CN114621168A - Preparation method of furan-2, 5-dicarboxylic acid - Google Patents
Preparation method of furan-2, 5-dicarboxylic acid Download PDFInfo
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- CN114621168A CN114621168A CN202210245236.6A CN202210245236A CN114621168A CN 114621168 A CN114621168 A CN 114621168A CN 202210245236 A CN202210245236 A CN 202210245236A CN 114621168 A CN114621168 A CN 114621168A
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- reaction
- methyl
- acetylfuran
- furan
- dicarboxylic acid
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- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- KEFJLCGVTHRGAH-UHFFFAOYSA-N 2-acetyl-5-methylfuran Chemical compound CC(=O)C1=CC=C(C)O1 KEFJLCGVTHRGAH-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- OVOCLWJUABOAPL-UHFFFAOYSA-N 5-methylfuran-2-carboxylic acid Chemical compound CC1=CC=C(C(O)=O)O1 OVOCLWJUABOAPL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000012043 crude product Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 11
- 229960000583 acetic acid Drugs 0.000 claims abstract description 10
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 10
- 230000001502 supplementing effect Effects 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000007858 starting material Substances 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 15
- 229940011182 cobalt acetate Drugs 0.000 claims description 10
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 10
- 229940071125 manganese acetate Drugs 0.000 claims description 10
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 10
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 229940094035 potassium bromide Drugs 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- 238000007039 two-step reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 description 12
- 238000010992 reflux Methods 0.000 description 11
- 238000004364 calculation method Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- NBXLPPVOZWYADY-UHFFFAOYSA-N 2-ethyl-5-methylfuran Chemical compound CCC1=CC=C(C)O1 NBXLPPVOZWYADY-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- UXTFKIJKRJJXNV-UHFFFAOYSA-N 1-$l^{1}-oxidanylethanone Chemical compound CC([O])=O UXTFKIJKRJJXNV-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of furan-2, 5-dicarboxylic acid, which is characterized by comprising the following steps: 5-methyl-2-acetylfuran is used as a starting material, glacial acetic acid is used as a solvent, and the following reactions are carried out in an oxygen atmosphere according to the difficulty of oxidation: (1) oxidizing acetyl in the 5-methyl-2-acetylfuran serving as a raw material into carboxyl by using a first catalyst to obtain an intermediate 5-methyl-2-carboxyfuran; (2) and supplementing a second catalyst, and oxidizing methyl in the 5-methyl-2-carboxyfuran serving as an intermediate into carboxyl to obtain a furan-2, 5-dicarboxylic acid crude product. The method provided by the invention has the advantages of few reaction steps and low cost; the reaction does not need to be carried out at high temperature and high pressure like the prior art, so the reaction is safe; and the yield of the furan-2, 5-dicarboxylic acid product is high, and the method is suitable for industrial mass production.
Description
Technical Field
The invention relates to a preparation method of furan-2, 5-dicarboxylic acid.
Background
Furan-2, 5-dicarboxylic acid is an important intermediate for pharmaceuticals and pesticides, and can also be used to prepare polymers, such as: many people have studied degradable engineering plastics in recent years, but no industrialized process is formed.
For this purpose, patent application publication No. CN 111187238A discloses a method for synthesizing 2, 5-furandicarboxylic acid. The synthesis method comprises the following steps:
(1) mixing furfural, a hydrogenation catalyst and a solvent, adding the mixture into a reactor, introducing inert gas to replace air in the reactor, then introducing hydrogen to replace the inert gas, keeping the pressure of the hydrogen at 0.1-4MPa, heating the temperature of the reactor to 180 ℃ and 280 ℃, continuously reacting for 0.1-24 hours, and separating to obtain methylfuran;
(2) mixing methylfuran with acetic anhydride, dissolving in a solvent, introducing into a normal-pressure fixed bed reactor filled with a solid acid catalyst, wherein the temperature of the reactor is 30-150 ℃, and separating to obtain 5-methyl-2-acetylfuran;
(3) adding 5-methyl-2-acetylfuran, a supported metal catalyst and a solvent into a reactor, introducing inert gas to replace air in the reactor, subsequently introducing hydrogen to replace the inert gas, keeping the pressure of the hydrogen at 1-4MPa, heating the reactor to 180 ℃ and 280 ℃, continuously reacting for 5 minutes-24 hours, and separating to obtain 2-methyl-5-ethylfuran;
(4) adding 2-methyl-5-ethyl furan into a reactor with a polytetrafluoroethylene lining, reacting for 0.1-6 hours under the catalytic action of a catalyst, and separating to obtain 2, 5-furandicarboxylic acid.
