CN112830915B - Low-temperature preparation method of 2, 5-furandicarboxylic acid - Google Patents
Low-temperature preparation method of 2, 5-furandicarboxylic acid Download PDFInfo
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- CN112830915B CN112830915B CN201911134925.4A CN201911134925A CN112830915B CN 112830915 B CN112830915 B CN 112830915B CN 201911134925 A CN201911134925 A CN 201911134925A CN 112830915 B CN112830915 B CN 112830915B
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- 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
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
Abstract
The application discloses a preparation method of 2, 5-furandicarboxylic acid, belonging to the technical field of organic chemistry. Continuously introducing reaction gas into a reactor, and carrying out catalytic oxidation reaction on a mixture in the reactor at 150 ℃ to generate 2, 5-furandicarboxylic acid; the mixture comprises a raw material, organic acid, halogen and a metal catalyst, wherein the raw material is 5-hydroxymethylfurfural or a 5-hydroxymethylfurfural derivative, and the reaction gas contains carbon dioxide and oxygen in a molar ratio of not less than 0.1: 1; the method effectively inhibits the combustion of a solvent and the occurrence of side reactions in the oxidation process by controlling the proportion of carbon dioxide and oxygen in reaction gas and controlling the reaction conditions at 150 ℃, thereby improving the safety of the reaction and simultaneously improving the selectivity and the yield of the FDCA (up to more than 91.8%).
Description
Technical Field
The application relates to the technical field of organic chemistry, in particular to a preparation method of 2, 5-furandicarboxylic acid.
Background
2, 5-Furanedicarboxylic acid (FDCA) is an important furan derivative, is determined by the United states department of energy as one of 12 compounds for establishing a future 'green' chemical industry platform, can be directly used for synthesizing high-performance materials such as polyester, polyurethane and the like due to the similarity of the structure of the FDCA and terephthalic acid, is better than PET in barrier property and thermal stability, can be applied to the fields of medicines, pesticides and the like, and has a higher market prospect. However, since the first report in 1876, no specific commercially viable method for preparing the product has been available.
The synthesis route of FDCA mainly comprises a 5-Hydroxymethylfurfural (HMF) oxidation route, a adipic acid dehydration route, a furfural/furoic acid route and a diglycolic acid route, wherein the HMF oxidation route is the most promising method for realizing industrialization. The method for preparing FDCA by oxidizing HMF mainly comprises noble metal catalytic oxidation, metering oxidation and a metal catalyst co-catalytic oxidation method of bromine in organic acid. Wherein, a large amount of waste salt is generated in the preparation process of the noble metal oxidation method, and the cost of the catalyst is higher. The metering oxidation method only needs potassium permanganate oxidation, nitric acid oxidation and peroxide oxidation, so that equipment is seriously corroded in the preparation process, and a large amount of waste liquid and waste salt are generated. The production process of the organic acid bromine and metal catalyst co-catalytic oxidation method has no waste salt, the organic acid can be recycled, and the catalyst can be recycled, so that the method is an environment-friendly preparation method, and therefore, the method for preparing FDCA by using the organic acid bromine and metal catalyst co-catalytic oxidation method is the most promising way for realizing industrialization.
The reaction temperature of the catalytic system reported at present is mostly higher than 150 ℃, the solvent burning is serious, and the reaction danger coefficient is large. Several patents have reported that oxidation is carried out below 150 ℃, but the FDCA yields are low. Wherein, CN 101896476A is used for oxidizing HMF and ester thereof at 85-110 ℃ and 400-1000 psi, and the yield of FDCA is only about 55%; CN 104744414B is prepared by oxidizing HMF at 80-130 ℃ and 800-1000 psi to prepare FDCA, and the FDCA can be oxidized to about 55% by adding a bromine source in the presence of Co/Mn/Ce; WO 01/72732A 2 was oxidized at 50-160 ℃ and Co/Mn/Zr/Br of 1.0/1.0/0.1/2.0, and the yield of FDCA was only 55%.
Disclosure of Invention
According to an aspect of the present application, there is provided a method for producing 2, 5-furandicarboxylic acid, comprising: continuously introducing reaction gas into the reactor to enable the mixture in the reactor to have catalytic oxidation reaction at the temperature of below 150 ℃ to generate 2, 5-furandicarboxylic acid; the mixture comprises a raw material, organic acid, halogen and a metal catalyst, wherein the raw material is 5-hydroxymethylfurfural or 5-hydroxymethylfurfural derivative, the reaction gas contains carbon dioxide and oxygen, and the molar ratio of the carbon dioxide to the oxygen is not less than 0.1: 1; the method effectively inhibits the combustion of a solvent and the occurrence of side reactions in the oxidation process, improves the safety of the reaction, and simultaneously improves the selectivity and the yield of the FDCA (up to more than 91.8%) by controlling the reaction conditions below 150 ℃ and controlling the proportion of carbon dioxide and oxygen in the reaction gas.
