CN112898251A - Method for preparing 2, 5-furandicarboxylic acid - Google Patents

Method for preparing 2, 5-furandicarboxylic acid Download PDF

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CN112898251A
CN112898251A CN201911136112.9A CN201911136112A CN112898251A CN 112898251 A CN112898251 A CN 112898251A CN 201911136112 A CN201911136112 A CN 201911136112A CN 112898251 A CN112898251 A CN 112898251A
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metal catalyst
cobalt
acid
reaction
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马中森
张亚杰
陈金波
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Ningbo Huafu New Material Technology Co ltd
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Ningbo Institute of Material Technology and Engineering of CAS
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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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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The application discloses a preparation method of 2, 5-furandicarboxylic acid, belonging to the technical field of organic chemistry. The method effectively inhibits the occurrence of 5-hydroxymethylfurfural peroxidation, increases the selectivity of FDCA and improves the yield (which can reach more than 93.8 percent) by controlling the proportion of carbon dioxide and oxygen in reaction gas and controlling the reaction condition at 200 ℃, and simultaneously inhibits the combustion of a solvent due to the existence of carbon dioxide and improves the safety of the reaction.

Description

Method for preparing 2, 5-furandicarboxylic acid
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.
In several synthetic routes of FDCA, the method for preparing FDCA by using the co-catalytic oxidation method of bromine in organic acid and a metal catalyst is the most promising way for realizing industrialization, no waste salt is generated basically in the production process, the organic acid can be recycled, and the catalyst can be recycled, so that the method is an environment-friendly preparation method.
In US 8791277B 2, HMF is used as a substrate, FDCA is prepared by catalytic oxidation under the conditions of 0-15% of water content and 100-200 ℃, the yield can reach more than 90%, but the combustion of a solvent is aggravated due to high Co content (Co/Mn is 10-400, Co/Br is 0.7-3.5), the temperature rise speed is high, the safety coefficient is low, acetic acid is excessively combusted, and the cost is high.
In EP 2486027B 1, HMF is used as a substrate, and FDCA is prepared by catalytic oxidation under the conditions of Co/Mn 1/1000-100/1, Br/(Co + Mn) 0.001-5, and (Co + Mn)/substrate 0.1-10% at 160-190 ℃, wherein the yield is 70-80%, and the yield is low.
Under the condition of catalysts of 59-5900 ppm Co, 55-5500 ppm Mn and 203-20000 ppm Br based on the concentration of a substrate, Zr and Ce are selectively added to catalyze HMF and ester thereof to prepare FDCA, and the yield of the FDCA reaches about 80% and is low.
In US 9643945B 2, 5-methoxymethyl furfural and derivatives thereof are used as substrates, Co/Mn/Br is used as a main catalyst, Zr, Ce, Mo, Ni, Cr, Ru, Fe and Hf are added as promoters, wherein the catalyst ratio is Co/Mn 1: 1-100: 1, the content of Co in a reaction solution is 500-6000 ppm, the content of Mn is 20-6000 ppm, the content of Br is 30-8000 ppm and the content of water is 1-15%, 5-methoxymethyl furfural and derivatives thereof are catalyzed under the conditions of 125-180 ℃ and 3-15 bar pressure to prepare FDCA, the yield of the FDCA can reach over 90% in a low-oxygen environment (6-22% vol oxygen), and about 15% of FDCA monoesters exist in the FDCA, so that the difficulty of subsequent purification and refining is increased.
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, and carrying out catalytic oxidation reaction on the mixture in the reactor at the temperature of 150-200 ℃ and under the pressure of 1-10 MPa 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-hydroxymethylfurfural or a 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 0.3: 1; according to the method, the proportion of carbon dioxide and oxygen in the reaction gas is controlled, the reaction conditions are controlled at 150-200 ℃ and 1-10 MPa, the occurrence of 5-hydroxymethylfurfural peroxidation is effectively inhibited, the selectivity of FDCA is increased, the yield is improved (over 93.8 percent), and meanwhile, due to the existence of the carbon dioxide, the combustion of a solvent is inhibited, and the reaction safety is improved.
Optionally, the molar ratio of carbon dioxide to oxygen in the reaction gas is 0.5-5: 1.
Optionally, the catalytic oxidation reaction temperature is 150-180 ℃, and the reaction pressure is 1-5 MPa, more preferably 3-4 MPa.
Optionally, the addition amount of the raw materials is 10-30% of the mass of the solvent.
Optionally, the mixture further comprises water, and the mass of the water is 1-20%, preferably 2-10% of the total mass of the mixture.
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 0.05-2.5% of the mass of the raw material, the lower limit may be selected from 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 2%, 3%, 4%, and the upper limit may 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 18-100% 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 18-100% of the total mass of the metal elements in the metal catalyst;