Therefore, the 5-methyl-2-acetylfuran is synthesized by the technology; then 5-methyl-2-acetylfuran is used as a raw material to carry out reduction reaction under the hydrogen atmosphere and under the high pressure of 1-4MPa and the high temperature of 180-280 ℃ to prepare 2-methyl-5-ethylfuran; finally, under the action of a strong oxidant, the 2, 5-furandicarboxylic acid is obtained through one-step reaction.
The prior art has more reaction steps and high cost; and the reaction must be carried out at high temperature and high pressure, which is unsafe, and therefore, the method is not suitable for industrial mass production.
Disclosure of Invention
Based on the above situation, the invention develops a preparation process of furan-2, 5-dicarboxylic acid suitable for industrial production.
The invention provides a preparation method of furan-2, 5-dicarboxylic acid suitable for industrial production, which takes 5-methyl-2-acetylfuran as a starting material and glacial acetic acid as a solvent, firstly uses a weak catalyst to oxidize acetyl oxygen into carboxyl according to the difficulty degree of oxidation, and then supplements a strong catalyst to oxidize methyl oxygen into carboxyl, so as to obtain a furan-2, 5-dicarboxylic acid product with the content of more than 99 percent, wherein the yield is more than 98 percent.
The principle of the chemical reaction is as follows:
the method provided by the invention has the advantages of few reaction steps and low cost; the reaction does not need to be carried out at high temperature and high pressure like the prior art, so the reaction is safe; and the yield of the furan-2, 5-dicarboxylic acid product is high, and the method is suitable for industrial mass production.
Detailed Description
The invention provides a preparation method of furan-2, 5-dicarboxylic acid, which is characterized by comprising the following steps: taking 5-methyl-2-acetylfuran as a starting material, taking glacial acetic acid as a solvent, and carrying out the following reactions in an oxygen atmosphere according to the difficulty degree of oxidation:
(1) oxidizing acetyl in the 5-methyl-2-acetylfuran serving as a raw material into carboxyl by using a first catalyst to obtain an intermediate 5-methyl-2-carboxyfuran;
(2) supplementing a second catalyst, and oxidizing methyl in the 5-methyl-2-carboxyfuran serving as an intermediate into carboxyl to obtain a furan-2, 5-dicarboxylic acid crude product;
the chemical reaction principle is as follows:
in step (1), the lower the content of the raw material in the reaction system, the more the reaction in step (1) proceeds, and therefore, the lower the content of the raw material in the reaction system, the better the procedure for proceeding to step (2). Preferably, when the content of the 5-methyl-2-acetylfuran as the raw material in the reaction system is less than 0.5% after the reaction of the step (1), the procedure of the step (2) is entered. If the content of the raw materials is more than 0.5%, continuously introducing oxygen to carry out reaction until the content of the 5-methyl-2-acetylfuran is less than 0.5%, and controlling the content of the 5-methyl-2-carboxyfuran to be more than 98%.
In addition, the first catalyst is cobalt acetate, manganese acetate and triethanolamine, and the using amount of the first catalyst is 1.5-2% of the mass of the 5-methyl-2-acetylfuran; the second catalyst is cobalt acetate, manganese acetate, potassium bromide and zirconium acetate, and the dosage of the second catalyst is respectively 2.3-3%, 2.3-3%, 1.5-2% and 1.5-2% of the mass of the 5-methyl-2-acetylfuran; the dosage of the solvent is 12-14 times of the mass of the 5-methyl-2-acetylfuran.
The amount of oxygen introduced may be 8 to 10 cubic/hour throughout the reaction.
In addition, the method further comprises: before and in the middle of the reaction, testing the moisture in the reaction system, and adding acetic anhydride to absorb the water generated by the reaction so as to promote the reaction to rapidly proceed. Preferably, the water content in the reaction system is not more than 1%, otherwise the activity of the catalyst is reduced, and in order to ensure that the reaction is carried out smoothly, the amount of the acetic anhydride to be supplemented needs to be calculated according to the measured water content and the acetic anhydride needs to be supplemented. More preferably, the water content in the reaction system is monitored periodically, and when the water content in the reaction system is not more than 1%, the amount of the acetic anhydride to be supplemented is calculated actively according to the measured water content, and the acetic anhydride is supplemented.