Optionally, the metal catalyst comprises at least a compound of one of the following metal elements: cobalt, manganese, iron, zirconium, cerium, selenium, copper, vanadium, ruthenium or nickel; wherein, the valence of the metal ion in the compound is not limited, and the anion in the compound comprises but not limited to carbonate, acetate, tetrahydrate acetate or halide.
Optionally, the halogen comprises chlorine, bromine, fluorine or iodine; the halogen is preferably added to the mixture in the form of hydrogen halide, sodium halide, ammonium halide or potassium halide.
Optionally, the mass of the metal element in the metal catalyst is 0.4-10% of the mass of the raw material, the lower limit can be selected from 1%, 2%, 3% or 4%, and the upper limit can be selected from 5%, 6%, 7%, 8%, 9% or 10%.
Optionally, the metal catalyst at least comprises cobalt and/or cerium, when cobalt or cerium is included, the cobalt or cerium accounts for 40-100% of the total mass of the metal elements in the metal catalyst, and when cobalt and cerium are included, the sum of the mass of the cobalt and cerium accounts for 40-100% of the total mass of the metal elements in the metal catalyst;
in a specific embodiment, the metal catalyst is composed of a cobalt compound and a cerium compound, the mass ratio of cobalt to cerium in the metal catalyst is 1: 0.5-1, and the mass of the metal element in the metal catalyst is 7-8% of the mass of the raw material. The selectivity and yield of the FDCA are further improved by optimizing the using amount of the catalyst and the ratio of metal elements in the catalyst.
Optionally, the molar ratio of the metal element in the metal catalyst to the halogen is 0.8-12: 1, preferably 10-12: 1.
The yield of the FDCA is further improved by optimizing the ratio of the metal elements to the halogen.
Optionally, the molar ratio of carbon dioxide to oxygen in the reaction gas is 0.1-5: 1, preferably 0.5 to 3: 1.
optionally, the catalytic oxidation reaction temperature is 100-145 ℃, preferably 120-145 ℃, and the reaction pressure is 1-10 MPa, preferably 1-5 MPa, and more preferably 3-4 MPa.
Alternatively, the organic acid is a monocarboxylic acid, including but not limited to an aliphatic monocarboxylic acid such as acetic acid, propionic acid, butyric acid, or valeric acid, preferably acetic acid. Alternatively, the reaction gas can be formed by mixing carbon dioxide and oxygen, or carbon dioxide and oxygen-enriched air, or carbon dioxide and air.
Alternatively, the 5-hydroxymethylfurfural derivative is a 5-hydroxymethylfurfural ether derivative and/or a 5-hydroxymethylfurfural ester derivative, and specifically includes, but is not limited to, 5- (alkoxymethyl) furfural (AMF), 5- (aryloxymethyl) furfural, 5- (cycloalkoxymethyl) furfural, 5- (alkoxycarbonyl) furfural or 5-acetoxymethyl-2-furfural.
Optionally, the addition amount of the raw materials is 10-30% of the mass of the organic acid.
Optionally, the mixture further comprises water, and the mass of the water is 0.8-10%, preferably 0.8-5% of the total mass of the mixture.
The beneficial effects that this application can produce include:
the application provides a preparation method of 2, 5-furandicarboxylic acid, which effectively inhibits the combustion of a solvent and the occurrence of side reactions in the oxidation process and improves the safety of the reaction by controlling the proportion of carbon dioxide and oxygen in reaction gas and controlling the reaction conditions below 150 ℃, and simultaneously promotes the conversion of a metal catalyst from a low valence state to a high valence state by adding a certain amount of carbon dioxide into the reaction gas, accelerates the oxidation of HMF, so that the HMF is quickly converted into an intermediate product, reduces the self-polymerization of the HMF, and improves the selectivity and the yield of FDCA (up to more than 91.8%);
the yield of the FDCA is further improved (up to 97.9%) by optimizing the proportion of the metal elements in the catalyst and the proportion of the metal elements and the halogen.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
Wherein the HMF was purchased from Wutong perfumery, Tenn.
