CN106565647B - Method for preparing 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural - Google Patents
Method for preparing 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural Download PDFInfo
- Publication number
- CN106565647B CN106565647B CN201610924322.4A CN201610924322A CN106565647B CN 106565647 B CN106565647 B CN 106565647B CN 201610924322 A CN201610924322 A CN 201610924322A CN 106565647 B CN106565647 B CN 106565647B
- Authority
- CN
- China
- Prior art keywords
- cerium
- composite oxide
- hydroxymethylfurfural
- catalyst
- hmf
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C07D307/56—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- 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
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/83—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 rare earths or actinides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing 2, 5-furandicarboxylic acid (FDCA) by catalytic oxidation of a biomass derivative, namely 5-Hydroxymethylfurfural (HMF), and belongs to the field of preparation of renewable chemicals synthesized by using biomass and the derivative. The method comprises the following steps: the non-noble metal cerium-based composite oxide is used as a catalyst, oxygen or air is used as an oxidant, and the 5-hydroxymethylfurfural is effectively catalyzed and oxidized to synthesize the 2, 5-furandicarboxylic acid. The method is simple to operate, mild in condition, high in yield of the 2, 5-furandicarboxylic acid up to 86.7%, easy to separate and recycle the catalyst, good in reusability and good in industrial application prospect.
Description
Technical Field
The invention relates to a method for preparing 2, 5-furandicarboxylic acid (FDCA), belonging to the field of preparation of renewable chemicals synthesized by using biomass and derivatives. More particularly relates to a method for preparing 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural.
Background
2, 5-Furanedicarboxylic acid (FDCA), which is a furan-like compound that can be produced from biomass, was identified in 2004 by the U.S. department of energy as one of 12 "platform compounds". The polyester has furan rings and two carboxyl groups, and is expected to replace petroleum-based monomer terephthalic acid in the polyester industry to synthesize green degradable plastics; can also be used to substitute phthalic acid to synthesize green nontoxic plasticizer. The utilization of the biomass is introduced into the polyester industry, so that the dependence of the polyester industry on petroleum energy can be reduced, and the pollution to the environment is reduced. In addition, derivatives having bactericidal and anesthetic functions, such as succinic acid, dichlorofurandicarboxylic acid, and dimethyl furandicarboxylate, can be synthesized from 2, 5-furandicarboxylic acid.
Currently, 2, 5-furandicarboxylic acid is mainly prepared by oxidizing 5-Hydroxymethylfurfural (HMF), and a catalyst is generally added, and the catalyst is divided into a heterogeneous catalyst and a homogeneous catalyst. The homogeneous catalyst is mainly transition metal salt of Co, Mn, etc., for example, the group of Grushin subjects adopts cobalt salt homogeneous catalytic oxidationHMF, initial concentration of HMF about 8%, at 7MPa air, 125%oAnd C, carrying out a Co/Mn/Br/Zr catalytic reaction for 3 hours to obtain the FDCA with the yield of 60% (W. Partenheimer, V.V. Grushin, adv. Synth. Catal., 2001, 343: 102-) -111). In the patent of Japan Canon corporation (patent No. 201010516208.0), HMF is reacted with an oxidizing agent in an organic acid solvent in the presence of bromine and a metal catalyst to prepare FDCA with high purity. These homogeneous catalytic reaction systems have the disadvantages of low yield, difficult separation of metal salts, serious bromine environmental pollution and the like. In contrast, the multi-phase catalytic method has the advantages of high selectivity, environmental protection, easy product separation and the like. For HMF oxidation, there are two main classes of noble metal catalysts and non-noble metal catalysts. The noble metal catalyst includes Pt, Au, Pd, etc., for example, Miao Zhen et al uses CeBi composite oxide supported noble metal Au as catalyst to catalyze and oxidize HMF, and high-efficiency conversion of HMF can be realized at room temperature (ZHenzhen Miao, Yibo Zhang, Catal. Sci. Technol., 2015, 5: 1314) 1322). Korean Schwann et al, which uses carbon-magnesia as an alkaline carrier and