The reaction of step (1) comprises: reacting at 113-117 ℃ for 11-14 hours, wherein the reaction of the step (2) comprises the following steps: the reaction was carried out at 112 ℃ and 115 ℃ for 8-12 hours.
In addition, the method further comprises: carrying out post-treatment on a furan-2, 5-dicarboxylic acid crude product feed liquid obtained by the two-step reaction, wherein the post-treatment comprises the following steps: and carrying out solid-liquid separation and refining on the crude feed liquid to obtain a furan-2, 5-dicarboxylic acid product.
In the step (2), the lower the content of the intermediate in the reaction system, the more the reaction in the step (2) proceeds, and therefore, the lower the content of the intermediate in the reaction system, the better the reaction in the step (2) is terminated. Preferably, after the reaction in step (2) and when the content of the 5-methyl-2-carboxyfuran as the intermediate in the reaction system is less than 0.5%, the reaction is ended and the post-treatment procedure is performed. If the content of the 5-methyl-2-carboxyl furan is more than 0.5 percent, oxygen is continuously introduced for reaction until the content of the 5-methyl-2-carboxyl furan is less than 0.5 percent, and the content of the medium-control furan-2, 5-dicarboxylic acid is more than 99 percent.
The present invention will be described more specifically with reference to examples. In the following examples, the starting materials are all conventional in the art and are commercially available.
Examples
Example 1
1500L of glacial acetic acid (the using amount is 12 times of the mass of 5-methyl-2-acetylfuran), 124kg of 5-methyl-2-acetylfuran, 2kg of cobalt acetate as a first catalyst, 2kg of manganese acetate and 2kg of triethanolamine (the using amounts are 1.6 percent of the mass of 5-methyl-2-acetylfuran) are added into a 2000L glass lining reaction kettle with a condenser and a tail gas absorption device, stirring is started, the water content is measured to be 0.5 percent, 42kg of acetic anhydride is supplemented through calculation, the temperature is raised to reflux (the solvent is refluxed, the reaction is started, the temperature is 117 ℃ at the beginning, the temperature is reduced to 113 ℃ along with the progress of the reaction, oxygen is introduced through 10 cubic/hour reflux, the water content is measured to be 0.9 percent in 10 hours, 77kg of acetic anhydride is supplemented through calculation, the content of 5-methyl-2-acetylfuran as a raw material is controlled to be 0.3 percent in 13-hour sampling, at this time, the content of the medium-controlled 5-methyl-2-carboxyfuran was 99%.
Cooling to 60 ℃, adding 3kg of cobalt acetate, 3kg of manganese acetate, 2.5kg of potassium bromide and 2.5kg of zirconium acetate (the dosage is respectively 2.4%, 2.4%, 2% and 2% of the mass of 5-methyl-2-acetylfuran) as a second catalyst, uniformly stirring, measuring the water content to be 0.3%, calculating, supplementing 25kg of acetic anhydride, heating to reflux (the solvent is refluxed, the reaction starts, the temperature is 115 ℃, the temperature is reduced to 112 ℃ along with the reaction), introducing oxygen by 10 cubic/hour reflux, measuring the water content to be 0.85% in 7 hours, supplementing 72kg of acetic anhydride by calculation, sampling and controlling in 10 hours, wherein the raw material 5-methyl-2-acetylfuran does not exist, the content of 5-methyl-2-carboxyfuran is 0.4%, the content of medium-controlled furan-2, 5-dicarboxylic acid is 99.3%, to prepare the furan-2, 5-dicarboxylic acid crude product feed liquid.
And (3) turning off oxygen, cooling to 35 ℃, putting the crude feed liquid into a centrifuge for spin-drying to obtain mother liquid and crude products, putting the mother liquid into a distillation still, recovering glacial acetic acid for the next reaction, rinsing the crude products on the centrifuge by using tap water, spin-drying, putting the products into a drying room for drying to obtain 154kg of furan-2, 5-dicarboxylic acid products, wherein the content is 99.2%, the melting point is more than 310 ℃, and the yield is 98.7%.