The yields of 2, 5-furandicarboxylic acid in the examples and comparative examples of the present application were calculated by the formula (molar amount of 2, 5-furandicarboxylic acid)/(molar amount of 5-hydroxymethylfurfural added). times.100%.
After the reaction of each example and comparative example was completed, quantitative measurement of FDCA was performed in solid and liquid phases using HPLC, respectively, and the total yield of FDCA was calculated using the sum of the two.
Example 1:
500g of acetic acid, 75g of HMF, 0.6g of cobalt acetate tetrahydrate, 0.7g of manganese acetate tetrahydrate, 55g of water, 0.5g of hydrogen bromide and 0.1g of cerium acetate tetrahydrate are weighed in a 1L oxidation reaction kettle, and CO is obtained by mixing carbon dioxide and oxygen2And introducing the obtained gas into a reaction kettle at the reaction pressure of 3MPa, heating to 120 ℃, continuously introducing the gas at the ratio for carrying out oxidation reaction for 1.5h, cooling to room temperature after the reaction is finished, filtering to obtain a product, quantifying the FDCA content in the solid and the solution by using HPLC respectively, and calculating to obtain the total yield of the FDCA of 91.8%.
Example 2:
500g of acetic acid, 75g of HMF, 3.0g of cobalt acetate tetrahydrate, 3.5g of manganese acetate tetrahydrate, 30g of water, 0.5g of hydrogen bromide and 0.5g of zirconium acetate are weighed in a 1L oxidation reaction kettle, and CO is obtained by mixing carbon dioxide and oxygen2And introducing the obtained gas into a reaction kettle at the reaction pressure of 3MPa, heating to 145 ℃, continuously introducing the gas at the ratio for carrying out oxidation reaction for 1h, cooling to room temperature after the reaction is finished, filtering to obtain a product, quantifying the FDCA content in the solid and the solution by using HPLC respectively, and calculating to obtain the total yield of the FDCA of 95.7%.
Example 3:
500g of acetic acid, 75g of HMF, 10.0g of cobalt acetate tetrahydrate, 16.5g of manganese acetate tetrahydrate, 10g of water and 1.0g of hydrogen bromide are weighed into a 1L oxidation reaction kettle, and CO is obtained by mixing carbon dioxide and oxygen2A gas having a molar ratio of 3:1 to oxygen, andand introducing gas into the reaction kettle, heating to 140 ℃ under the reaction pressure of 4MPa, continuously introducing the gas in the proportion for carrying out oxidation reaction for 1.5h, cooling to room temperature after the reaction is finished, filtering to obtain a product, quantifying the FDCA content in the solid and the solution by using HPLC respectively, and calculating to obtain the total yield of the FDCA of 96.5%.
Example 4:
500g of acetic acid, 75g of HMF, 15.0g of cobalt acetate tetrahydrate, 5g of cerium acetate tetrahydrate and 0.5g of hydrogen bromide are weighed into a 1L oxidation reaction kettle, and CO is obtained by mixing carbon dioxide and air2And oxygen in a molar ratio of 1: 5, introducing the obtained gas into a reaction kettle, heating to 145 ℃ under the reaction pressure of 3MPa, continuously introducing the gas in the proportion for oxidation reaction for 1.5h, cooling to room temperature after the reaction is finished, filtering to obtain a product, quantifying the FDCA content in the solid and the solution by using HPLC respectively, and calculating to obtain the total yield of the FDCA of 97.9%.
Example 5:
500g of acetic acid, 75g of HMF, 20g of cobalt acetate tetrahydrate, 5g of water and 1.0g of hydrogen bromide are weighed into a 1L oxidation reaction kettle, and CO is obtained by mixing carbon dioxide and oxygen2And introducing the obtained gas into a reaction kettle at the reaction pressure of 3MPa, heating to 130 ℃, continuously introducing the gas at the ratio for oxidation reaction for 1h, cooling to room temperature after the reaction is finished, filtering to obtain a product, quantifying the FDCA content in the solid and the solution by using HPLC respectively, and calculating to obtain the total yield of the FDCA of 96.8%.
Example 6:
500g of acetic acid, 100g of HMF, 15g of cobalt acetate tetrahydrate, 5g of cerium vanadate, 25g of water and 1.0g of hydrogen bromide are weighed in a 1L oxidation reaction kettle, and CO is obtained by mixing carbon dioxide and air2And introducing the obtained gas into a reaction kettle at the reaction pressure of 3MPa, heating to 140 ℃, continuously introducing the gas at the ratio for oxidation reaction for 2 hours, cooling to room temperature after the reaction is finished, filtering to obtain a product, quantifying the FDCA content in the solid and the solution by using HPLC respectively, and calculating to obtain the total yield of the FDCA of 95.3%.