noble metal Pt as a carrier, have excellent effects under the alkali-free condition, and the yield of FDCA can reach 95% (Xuewang Han, Liang Geng, Green Chemistry 2015,14: 4-17). Malanhong et al in its patent (patent No. 201210390203.7) utilize noble metals (Au, Ag, Pd, Pt, Ru) supported on basic carriers to catalytically oxidize HMF with a selectivity of up to 99%. Linlu et al in their patent (patent No. 201010228459) use of Pt, Au, Pd supported C or CuO-Ag2And (3) using O as a catalyst to prepare FDCA by catalytic oxidation of HMF in an alkaline solution, thereby obtaining higher yield of FDCA. Although the noble metal catalysts have good catalytic selectivity and high stability, the noble metals are expensive and are not suitable for industrial large-scale production. The prior non-noble metal heterogeneous catalyst generally has the problems of low selectivity and poor stability under the condition of oxygen or air, such as nano Fe used in Zhang Hui subject group3O4The yield of FDCA can reach 68.6% when HMF is catalytically oxidized by CoOx and tert-butyl peroxide is used as an oxidant, but the yield of FDCA is only 4.2% when oxygen is used as an oxidant (Shuguo Wang, Zehui Zhuang, ACS Sustainable chem. Eng. 2015, 3: 406-. Porphyrin cobalt loaded with chloromethyl resinThe catalyst, which can also be used with tert-butyl peroxide as oxidant, can produce higher FDCA yield, but with oxygen as oxidant, the FDCA yield is very low (Langchang Gao, Kejian Deng, Zehui Zhuang, chemical engineering Journal, 2015, 270: 444-. Therefore, there is an urgent need to find a stable and efficient non-noble metal catalyst for the oxygen or air oxidation of HMF to produce FDCA.
Compared with the prior reports, the invention takes the non-noble metal cerium-based composite oxide as the catalyst and has the following advantages: (1) the reaction condition is mild, the conversion rate of HMF is high, and the yield of FDCA can reach 86.7%. (2) The non-noble metal is used as an active component, and the catalyst is low in cost. (3) The catalyst prepared and used by the invention has good reusability. The synthesis method of 2, 5-furandicarboxylic acid provided by the invention has innovativeness and strong popularization and application values.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the FDCA preparation method which is mild in reaction condition, low in cost and high in yield.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
mixing an aqueous solution containing 5-Hydroxymethylfurfural (HMF) with a non-noble metal cerium-based composite oxide catalyst, reacting with oxygen in the presence of a basic additive to prepare 2, 5-furandicarboxylic acid (FDCA), filtering the reaction mixed solution to separate out the catalyst, acidifying the obtained filtrate, and separating out crystals, wherein the obtained crystals are the 2, 5-furandicarboxylic acid (FDCA), and the catalyst can be recycled after washing and drying.
The non-noble metal cerium-based composite oxide comprises one or two of cerium, manganese, iron, cobalt, copper, titanium, zirconium, zinc, chromium, vanadium and nickel, wherein the mass percentage of cerium oxide is 1-90%, and preferably 10-50%.
The non-noble metal cerium-based composite oxide can be prepared by a hydrothermal method, a sol-gel method, a coprecipitation method and the like. A coprecipitation method: weighing cerium nitrate and another metal salt, and adding deionized water for dissolving. And dropwise adding the alkali solution into the mixed solution under the condition of water bath. After the dripping is finished, filtering and washing to obtain a precipitate, drying, grinding and calcining to obtain the non-noble metal cerium-based composite oxide. Hydrothermal method: weighing cerium nitrate and another metal salt, and adding deionized water to dissolve to obtain a mixed solution. And dropwise adding ammonia water until the precipitation is complete. Continuously stirring uniformly, transferring into a stainless steel pressure kettle with a polytetrafluoroethylene lining, and crystallizing to obtain a solid. Drying, grinding and calcining to obtain the non-noble metal cerium-based composite oxide. Sol-gel method: cerium nitrate and another metal salt are weighed and added with deionized water and citric acid to be completely dissolved. The mixed solution was evaporated to a transparent gel under magnetic stirring at 80 ℃ and dried overnight. Drying, grinding and calcining to obtain the non-noble metal cerium-based composite oxide.
