CN114539047A - Preparation method of 1,2, 3-hemimellitic acid - Google Patents
Preparation method of 1,2, 3-hemimellitic acid Download PDFInfo
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- CN114539047A CN114539047A CN202210305055.8A CN202210305055A CN114539047A CN 114539047 A CN114539047 A CN 114539047A CN 202210305055 A CN202210305055 A CN 202210305055A CN 114539047 A CN114539047 A CN 114539047A
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- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 22
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229960000583 acetic acid Drugs 0.000 claims abstract description 11
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 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 abstract description 10
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 10
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 10
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 10
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 229940094035 potassium bromide Drugs 0.000 claims abstract description 5
- 239000007858 starting material Substances 0.000 claims abstract description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000010992 reflux Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 230000001502 supplementing effect Effects 0.000 description 6
- 238000003916 acid precipitation Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- NBIJDQIBCRZHFK-UHFFFAOYSA-N 1,3,5-trihydroxy-1,3,5-triazinane-2,4,6-trione Chemical compound ON1C(=O)N(O)C(=O)N(O)C1=O NBIJDQIBCRZHFK-UHFFFAOYSA-N 0.000 description 1
- -1 THICA Chemical compound 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- 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
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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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
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a preparation method of 1,2, 3-hemimellitic acid, which is characterized by comprising the following steps: 1,2, 3-hemimellitene is used as a starting material, glacial acetic acid is used as a solvent, cobalt acetate, manganese acetate and potassium bromide are used as catalysts, zirconium acetate is used as a cocatalyst, and didodecyldimethylammonium bromide used as a phase transfer catalyst is added to perform an oxidation reaction in an oxygen atmosphere. The method provided by the invention does not use expensive raw materials and equipment, and has 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 due to the reasonable selection of the catalyst and the cocatalyst and the application of the phase transfer catalyst, the yield of the 1,2, 3-hemimellitic acid product is high, and the method is suitable for industrial mass production.
Description
Technical Field
The invention relates to a preparation method of 1,2, 3-hemimellitic acid.
Background
1,2, 3-hemimellitic acid is an important organic synthesis intermediate, the market price is 70 ten thousand yuan/ton at present, but the intermediate is still valuable and has no goods.
The preparation method of the 1,2, 3-hemimellitic acid reported at home and abroad at present comprises the following steps: oxidizing 1,2, 3-hemimellitene with potassium permanganate or hyperbaric oxygen to produce 1,2, 3-hemimellitene.
Wherein, the potassium permanganate oxidation method can generate decarboxylation, has low yield, large pollution, high cost and poor quality and is difficult to meet the requirements of customers; the high-pressure oxygen oxidation method has low safety coefficient, is easy to explode, is not suitable for industrial production, and has improper catalyst, low yield, more tar and poor product quality.
Disclosure of Invention
Based on the condition of the prior art, the invention provides the method for preparing the 1,2, 3-hemimellitic acid by catalyzing the 1,2, 3-hemimellitene to oxidize the 1,2, 3-hemimellitene into the 1,2, 3-hemimellitene under the liquid phase and the normal pressure, which has high yield, good product quality and low cost, and the produced product is satisfied by customers and meets the market demand.
The inventor of the invention finds out through repeated research that the yield of the 1,2, 3-hemimellitic acid can be improved and the 1,2, 3-hemimellitic acid with high purity can be prepared by reasonably selecting the catalyst and the cocatalyst and applying the phase transfer catalyst.
Specifically, glacial acetic acid is used as a solvent, cobalt acetate, manganese acetate and potassium bromide are used as catalysts, zirconium acetate is used as a cocatalyst, a phase transfer catalyst didodecyldimethylammonium bromide is added, the raw material 1,2, 3-hemimellitene is added, the temperature is raised to reflux (the solvent glacial acetic acid is refluxed at the starting temperature of 117 ℃, and the temperature is 112 ℃ after the later reaction is finished), oxygen is introduced for oxidation reaction, water is measured midway to supplement acetic anhydride, the reaction is thorough, and finally the 1,2, 3-hemimellitene is completely converted.
The principle of the chemical reaction is as follows:
the method provided by the invention does not use expensive raw materials and equipment, and has 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 due to the reasonable selection of the catalyst and the cocatalyst and the application of the phase transfer catalyst, the yield of the 1,2, 3-hemimellitic acid product is high, and the method is suitable for industrial mass production.
