80%), 10mL of 0.05mol/L HMF aqueous solution, 0.2g of calcium carbonate, into a stainless steel autoclave, and fill it with a 2MPa Oxygen was used as an oxygen source, and the reaction was performed at 110° C. for 12 hours while magnetically stirring. The conversion rate of HMF was 69.3%, and the yield of FDCA was 22.1%.

Example 7

Put 100mg of cerium-cobalt composite oxide catalyst prepared by hydrothermal method (the mass percentage of cerium oxide is 30%), 10mL of 0.05mol/L HMF aqueous solution, 0.252g of sodium bicarbonate, add stainless steel autoclave, and fill it with 0.5MPa Oxygen was used as an oxygen source, and the reaction was carried out at 60°C for 3 hours while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion rate and product yield. The conversion rate of HMF was 74.2%, and the yield of FDCA was 15.8%.

Example 8

Put 100mg of cerium-manganese composite oxide catalyst prepared by sol-gel method (the mass percentage of cerium oxide is 30%), 10mL of 0.05mol/L HMF aqueous solution, 0.03g of potassium carbonate, into a stainless steel autoclave, and fill it with a 6MPa Oxygen was used as an oxygen source, and the reaction was carried out at 150° C. for 3 hours while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion rate and product yield. The conversion rate of HMF was 97.2%, and the yield of FDCA was 60.3%.

Example 9

Add 130mg of cerium-iron composite oxide catalyst prepared by precipitation method (the mass percentage of cerium oxide is 60%), 10mL of 0.05mol/L HMF aqueous solution, 0.16g of sodium hydroxide, into a stainless steel autoclave, and fill it with 1MPa oxygen As an oxygen source, the reaction was performed at 100° C. for 5 hours while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion rate and product yield. The conversion rate of HMF was 99.2%, and the yield of FDCA was 20.3%.

Example 10

Cyclic stability of non-noble metal cerium-iron composite oxide catalysts for catalytic oxidation

Put 100mg of cerium-iron composite oxide catalyst prepared by co-precipitation method (the mass percentage of cerium oxide is 20%), 10mL of 0.05mol/L HMF aqueous solution, 0.112g of potassium hydroxide, into a stainless steel autoclave, and fill it with a 1MPa Oxygen was used as an oxygen source, and the reaction was performed at 130° C. for 1 hour while magnetically stirring. After the reaction, centrifuge and analyze the reaction solution to obtain the conversion rate of 5-HMF and the yield of FDCA. After the catalyst is washed with deionized water, the next reaction is continued. The reaction is applied 8 times in total, and the activity remains basically unchanged.

Example 11

Add 50mg of cerium-manganese composite oxide catalyst prepared by co-precipitation method (the mass percentage of cerium oxide is 40%), 10mL of HMF aqueous solution obtained by dehydration of 0.05mol/L glucose, and 0.12g of urea into a stainless steel autoclave. 3 MPa of oxygen was introduced as an oxygen source, and the reaction was carried out at 100° C. for 24 hours while stirring by magnetic force. Finally, the reaction solution was analyzed by HPLC for substrate conversion rate and product yield. The conversion rate of HMF was 79.2%, and the yield of FDCA was 30.3%.

Example 12

Put 120mg of cerium vanadium composite oxide catalyst prepared by hydrothermal method (the mass percentage of cerium oxide is 60%), 10mL of 0.05mol/L HMF aqueous solution, 0.1g of potassium bicarbonate, add stainless steel autoclave, and fill it with 1MPa Oxygen was used as an oxygen source, and the reaction was carried out at 20° C. for 5 hours while being magnetically stirred. Finally, the reaction solution was analyzed by HPLC for substrate conversion rate and product yield. The conversion of HMF was 59.2%, and the yield of FDCA was 10.3%.

Example 13

Add 100mg of cerium-iron composite oxide catalyst prepared by co-precipitation method (the mass percentage of cerium oxide is 30%), 10mL of 0.05mol/L glucose dehydration HMF aqueous solution, 0.16g of sodium hydroxide, into a stainless steel autoclave , filled with 4MPa oxygen as an oxygen source, and reacted at 70° C. for 28 hours while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion rate and product yield. The conversion rate of HMF was 99.2%, and the yield of FDCA was 12.3%.

Example 14

Put 80mg of cerium-titanium composite oxide catalyst prepared by hydrothermal method (the mass percentage of cerium oxide is 35%), 10mL of 0.05mol/L glucose dehydrated HMF aqueous solution, 0.3g of triethylamine, and put them into a stainless steel autoclave , filled with 2MPa oxygen as an oxygen source, and reacted at 60° C. for 24 hours while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion rate and product yield. The conversion rate of HMF was 69.2%, and the yield of FDCA was 2.3%.

Example 15

Add 100 mg of cerium-zirconium composite oxide catalyst prepared by sol-gel method (the mass percentage of cerium oxide is 70%), 10 mL of HMF aqueous solution dehydrated from 0.05 mol/L glucose, and 0.16 g of pyridine into a stainless steel autoclave, Charge 3.6 MPa of oxygen as an oxygen source, and react at 150° C. for 18 hours while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion rate and product yield. The conversion rate of HMF was 79.4%, and the yield of FDCA was 22.2%.

Claims (9)

1. A method for preparing 2,5-furandicarboxylic acid (FDCA) by catalytic oxidation of 5-hydroxymethylfurfural (HMF), characterized in that: non-noble metal cerium-based composite oxide is used as a catalyst, and oxygen or air is used as an oxygen source , in the presence of basic additives, catalyzed oxidation of 5-hydroxymethylfurfural (HMF) to 2, 5-furandicarboxylic acid (FDCA) in aqueous solution; after the reaction was completed, the reaction mixture was filtered to separate the catalyst, and the obtained The filtrate is acidified to precipitate crystals, which are 2, 5-furandicarboxylic acid (FDCA), and the catalyst can be recycled after being washed and dried. 2. The method according to claim 1, wherein the non-noble metal cerium-based composite oxide contains one of cerium and manganese, iron, cobalt, copper, titanium, zirconium, zinc, chromium, vanadium, nickel or two, wherein the mass percentage of cerium oxide is 1%-90%, preferably 10%-50%. 3. The method according to claim 1, characterized in that: the non-noble metal cerium-based composite oxide can be prepared by hydrothermal method, sol-gel method, co-precipitation method and other methods. 4. The method according to claim 1, characterized in that: the HMF can be pure HMF, or HMF obtained by dehydration of six-carbon sugar. 5. The method according to claim 1, characterized in that the oxidizing agent is molecular oxygen or air, and the reaction pressure is 0.1MPa-6.0MPa, preferably 0.5-3.0MPa. 6. The method according to claim 1, characterized in that: said alkaline additives include inorganic bases such as sodium hydroxide, potassium hydroxide, and calcium hydroxide, organic bases such as urea, pyridine, triethylamine, and ethylenediamine , one or more of inorganic salts such as sodium carbonate, potassium carbonate, potassium bicarbonate, and sodium bicarbonate. 7. The method according to claim 1, characterized in that: the molar ratio of the basic additive to HMF is 0-20, preferably 0.5-8.0. 8. The method according to claim 1, characterized in that: the mass ratio of the cerium-based composite oxide to HMF is 0.1-50, preferably 0.5-10. 9. The method according to claim 1, characterized in that: the reaction temperature is 10-200°C, preferably 70-150°C; the reaction time is 1-48 hours, preferably 6-12 hours.