The HMF can be pure HMF or HMF obtained by dehydration of a six-carbon sugar.
The oxidant is molecular oxygen or air, and the reaction pressure is 0.1-6.0 MPa, preferably 0.5-3.0 MPa.
The alkaline additive comprises one or more of alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide and the like, organic alkali such as urea, pyridine, triethylamine, ethylenediamine and the like, and inorganic salt such as sodium carbonate, potassium bicarbonate, sodium bicarbonate and the like.
The molar ratio of the basic additive to HMF is 0 to 20, preferably 0.5 to 8.0.
The mass ratio of the cerium-based composite oxide to HMF is 0.1 to 50, preferably 0.5 to 10.
The reaction temperature is 10-200 ℃, and preferably 70-150 ℃;
the reaction time is from 1 to 48 hours, preferably from 6 to 12 hours.
The invention has mild reaction conditions, high HMF conversion rate and high FDCA yield and selectivity; non-noble metal is used as the active component of the catalyst, so that the cost is low and the reusability of the catalyst is good.
The reaction solution is analyzed by high performance liquid chromatography, a chromatographic column adopts AminexHPX-87H (Biorad), a mobile phase adopts 0.004mol/L sulfuric acid aqueous solution, the temperature of the chromatographic column is constant at 55 ℃, an ultraviolet detector is adopted, and a signal with the wavelength of 260nm is collected.
The product quantitative analysis adopts an external standard method. Preparing standard solutions of the product standard samples with different concentrations, measuring the liquid chromatogram peak area, and making a standard curve according to the relation between the concentration and the peak area.
Drawings
Fig. 1 is an XRD spectrum of the cerium-chromium composite oxide catalyst (cerium oxide 50% by mass) prepared in example 1.
FIG. 2 is a chart of H-TPR (20% by mass of cerium oxide) of the cerium manganese composite oxide catalyst prepared in example 2
FIG. 3 is a graph showing the cycling stability of the cerium-iron composite oxide catalyst (cerium oxide in 20% by weight) used in the oxidation of 5-HMF to prepare FDCA in example 10.
Detailed Description
For the convenience of understanding the present invention, the present invention will be described below with reference to examples, which are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
Example 1
Adding 10mL of 0.05mol/L HMF aqueous solution and 0.424g of sodium carbonate into a stainless steel high-pressure reaction kettle by using a cerium-chromium composite oxide catalyst (the mass percentage of cerium oxide is 50%) prepared by a 600mg coprecipitation method, filling 3MPa oxygen as an oxygen source, and reacting for 12 hours at 150 ℃ while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 97.7% and FDCA yield was 86.7%.
Example 2
Adding 10mL of 0.05mol/L HMF aqueous solution and 0.08g of sodium hydroxide into a stainless steel high-pressure reaction kettle by using 100mg of a cerium-manganese composite oxide catalyst (the mass percentage of cerium oxide is 30%) prepared by a hydrothermal method, filling 2MPa of oxygen as an oxygen source, and reacting for 8 hours at 110 ℃ while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 98.5% and FDCA yield was 81.8%.
Example 3
Adding 10mL of 0.05mol/L HMF aqueous solution and 0.015g of ethylenediamine into a stainless steel high-pressure reaction kettle by using 30mg of cerium-iron composite oxide catalyst (the mass percentage of cerium oxide is 10%) prepared by a sol-gel method, filling 0.5MPa of oxygen as an oxygen source, and reacting for 6 hours at 70 ℃ while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 98.6% and FDCA yield was 84.8%.
Example 4
Adding 10mL of 0.05mol/L HMF aqueous solution and 0.106g of sodium carbonate into a stainless steel high-pressure reaction kettle by using 100mg of a cerium-copper composite oxide catalyst (the mass percentage of cerium oxide is 50%) prepared by a coprecipitation method, filling 1MPa of oxygen as an oxygen source, and reacting for 10 hours at 110 ℃ while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 84.5% and FDCA yield was 27.0%.