Detailed Description
The invention provides a preparation method of 1,2, 3-hemimellitic acid, which is characterized by comprising the following steps: 1,2, 3-hemimellitene is used as a starting material, glacial acetic acid is used as a solvent, cobalt acetate, manganese acetate and potassium bromide are used as catalysts, zirconium acetate is used as a cocatalyst, and didodecyldimethylammonium bromide used as a phase transfer catalyst is added to perform an oxidation reaction in an oxygen atmosphere.
The chemical reaction principle is as follows:
the catalyst comprises a solvent, a cocatalyst and a phase transfer catalyst, wherein the dosage of the solvent is 9-11 times of the mass of 1,2, 3-hemimellitene, the dosages of the cobalt acetate, the manganese acetate and the potassium bromide in the catalyst are all 2-2.5% of the mass of 1,2, 3-hemimellitene, the dosage of the cocatalyst is 1.3-1.6% of the mass of 1,2, 3-hemimellitene, and the dosage of the phase transfer catalyst is 1.3-1.6% of the mass of 1,2, 3-hemimellitene.
The amount of oxygen introduced may be 8 to 10 cubic/hour.
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, when the moisture in the reaction system is more than 3%, 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 moisture amount and the acetic anhydride needs to be supplemented. More preferably, the water content in the reaction system is monitored regularly, the water content in the reaction system is not more than 3%, the amount of the acetic anhydride to be supplemented is calculated actively in the midway according to the actually measured water content, and the acetic anhydride is supplemented.
Preferably, the reaction is carried out at 112 ℃ and 117 ℃ for 17 to 20 hours.
In addition, the method further comprises: carrying out post-treatment on the crude feed liquid of the 1,2, 3-hemimellitic acid obtained by the reaction, wherein the post-treatment comprises the following steps: and refining the crude feed liquid to obtain a 1,2, 3-hemimellitic acid product.
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
1500kg of glacial acetic acid (the amount is 10 times of the mass of 1,2, 3-hemimellitene), 150kg of 1,2, 3-hemimellitene, 3kg of cobalt acetate, 3kg of manganese acetate, 3kg of potassium bromide (the amounts are 2% of the mass of 1,2, 3-hemimellitene), 2kg of zirconium acetate (the amount is 1.3% of the mass of 1,2, 3-hemimellitene), 2kg of didodecyldimethylammonium bromide (the amount is 1.3% of the mass of 1,2, 3-hemimellitene), 2kg of a cocatalyst, 2kg of a phase transfer catalyst, 0.3% of water content after stirring, adding 25kg of acetic anhydride after calculation, heating to reflux (solvent reflux, reaction start, temperature is 117 ℃ at the beginning, and temperature is reduced to 112 ℃ along with the progress of the reaction), and (3) introducing oxygen by refluxing for 10 cubic meters per hour, testing that the water content is 2.4 percent after 10 hours, supplementing 204kg of acetic anhydride by calculation, testing that the water content is 1.1 percent after 15 hours, supplementing 94kg of acetic anhydride by calculation, controlling the existence of the raw material 1,2, 3-hemimellitene in a 20-hour sampling process, and completely converting the raw material 1,2, 3-hemimellitene into the 1,2, 3-hemimellitene.
Stopping introducing oxygen, cooling to 60 ℃, transferring to a 3000L distillation kettle, evaporating glacial acetic acid to dryness for next batch reaction, slightly cooling, adding 1000L water into the kettle, dropwise adding 800L 30% liquid caustic soda, stirring for complete dissolution, adjusting the pH value to 4.1 by using 10% dilute sulfuric acid, adding 3kg of active carbon, heating to 80 ℃, stirring for decolorization for 20 minutes, press-filtering, heating the filtrate to 92 ℃, carrying out acid precipitation by using 10% dilute sulfuric acid until the pH value is less than 0.5, cooling to room temperature, carrying out spin-drying, carrying out drip-washing on a centrifuge by using water, carrying out spin-drying, and drying to obtain 257.3kg of 1,2, 3-hemimellitic acid product with the content of 99.5%, the melting range of 190 and 192 ℃ and the yield of 98%.