Example 7:
500g of acetic acid, 100g of HMF, 1.0g of cobalt acetate tetrahydrate, 0.6g of zirconium acetate tetrahydrate, 1.0g of cerium acetate tetrahydrate, 10g of water and 0.5g of hydrogen bromide are weighed in a 1L oxidation reaction kettle, and CO is obtained by mixing carbon dioxide and air2And oxygen in a molar ratio of 1:2, introducing the obtained gas into a reaction kettle, heating to 145 ℃ under the reaction pressure of 3MPa, continuously introducing the gas in the proportion for oxidation reaction for 2 hours, cooling to room temperature after the reaction is finished, filtering to obtain a product, quantifying the FDCA content in the solid and the solution by using HPLC respectively, and calculating to obtain the total yield of the FDCA of 96.8%.
Example 8
The preparation method is basically the same as that of example 4, except that the dosage of the cobalt acetate tetrahydrate is 1.5g, the dosage of the cerium acetate tetrahydrate is 4g, and the total yield of the FDCA is calculated to be 91.3%.
Comparative example 1
The procedure was essentially the same as in example 4, except that air was introduced into the reactor, and the total yield of FDCA was calculated to be 71.3%.
Comparative example 2
The preparation method was substantially the same as in example 4, except that CO was reacted at a pressure of 0.5MPa before the reaction2Dispersing in acetic acid for 1.5h, introducing air into the reaction kettle after the reaction starts, and calculating to obtain the total yield of the FDCA of 75.3%.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (12)
1. A method for preparing 2, 5-furandicarboxylic acid, comprising:
continuously introducing reaction gas into the reactor to enable the mixture in the reactor to have catalytic oxidation reaction at the temperature of below 150 ℃ to generate 2, 5-furandicarboxylic acid;
wherein the mixture comprises a feedstock, an organic acid, a halogen, and a metal catalyst;
the raw material is 5-hydroxymethyl furfural;
the reaction gas contains carbon dioxide and oxygen, and the molar ratio of the carbon dioxide to the oxygen is not less than 0.1: 1;
the metal catalyst comprises a compound of cobalt and cerium, and the sum of the mass of the cobalt and the cerium accounts for 40-100% of the total mass of the metal elements in the metal catalyst; the mass ratio of cobalt to cerium in the metal catalyst is 1: 0.5-1;
the mass of the metal elements in the metal catalyst is 0.4-10% of the mass of the raw materials;
the temperature of the catalytic oxidation reaction is 100-145 ℃.
2. The production method according to claim 1, wherein the metal catalyst contains at least a compound of one of the following metal elements:
manganese, iron, zirconium, selenium, copper, vanadium, ruthenium or nickel.
3. The preparation method according to claim 1, wherein the mass of the metal element in the metal catalyst is 7-8% of the mass of the raw material.
4. The method of claim 1, wherein the halogen is selected from chlorine, bromine, fluorine or iodine; the halogen is present in the mixture in the form of hydrogen halide, sodium halide, ammonium halide or potassium halide.
5. The method according to claim 1, wherein the molar ratio of the metal element to the halogen element in the metal catalyst is 0.8 to 12: 1.
6. The method according to claim 1, wherein the molar ratio of the metal element to the halogen element in the metal catalyst is 10 to 12: 1.
7. The preparation method according to claim 1, wherein the catalytic oxidation reaction temperature is 120-145%oAnd C, the reaction pressure is 1-10 MPa.
8. The method according to claim 1, wherein the amount of the raw material added is 10 to 30% by mass of the organic acid.
9. The production method according to claim 1, wherein the organic acid is a monocarboxylic acid; the monocarboxylic acid is acetic acid, propionic acid, butyric acid or valeric acid.
10. The method of claim 1, wherein the reactant gas is formed by mixing carbon dioxide and at least one of the following gases:
oxygen, air or oxygen enriched.
11. The method according to claim 1, wherein the mixture further contains water in an amount of 0.8 to 10% by mass based on the total mass of the mixture.
12. The method according to claim 11, wherein the mixture further contains water, and the mass of the water is 0.8 to 5% of the total mass of the mixture.
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| CN115785038A (en) * | 2022-11-28 | 2023-03-14 | 濮阳拜奥迈斯生物技术有限公司 | Method for preparing 2,5-furandicarboxylic acid |
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