Example 5
Adding 10mL of 0.05mol/L HMF aqueous solution and 0.212g of sodium carbonate into a stainless steel high-pressure reaction kettle by using 200mg of a cerium-manganese composite oxide catalyst (the mass percentage of cerium oxide is 60%) prepared by a hydrothermal method, filling 5MPa of oxygen as an oxygen source, and reacting for 10 hours at 90 ℃ while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 99.3% and FDCA yield was 40.1%.
Example 6
1.0 g of cerium-chromium composite oxide catalyst (the mass percentage of cerium oxide is 80%) prepared by a coprecipitation method, 10mL of 0.05mol/L HMF aqueous solution and 0.2g of calcium carbonate are added into a stainless steel high-pressure reaction kettle, 2MPa of oxygen is filled as an oxygen source, and the mixture reacts for 12 hours at 110 ℃ while being magnetically stirred. HMF conversion was 69.3% and FDCA yield was 22.1%.
Example 7
Adding 10mL of 0.05mol/L HMF aqueous solution and 0.252 g of sodium bicarbonate into a stainless steel high-pressure reaction kettle, adding 100mg of a cerium-cobalt composite oxide catalyst (the mass percentage of cerium oxide is 30%) prepared by a hydrothermal method, introducing 0.5MPa of oxygen as an oxygen source, and reacting for 3 hours at 60 ℃ while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 74.2% and FDCA yield was 15.8%.
Example 8
Adding 10mL of 0.05mol/L HMF aqueous solution and 0.03g of potassium carbonate into a stainless steel high-pressure reaction kettle by using 100mg of a cerium-manganese composite oxide catalyst (the mass percentage of cerium oxide is 30%) prepared by a sol-gel method, introducing 6MPa of oxygen as an oxygen source, and reacting for 3 hours at 150 ℃ while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. The HMF conversion was 97.2% and FDCA yield was 60.3%.
Example 9
Adding 10mL of 0.05mol/L HMF aqueous solution and 0.16g of sodium hydroxide into a stainless steel high-pressure reaction kettle by using 130mg of cerium-iron composite oxide catalyst (the mass percentage of cerium oxide is 60%) prepared by a precipitation method, filling 1MPa of oxygen as an oxygen source, and reacting for 5 hours at 100 ℃ while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 99.2% and FDCA yield was 20.3%.
Example 10
Circulation stability of catalytic oxidation of non-noble metal cerium-iron composite oxide catalyst
Adding 10mL of 0.05mol/L HMF aqueous solution and 0.112g of potassium hydroxide into a stainless steel high-pressure reaction kettle by using 100mg of a cerium-iron composite oxide catalyst (the mass percentage of cerium oxide is 20%) prepared by a coprecipitation method, filling 1MPa of oxygen as an oxygen source, and reacting for 1 hour at 130 ℃ while magnetically stirring. After the reaction is finished, centrifugal separation is carried out, the reaction solution is analyzed to obtain the conversion rate of 5-HMF and the yield of FDCA, the catalyst is washed by deionized water and then continues to carry out the next reaction, the reaction is used for 8 times totally, and the activity is basically unchanged.
Example 11
50mg of a cerium-manganese composite oxide catalyst (the mass percentage of cerium oxide is 40 percent) prepared by a coprecipitation method, 10mL of HMF aqueous solution obtained by dehydrating 0.05mol/L glucose and 0.12g of urea are added into a stainless steel high-pressure reaction kettle, 3MPa of oxygen is filled as an oxygen source, and the reaction is carried out for 24 hours at 100 ℃ while the magnetic stirring is carried out. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 79.2% and FDCA yield was 30.3%.
Example 12
Adding 10mL of 0.05mol/L HMF aqueous solution and 0.1g of potassium bicarbonate into a stainless steel high-pressure reaction kettle by using 120mg of a cerium-vanadium composite oxide catalyst (the mass percentage of cerium oxide is 60%) prepared by a hydrothermal method, filling 1MPa of oxygen as an oxygen source, and reacting for 5 hours at 20 ℃ while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 59.2% and FDCA yield was 10.3%.