Example 2
1350kg of glacial acetic acid (the dosage is 9 times of the mass of 1,2, 3-hemimellitene), 150kg of 1,2, 3-hemimellitene, 3.7kg of cobalt acetate as a catalyst, 3.7kg of manganese acetate, 3.7kg of potassium bromide (the dosages are all 2.5 percent of the mass of 1,2, 3-hemimellitene), 2.4kg of zirconium acetate as a cocatalyst (the dosages are 1.6 percent of the mass of 1,2, 3-hemimellitene), 2.3kg of didodecyldimethylammonium bromide as a phase transfer catalyst (the dosages are 1.5 percent of the mass of 1,2, 3-hemimellitene), 0.4 percent of moisture after uniform stirring, 30kg of acetic anhydride is added by calculation, the temperature is raised to reflux (the reflux of a solvent is carried out, the reaction is started, the temperature is 117 ℃, the temperature is reduced to 112 ℃ along with the progress of the reaction), and (3) introducing 8 cubic meters of oxygen for reflux at one hour, testing the water content to be 2.9 percent after 11 hours, supplementing 221kg of acetic anhydride by calculation, testing the water content to be 1 percent after 15 hours, supplementing 77kg of acetic anhydride by calculation, sampling for 17 hours, controlling the condition that no raw material 1,2, 3-hemimellitene exists, and completely converting into 1,2, 3-hemimellitene.
Stopping introducing oxygen, cooling to 60 ℃, transferring to a 3000L distillation kettle, evaporating glacial acetic acid to dryness for next batch reaction, slightly cooling, adding 1000L water into the kettle, dropwise adding 800L 30% liquid caustic soda, stirring to dissolve completely, adjusting the pH to 4.1 by using 10% dilute sulfuric acid, adding 3kg of active carbon, heating to 80 ℃, stirring, decoloring for 20 minutes, filter-pressing, heating the filtrate to 92 ℃, performing acid precipitation by using 10% dilute sulfuric acid until the pH is less than 0.5, cooling to room temperature, spin-drying, rinsing by using water on a centrifuge, spin-drying, and drying to obtain 260kg of 1,2, 3-hemimellitic acid product with the content of 99.7%, the melting range of 190 and 192 ℃, and the yield of 99%.
Example 3
1650kg of glacial acetic acid (the amount is 11 times of the mass of 1,2, 3-hemimellitene), 150kg of 1,2, 3-hemimellitene, 3.3kg of cobalt acetate as a catalyst, 3.3kg of manganese acetate, 3.3kg of potassium bromide (the amounts are 2.2% of the mass of 1,2, 3-hemimellitene), 2.3kg of zirconium acetate as a cocatalyst (the amount is 1.5% of the mass of 1,2, 3-hemimellitene), 2.4kg of didodecyldimethylammonium bromide as a phase transfer catalyst (the amount is 1.6% of the mass of 1,2, 3-hemimellitene), 0.5% of water content after uniform stirring, 47kg of acetic anhydride, heating to reflux (solvent reflux, reaction start, 117 ℃ at the beginning, and temperature lowering to 112 ℃ along with the progress of the reaction), and (3) introducing oxygen by refluxing for 10 cubic meters per hour, testing that the water content is 2.6 percent after 11 hours, supplementing 243kg of acetic anhydride by calculation, testing that the water content is 0.9 percent after 15 hours, supplementing 84kg of acetic anhydride by calculation, controlling that no raw material 1,2, 3-hemimellitene exists in 19-hour sampling, and completely converting the raw material 1,2, 3-hemimellitene into 1,2, 3-hemimellitene.
Stopping introducing oxygen, cooling to 60 ℃, transferring to a 3000L distillation kettle, evaporating glacial acetic acid to dryness for next batch reaction, slightly cooling, adding 1000L water into the kettle, dropwise adding 800L 30% liquid caustic soda, stirring to dissolve completely, adjusting the pH value to 4.1 by using 10% dilute sulfuric acid, adding 3kg of active carbon, heating to 80 ℃, stirring, decoloring for 20 minutes, filter-pressing, heating the filtrate to 92 ℃, performing acid precipitation by using 10% dilute sulfuric acid until the pH value is less than 0.5, cooling to room temperature, spin-drying, rinsing by using water on a centrifugal machine, spin-drying, and drying to obtain 261kg of 1,2, 3-hemimellitic acid product with the content of 99.8%, the melting range of 190 and 192 ℃ and the yield of 99.4%.