Example 2
1700L of glacial acetic acid (the dosage is 13.7 times of the mass of 5-methyl-2-acetylfuran), 124kg of 5-methyl-2-acetylfuran, 2.5kg of cobalt acetate as a first catalyst, 2.5kg of manganese acetate and 2.5kg of triethanolamine (the dosages are both 2 percent of the mass of 5-methyl-2-acetylfuran)) are put into a 2000L glass lining reaction kettle with a condenser and a tail gas absorption device, stirring is started, the water content is measured to be 0.4 percent, 38kg of acetic anhydride is added through calculation, the temperature is raised to reflux (the temperature is 117 ℃ at the beginning of the reaction and is reduced to 113 ℃ along with the progress of the reaction, oxygen is introduced for 8 cubic minutes/hour for reflux, the water content is measured to be 0.8 percent after 8 hours, 77kg of acetic anhydride is added through calculation, the content of 5-methyl-2-acetylfuran as a raw material is controlled to be 0.2 percent in 11 hour sampling, at this time, the content of 5-methyl-2-carboxyfuran was controlled to 99%.
Cooling to 60 ℃, adding 3.5kg of cobalt acetate, 3.5kg of manganese acetate, 2kg of potassium bromide and 2kg of zirconium acetate (the dosage is respectively 2.8%, 2.8%, 1.6% and 1.6% of the mass of 5-methyl-2-acetylfuran) as a second catalyst, uniformly stirring, measuring the water content by 0.26%, calculating, supplementing 25kg of acetic anhydride, heating to reflux (the solvent is refluxed, the reaction starts, the temperature is 115 ℃ at the beginning, the temperature is reduced to 112 ℃ along with the reaction, opening oxygen for 8 cubic/h, introducing oxygen by refluxing, measuring the water content by 0.85% after 9 hours, supplementing 82kg of acetic anhydride by calculation, sampling and controlling in 12 hours, wherein the raw material 5-methyl-2-acetylfuran does not exist, the content of 5-methyl-2-carboxyfuran is 0.45%, and the content of furan-2, 5-dicarboxylic acid is 99.3%, to prepare the furan-2, 5-dicarboxylic acid crude product feed liquid.
And (3) turning off oxygen, cooling to 35 ℃, putting the crude feed liquid into a centrifuge for spin-drying to obtain mother liquid and crude products, putting the mother liquid into a distillation still, recovering glacial acetic acid for the next reaction, rinsing the crude products on the centrifuge by using tap water, spin-drying, putting the products into a drying room for drying to obtain 154.6kg of furan-2, 5-dicarboxylic acid products, wherein the content is 99.4%, the melting point is more than 310 ℃, and the yield is 99.1%.
Example 3
1500L of glacial acetic acid (the dosage is 12 times of the mass of 5-methyl-2-acetylfuran), 124kg of 5-methyl-2-acetylfuran, 2kg of cobalt acetate as a first catalyst, 2kg of manganese acetate and 2kg of triethanolamine (the dosages are all 1.6 percent of the mass of 5-methyl-2-acetylfuran) are put into a 2000L glass lining reaction kettle with a condenser and a tail gas absorption device, stirring is started, the water content is measured to be 0.4 percent, 34kg of acetic anhydride is supplemented, the temperature is raised to reflux (the solvent is refluxed, the reaction is started, the temperature is 117 ℃ at the beginning, the temperature is reduced to 113 ℃ along with the reaction, the oxygen is opened for 10 cubic meters per hour to flow back and supply oxygen, the water content is measured to be 0.92 percent in 9 hours, 78kg of acetic anhydride is supplemented through calculation, the content of 5-methyl-2-acetylfuran as a raw material is controlled to be 0.1 percent in 13 hours of sampling, at this time, the content of the medium-controlled 5-methyl-2-carboxyfuran was 99.5%.
Cooling to 60 ℃, adding 3kg of cobalt acetate, 3kg of manganese acetate, 2kg of potassium bromide and 2.2kg of zirconium acetate (the dosage is respectively 2.4%, 2.4%, 1.6% and 1.8% of the mass of 5-methyl-2-acetylfuran) as a second catalyst, uniformly stirring, measuring the water content by 0.28%, calculating, supplementing 24kg of acetic anhydride, heating to reflux (the solvent is refluxed, the reaction starts, the temperature is 115 ℃, the temperature is reduced to 112 ℃ along with the reaction), introducing oxygen by 10 cubic/hour reflux after 10 cubic/hour, measuring the water content by 0.96% after 7 hours, supplementing 82kg of acetic anhydride by calculation, sampling and controlling in 9 hours, wherein the raw material 5-methyl-2-acetylfuran does not exist, the content of 5-methyl-2-carboxyfuran is 0.3%, the content of medium-controlled furan-2, 5-dicarboxylic acid is 99.3%, to prepare the furan-2, 5-dicarboxylic acid crude product feed liquid.