Example 13
The preparation method comprises the steps of adding 10mL of 0.05mol/L glucose dehydrated HMF aqueous solution and 0.16g of sodium hydroxide into a stainless steel high-pressure reaction kettle by using 100mg of cerium-iron composite oxide catalyst (the mass percentage of cerium oxide is 30%) prepared by a coprecipitation method, filling 4MPa of oxygen as an oxygen source, and reacting at 70 ℃ for 28 hours while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 99.2% and FDCA yield was 12.3%.
Example 14
80mg of a cerium-titanium composite oxide catalyst (35% by mass of cerium oxide) prepared by a hydrothermal method, 10mL of an HMF aqueous solution obtained by dehydration of 0.05mol/L glucose and 0.3g of triethylamine are added into a stainless steel high-pressure reaction kettle, 2MPa of oxygen is filled as an oxygen source, and the reaction is carried out for 24 hours at 60 ℃ while magnetic stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 69.2% and FDCA yield was 2.3%.
Example 15
The preparation method comprises the steps of adding 10mL of 0.05mol/L glucose dehydrated HMF aqueous solution and 0.16g of pyridine into a stainless steel high-pressure reaction kettle by using 100mg of cerium-zirconium composite oxide catalyst (the mass percentage of cerium oxide is 70%) prepared by a sol-gel method, filling 3.6MPa of oxygen as an oxygen source, and reacting for 18 hours at 150 ℃ while magnetically stirring. Finally, the reaction solution was analyzed by HPLC for substrate conversion and product yield. HMF conversion was 79.4% and FDCA yield was 22.2%.
Claims (12)
1. A method for preparing 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural is characterized by comprising the following steps: taking non-noble metal cerium-based composite oxide as a catalyst, taking oxygen or air as an oxygen source, and catalytically oxidizing 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid in an aqueous solution in the presence of an alkaline additive; after the reaction is finished, filtering the reaction mixed solution, separating out the catalyst, acidifying the obtained filtrate, and separating out crystals, wherein the obtained crystals are 2, 5-furandicarboxylic acid, the catalyst can be recycled after being washed and dried, and the non-noble metal cerium-based composite oxide consists of cerium and one or two of manganese, iron, cobalt, copper, titanium, zirconium, zinc, chromium, vanadium and nickel; the alkaline additive is selected from one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, urea, pyridine, triethylamine, ethylenediamine, sodium carbonate, potassium bicarbonate and sodium bicarbonate.
2. The method of claim 1, wherein: the mass percentage of cerium oxide in the non-noble metal cerium-based composite oxide is 1-90%.
3. The method of claim 2, wherein: the mass percentage of the cerium oxide is 10-50%.
4. The method of claim 1, wherein: the non-noble metal cerium-based composite oxide is prepared by a hydrothermal method, a sol-gel method or a coprecipitation method.
5. The method of claim 1, wherein: the 5-hydroxymethylfurfural is obtained by dehydrating hexose.
6. The method of claim 1, wherein the oxygen source has a reaction pressure of 0.1MPa to 6.0 MPa.
7. The method of claim 6, wherein: the reaction pressure of the oxygen source is 0.5-3.0 MPa.
8. The method of claim 1, wherein: the molar ratio of the alkaline additive to the 5-hydroxymethylfurfural is 0.5-8.0.
9. The method of claim 1, wherein: the mass ratio of the cerium-based composite oxide to the 5-hydroxymethylfurfural is 0.1-50.
10. The method of claim 9, wherein: the mass ratio of the cerium-based composite oxide to the 5-hydroxymethylfurfural is 0.5-10.