Comparative example 1
Comparative example 1 is intended to show that the yield of 1,2, 3-hemimellitic acid product is low when zirconium acetate is not used as a co-catalyst.
140kg of 1,2, 3-hemimellitic acid product having a 97% content, a melting range of 188-.
Comparative example 2
Comparative example 2 is intended to show that the yield of 1,2, 3-hemimellitic acid product is low when didodecyldimethylammonium bromide is not used as a phase transfer catalyst.
100kg of 1,2, 3-hemimellitic acid product having a 96% content, a melting range of 186-.
Comparative example 3
Comparative example 3 is intended to illustrate the low yield of 1,2, 3-hemimellitic acid product when using the existing catalyst.
160kg of 1,2, 3-hemimellitic acid product was obtained in the same manner as in example 1 except that zirconium acetate as a co-catalyst and didodecyldimethylammonium bromide as a phase transfer catalyst were not used and 3kg of trihydroxyisocyanuric acid (THICA) was used in place of potassium bromide (i.e., THICA, cobalt acetate and manganese acetate were used as catalysts in comparative example 3), and the yield was 61%, the content was 98%, the melting range was 189-.
The yields of 1,2, 3-hemimellitic acid product in the above examples and comparative examples are shown in the following table 1:
TABLE 1
From the data of examples 1-3 above, it can be seen that the yield of 1,2, 3-hemimellitic 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 the 1,2, 3-hemimellitic acid product.
In addition, as can be seen from the comparison of the data of comparative examples 1 and 2 with example 1, the method of the present invention uses a cocatalyst and a phase transfer catalyst which both work well for the reaction, and the yield of hemimellitic acid is very low in comparative example 1 in which zirconium acetate is not used as the cocatalyst and in comparative example 2, 1,2, 3-hemimellitic acid in which didodecyldimethylammonium bromide is not used as the phase transfer catalyst.
In addition, the yield of 1,2, 3-hemimellitic acid product is low when the conventional catalyst is used.
Claims (8)
1. A method for preparing 1,2, 3-hemimellitic acid, comprising: taking 1,2, 3-hemimellitene as a starting material, glacial acetic acid as a solvent, cobalt acetate, manganese acetate and potassium bromide as catalysts, zirconium acetate as a cocatalyst, and adding didodecyldimethylammonium bromide as a phase transfer catalyst to perform an oxidation reaction in an oxygen atmosphere;
the chemical reaction principle is as follows:
2. the method according to claim 1, wherein the solvent is used in an amount of 9 to 11 times by mass of the 1,2, 3-hemimellitene,
in the catalyst, the dosage of cobalt acetate, manganese acetate and potassium bromide is 2-2.5% of the mass of the 1,2, 3-hemimellitene,
the dosage of the cocatalyst is 1.3-1.6% of the mass of the 1,2, 3-hemimellitene,
the dosage of the phase transfer catalyst is 1.3-1.6% of the mass of the 1,2, 3-hemimellitene.
3. The method according to claim 1, wherein the oxygen is introduced in an amount of 8 to 10 cubic/hour.
4. The method of claim 1, wherein the method further comprises: during the reaction, testing the water content in the reaction system, and adding acetic anhydride to absorb the water generated by the reaction and promote the reaction.
5. The method as claimed in claim 4, wherein the water content in the reaction system is not more than 3%, and the amount of the acetic anhydride to be added is calculated according to the measured water content and added in the midway.
6. The method as claimed in claim 4, wherein the reaction is carried out at 112-117 ℃ for 17-20 hours.
7. The method of claim 1, wherein the method further comprises: carrying out post-treatment on the crude feed liquid of the 1,2, 3-hemimellitic acid obtained by the reaction, wherein the post-treatment comprises the following steps: and (3) refining the crude feed liquid, and decoloring by using a decoloring agent to obtain a 1,2, 3-hemimellitic acid product.
8. The method of claim 7, wherein the decolorizing agents include: activated carbon.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210305055.8A CN114539047B (en) | 2022-03-25 | 2022-03-25 | Preparation method of 1,2, 3-benzene tricarboxylic acid |
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| CN202210305055.8A CN114539047B (en) | 2022-03-25 | 2022-03-25 | Preparation method of 1,2, 3-benzene tricarboxylic acid |
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| CN114539047A true CN114539047A (en) | 2022-05-27 |
| CN114539047B CN114539047B (en) | 2024-01-30 |
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