optionally, the metal catalyst at least comprises cobalt and manganese elements, the mass ratio of the cobalt to the manganese elements is 1: 3-4, and the mass of the metal elements in the metal catalyst is 1.5-1.7% of the mass of the raw materials. By controlling the dosage of the metal catalyst and the proportion of cobalt and manganese in the metal catalyst, the solvent combustion is further avoided, the solvent loss is reduced, the selectivity and yield of the FDCA are improved, and the reaction cost is reduced.
Optionally, the molar ratio of the metal element in the metal catalyst to the halogen is 1-20: 1, preferably 3-5: 1. The yield of the FDCA is further improved by optimizing the ratio of the metal elements in the catalyst and the ratio of the metal elements to the halogen.
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 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.
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.
The beneficial effects that this application can produce include:
by controlling the proportion of carbon dioxide and oxygen in the reaction gas and controlling the reaction condition at 200 ℃, the generation of 5-hydroxymethylfurfural peroxidation is effectively inhibited, the selectivity of FDCA is increased, the yield is improved (over 93.8 percent), and simultaneously, due to the existence of carbon dioxide, the combustion of a solvent is inhibited, and the safety of the reaction is improved;
the yield of the FDCA is further improved (up to 98.7%) 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, 0.1g of cobalt acetate tetrahydrate, 0.1g of manganese acetate tetrahydrate, 65g of water, 0.1g of hydrogen bromide and 0.1g of cerium acetate tetrahydrate are weighed into a 1L oxidation reaction kettle, and CO is added2Mixing with oxygen to obtain CO2And introducing the obtained gas into a reaction kettle at the reaction pressure of 3MPa, heating to 200 ℃, continuously introducing the gas at the ratio for oxidation reaction for 0.5h, 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 93.8%.
Example 2:
500g of acetic acid, 75g of HMF, 1.0g of cobalt acetate tetrahydrate, 3.3g of manganese acetate tetrahydrate, 30g of water, 0.5g of hydrogen bromide and 0.5g of zirconium acetate were weighed into a 1L oxidation reactor by introducing CO2Mixing with air to obtain CO2And introducing the obtained gas into a reaction kettle at the reaction pressure of 3MPa, heating to 180 ℃, 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 98.7%.
Example 3:
500g of acetic acid, 75g of HMF, 1.0g of cobalt acetate tetrahydrate, 4.5g of manganese acetate tetrahydrate, 15g of water and 1.0g of hydrogen bromide are weighed into a 1L oxidation reaction kettle, and CO is added2Mixing with oxygen to obtain CO2And introducing the obtained gas into a reaction kettle at the reaction pressure of 4MPa, heating to 180 ℃, 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 96.5%.
Example 4:
500g of acetic acid, 75g of HMF, 2.0g of cobalt acetate tetrahydrate, 3.2g of cerium acetate tetrahydrate, 20g of water and 0.5g of hydrogen bromide are weighed into a 1L oxidation reaction kettle, and CO is added2Mixing with oxygen to obtain CO2And oxygen in a molar ratio of 1:3, introducing the obtained gas into a reaction kettle, heating to 150 ℃ under the reaction pressure of 3MPa, continuously introducing the gas in the proportion 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 95.7%.
Example 5:
500g of acetic acid, 75g of HMF, 3.0g of cobalt acetate tetrahydrate, 20g of water and 1.0g of hydrogen bromide were weighed into a 1L oxidation reactor by introducing CO2Mixing with oxygen to obtain CO2And introducing the obtained gas into a reaction kettle at the reaction pressure of 3MPa, heating to 160 ℃, 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 95.9%.
Example 6:
500g of acetic acid, 100g of HMF, 1.5g of cobalt acetate tetrahydrate, 1.5g of cerium vanadate, 25g of water and 1.0g of hydrogen bromide are weighed into a 1L oxidation reaction kettle, and CO is added2Mixing with oxygen to obtain CO2Introducing the obtained gas into a reaction kettle at a reaction pressure of 3MPa and a temperature of 170 ℃ with the molar ratio of the gas to oxygen being 3:1And continuously introducing the gas with the proportion 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 96.8%.
Example 7:
500g of acetic acid, 100g of HMF, 1.0g of cobalt acetate tetrahydrate, 1.0g of zirconium acetate tetrahydrate, 1.0g of cerium acetate tetrahydrate, 10g of water and 0.1g of hydrogen bromide were weighed into a 1L oxidation reaction kettle, and CO was added2Mixing with oxygen to obtain CO2And introducing the obtained gas into a reaction kettle at the reaction pressure of 3MPa, heating to 160 ℃, 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 95.8%.
Example 8
The procedure was essentially the same as in example 2, except that manganese acetate tetrahydrate was used in an amount of 2.5g, and the overall yield of FDCA was calculated to be 93.9%.
Comparative example 1
The procedure was essentially the same as in example 2, except that air was introduced into the reactor, and the total yield of FDCA was calculated to be 70.3%.
Comparative example 2
The preparation method was substantially the same as in example 2, except that CO was reacted at a pressure of 0.5MPa before the reaction2Dispersing in acetic acid for 1h, introducing air into the reaction kettle after the reaction starts, and calculating to obtain the total yield of the FDCA of 73.8 percent.
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 (10)