And (3) turning off oxygen, cooling to 35 ℃, putting the crude feed liquid into a centrifuge for spin-drying to obtain mother liquid and crude products, putting the mother liquid into a distillation still, recovering glacial acetic acid for the next reaction, rinsing the crude products on the centrifuge by using tap water, spin-drying, putting the products into a drying room for drying to obtain 155kg of furan-2, 5-dicarboxylic acid products, wherein the content is 99.8%, the melting point is more than 310 ℃, and the yield is 99.3%.
The yields of furan-2, 5-dicarboxylic acid in the above examples are shown in table 1 below:
TABLE 1
| Example 1 | Example 2 | Example 3 | |
| Yield of furan-2, 5-dicarboxylic acid | 98.7％ | 99.1％ | 99.3％ |
From the data of examples 1-3 above, it can be seen that the yield of furan-2, 5-dicarboxylic acid produced by the method of the present invention can be more than 98%. Therefore, the method provided by the invention can meet the requirement of the market on industrial mass production of furan-2, 5-dicarboxylic acid.
Claims (9)
1. A process for the preparation of furan-2, 5-dicarboxylic acid, comprising: taking 5-methyl-2-acetylfuran as a starting material, taking glacial acetic acid as a solvent, and carrying out the following reactions in an oxygen atmosphere according to the difficulty degree of oxidation:
(1) oxidizing acetyl in the 5-methyl-2-acetylfuran serving as a raw material into carboxyl by using a first catalyst to obtain an intermediate 5-methyl-2-carboxyfuran;
(2) supplementing a second catalyst, and oxidizing methyl in the 5-methyl-2-carboxyfuran serving as an intermediate into carboxyl to obtain a furan-2, 5-dicarboxylic acid crude product;
the principle of the chemical reaction is as follows:
2. the method according to claim 1, wherein the reaction in step (2) is carried out when the content of 5-methyl-2-acetylfuran as the raw material in the reaction system is less than 0.5% after the reaction in step (1).
3. The method of claim 1, wherein the first catalyst is cobalt acetate, manganese acetate, and triethanolamine, each in an amount of 1.5-2% by mass of the 5-methyl-2-acetylfuran;
the second catalyst is cobalt acetate, manganese acetate, potassium bromide and zirconium acetate, and the dosage of the second catalyst is respectively 2.3-3%, 2.3-3%, 1.5-2% and 1.5-2% of the mass of the 5-methyl-2-acetylfuran;
the dosage of the solvent is 12-14 times of the mass of the 5-methyl-2-acetylfuran.
4. The method according to claim 1, wherein the oxygen is introduced in an amount of 8 to 10 cubic/hour.
5. The method of claim 1, wherein the method further comprises: before the reaction starts and in the middle of the reaction, testing the moisture in the reaction system, and adding acetic anhydride to absorb the water generated by the reaction and promote the reaction.
6. The method as claimed in claim 5, wherein the water content in the reaction system is not more than 1%, and the amount of acetic anhydride to be added is calculated according to the measured water content in the midway and is added.
7. The method of claim 5, wherein the reaction of step (1) comprises: reacting at 113 ℃ and 117 ℃ for 11-14 hours, wherein the reaction in the step (2) comprises the following steps: the reaction was carried out at 112 ℃ and 115 ℃ for 8-12 hours.
8. The method of claim 1, wherein the method further comprises: after-treatment is carried out on the furan-2, 5-dicarboxylic acid crude product feed liquid obtained by the two-step reaction,
the post-treatment comprises the following steps: and carrying out solid-liquid separation and refining on the crude feed liquid to obtain a furan-2, 5-dicarboxylic acid product.
9. The method according to claim 8, wherein the post-treatment procedure is performed when the content of the 5-methyl-2-carboxyfuran as the intermediate in the reaction system is less than 0.5% after the reaction of the step (2).
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| CN202210245236.6A CN114621168A (en) | 2022-03-14 | 2022-03-14 | Preparation method of furan-2, 5-dicarboxylic acid |
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