11. The method of claim 1, wherein: the reaction temperature is 10-200 ℃; the reaction time is 1-48 hours.
12. The method of claim 11, wherein: the reaction temperature is 70-150 ℃; the reaction time is 6-12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610924322.4A CN106565647B (en) | 2016-10-29 | 2016-10-29 | Method for preparing 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610924322.4A CN106565647B (en) | 2016-10-29 | 2016-10-29 | Method for preparing 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106565647A CN106565647A (en) | 2017-04-19 |
| CN106565647B true CN106565647B (en) | 2020-01-10 |
Family
ID=58534145
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610924322.4A Active CN106565647B (en) | 2016-10-29 | 2016-10-29 | Method for preparing 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106565647B (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107117970A (en) * | 2017-04-21 | 2017-09-01 | 华东理工大学 | A kind of compound additive of new production low resistance high strength graphite material and the preparation method of the graphite material |
| CN107051585B (en) * | 2017-05-19 | 2020-06-19 | 中南民族大学 | Composite catalyst with high-efficiency photocatalytic oxidation and application thereof |
| CN111250126A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Catalyst, preparation method and application thereof |
| CN110180541B (en) * | 2019-06-28 | 2021-04-02 | 中国科学院大连化学物理研究所 | Application of gold-based catalyst in catalytic oxidation of aldehyde to generate ester |
| CN110437190B (en) * | 2019-07-29 | 2023-03-10 | 中国科学技术大学 | Method for preparing 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural |
| CN113117705B (en) * | 2019-12-31 | 2024-05-07 | 中国石油化工股份有限公司 | Modified ruthenium-based catalyst and method for preparing 2, 5-furan dicarboxylic acid by catalysis of modified ruthenium-based catalyst |
| CN113117706B (en) * | 2019-12-31 | 2024-04-12 | 中国石油化工股份有限公司 | Metal modified ruthenium-based catalyst and method for preparing 2, 5-furan dicarboxylic acid by catalysis of metal modified ruthenium-based catalyst |
| CN111153876B (en) * | 2020-01-13 | 2023-07-28 | 华东师范大学 | Method for producing furandicarboxylic acid and derivative thereof from furfural |
| CN111362892A (en) * | 2020-04-13 | 2020-07-03 | 南京工业大学 | Method for preparing 2, 5-furandicarboxylic acid by selective oxidation of 5-hydroxymethylfurfural on manganese-copper spinel catalyst |
| CN111606875B (en) * | 2020-06-15 | 2022-12-30 | 莆田达凯新材料有限公司 | Method for preparing furandicarboxylic acid monomer from bamboo biomass |
| CN112047912B (en) * | 2020-10-16 | 2022-07-15 | 中国科学技术大学 | Preparation method of furan dicarboxylic acid |
| CN112341415A (en) * | 2020-10-28 | 2021-02-09 | 南京先进生物材料与过程装备研究院有限公司 | Method for preparing 5-hydroxymethyl-2-furancarboxylic acid by photocatalytic oxidation |
| CN113041997A (en) * | 2021-03-05 | 2021-06-29 | 佛山科学技术学院 | Modified magnetic biochar and preparation method and application thereof |
| CN113121477A (en) * | 2021-06-02 | 2021-07-16 | 宁波国生科技有限公司 | Preparation method of 2, 5-tetrahydrofuran dicarboxylic acid |
| CN113996296A (en) * | 2021-11-30 | 2022-02-01 | 北京化工大学 | Silver catalyst for preparing bio-based 2,5-furandicarboxylic acid and preparation method and application thereof |
| CN114105917B (en) * | 2021-12-09 | 2023-03-28 | 万华化学集团股份有限公司 | Method for preparing 2,5-furandicarboxylic acid by efficiently catalyzing 5-hydroxymethylfurfural |
| CN114605359B (en) * | 2022-03-09 | 2024-05-31 | 苏州禾广吉智能装备有限公司 | Method for preparing FDCA and full bio-based filler by using non-grain biomass raw material |
| CN114703495B (en) * | 2022-03-10 | 2023-12-19 | 东北林业大学 | Method for preparing 2, 5-furandicarboxylic acid by electrocatalytic oxidation of 5-hydroxymethylfurfural on amorphous NiFeB catalyst |
| CN115073404B (en) * | 2022-07-14 | 2023-11-28 | 中科国生(杭州)科技有限公司 | Preparation method of 2, 5-furandicarboxylic acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666521A (en) * | 2009-10-07 | 2012-09-12 | 福兰尼克斯科技公司 | Method for the preparation of 2,5-furandicarboxylic acid and for the preparation of the dialkyl ester of 2,5-furandicarboxylic acid |
| CN104277021A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-furan diamide by catalytic conversion of 5-hydroxymethylfurfural |