1. A method for preparing 2, 5-furandicarboxylic acid, comprising:
continuously introducing reaction gas into the reactor, and carrying out catalytic oxidation reaction on the mixture in the reactor at the temperature of 150-200 ℃ and under the pressure of 1-10 MPa 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-hydroxymethylfurfural or a 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 0.3: 1.
2. The preparation method according to claim 1, wherein the molar ratio of carbon dioxide to oxygen in the reaction gas is 0.5-5: 1.
3. The preparation method according to claim 1, wherein the catalytic oxidation reaction temperature is 150 to 180 ℃ and the reaction pressure is 1 to 5 MPa.
4. The preparation method according to claim 1, characterized in that the mixture further comprises water, and the mass of the water is 1-20% of the total mass of the mixture;
preferably, the mass of the water is 2-10% of the total mass of the mixture.
5. The production method according to claim 1, wherein the metal catalyst contains at least a compound of one of the following metal elements:
cobalt, manganese, iron, zirconium, cerium, selenium, copper, vanadium, ruthenium or nickel; preferably, the mass of the metal element in the metal catalyst is 0.05-2.5% of the mass of the raw material;
preferably, the metal catalyst at least comprises cobalt and/or cerium, when the cobalt or cerium is included, the cobalt or cerium accounts for 18-100% of the total mass of the metal elements in the metal catalyst, and when the cobalt and cerium are included, the sum of the mass of the cobalt and cerium accounts for 18-100% of the total mass of the metal elements in the metal catalyst;
preferably, the metal catalyst at least comprises cobalt and manganese elements, the mass ratio of the cobalt to the manganese elements is 1: 3-4, and the mass of the metal elements in the metal catalyst is 1.5-1.7% of the mass of the raw materials.
6. The method of claim 1, wherein the halogen comprises 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.
7. The preparation method according to claim 1 or 6, wherein the molar ratio of the metal element in the metal catalyst to the halogen is 1-20: 1;
preferably, the molar ratio of the metal element in the metal catalyst to the halogen is 3-5: 1.
8. The production method according to claim 1, wherein the organic acid is a monocarboxylic acid; the organic acid is acetic acid, propionic acid, butyric acid or valeric acid.
9. The production method according to claim 1, wherein the 5-hydroxymethylfurfural derivative is a 5-hydroxymethylfurfural ether derivative and/or a 5-hydroxymethylfurfural ester derivative;
preferably, the addition amount of the raw materials is 10-30% of the mass of the organic 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.
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