| WO2016028488A1 (en) * | 2014-08-19 | 2016-02-25 | Archer Daniels Midland Company | Catalyst and process for producing 2,5-furandicarboxylic acid from hydromethylfurfural in water |
| CN105859662A (en) * | 2016-04-18 | 2016-08-17 | 天津理工大学 | Method for catalyzing selective oxidation of 5-hydroxymethyl furfural through manganese oxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015083559A (en) * | 2013-09-19 | 2015-04-30 | 花王株式会社 | Method for producing 2,5-furan dicarboxylic acid |
-
2016
- 2016-10-29 CN CN201610924322.4A patent/CN106565647B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102666521A (en) * | 2009-10-07 | 2012-09-12 | 福兰尼克斯科技公司 | Method for the preparation of 2,5-furandicarboxylic acid and for the preparation of the dialkyl ester of 2,5-furandicarboxylic acid |
| CN104277021A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院大连化学物理研究所 | Method for preparing 2, 5-furan diamide by catalytic conversion of 5-hydroxymethylfurfural |
| WO2016028488A1 (en) * | 2014-08-19 | 2016-02-25 | Archer Daniels Midland Company | Catalyst and process for producing 2,5-furandicarboxylic acid from hydromethylfurfural in water |
| CN105859662A (en) * | 2016-04-18 | 2016-08-17 | 天津理工大学 | Method for catalyzing selective oxidation of 5-hydroxymethyl furfural through manganese oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106565647A (en) | 2017-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106565647B (en) | Method for preparing 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural | |
| CN108484545B (en) | Method and system for continuously synthesizing furan dicarboxylic acid | |
| CN108299358B (en) | Process for the selective oxidation of furan alcohols or aldehydes | |
| CN110102350B (en) | Catalyst for oxidative synthesis of 2, 5-furandicarboxylic acid and preparation method and application thereof | |
| CN105418561B (en) | Method for preparing 2, 5-furandicarboxylic acid by catalyzing fructose through supported bifunctional catalyst | |
| CN111153876B (en) | Method for producing furandicarboxylic acid and derivative thereof from furfural | |
| Chen et al. | Binuclear molybdenum alkoxide as the versatile catalyst for the conversion of carbon dioxide | |
| CN103068809A (en) | Process for the synthesis of 2,5-furandicarboxylic acid | |
| CN111377890B (en) | Method for producing 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural | |
| CA2949436A1 (en) | Process for the selective oxidation of 5-hydroxymethylfurfural | |
| KR101715169B1 (en) | Method for preparing 2,5-furandicarboxylic acid | |
| CN113563289B (en) | Method for preparing 2, 5-furandicarboxylic acid from furfural | |
| CN103570493A (en) | Method for synthesizing 1,2-orthodiol through immobilized type heteropolyacid phase-transfer catalytic oxidation | |
| TW202016083A (en) | Process for preparing 2,5-furandicarboxylic acid particularly relating to a process for preparing 2,5-furandicarboxylic acid in the presence of a basic aqueous solution and an oxidation catalyst containing a metal | |
| CN111187238B (en) | Synthetic method of 2, 5-furandicarboxylic acid | |
| CN114605362A (en) | Preparation method of 2, 5-furandicarboxylic acid | |
| CN109293608B (en) | Preparation method of 5-formyl furoic acid | |
| CN113698373A (en) | Method for preparing 2, 5-furandicarboxylic acid by high-efficiency photocatalytic oxidation | |
| CN102452918B (en) | Method for preparing corresponding dicarboxylic acid by catalytic oxidation of hydroxy acid | |
| CN104817524A (en) | Method for preparing 5-hydroxymethyl furoic acid through catalytic conversion on fructose | |
| CN108620095B (en) | Composite catalyst and application thereof in synthesis of glyceraldehyde | |
| Li | Current approaches of the functional and synergetic catalytic systems for converting renewable carbohydrates into 2, 5-diformylfuran | |
| CN113121481A (en) | Ruthenium-based catalyst and method for preparing 2, 5-furandicarboxylic acid by using same | |
| CN114478243A (en) | Method for synthesizing dihydroxy dimethyl terephthalate by oxygen catalytic oxidation method | |
| CN110256381A (en) | One-step method cleans the method for preparing 2,5- furandicarboxylic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |