CN112521266B - Process for producing adipic acid - Google Patents
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- 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
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
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Abstract
The invention relates to a method for producing adipic acid, which mainly solves the problems that in the prior art, a plurality of carboxylic acid byproducts, such as succinic acid, glutaric acid, 6-hydroxycaproic acid and the like, are generated in the reaction process of preparing adipic acid by directly oxidizing cyclohexane, and after the reaction is finished, the carboxylic acid byproducts are difficult to separate from adipic acid products and are coprecipitated along with the crystallization of the adipic acid products, so that the purity of the adipic acid products is reduced, and the production of high-purity adipic acid is difficult to realize. A production method using adipic acid, comprising reacting cyclohexane with an oxygen-containing gas in the presence of a catalyst selected from at least one of fourth-period transition metal salts, an initiator, a solvent, and an additive to produce adipic acid; the initiator is selected from at least one of small molecular organic aldehyde or ketone, the solvent is selected from at least one of polar protic solvents, and the additive is a technical scheme of organic acid with pKa less than or equal to 1, so that the problem is solved well, and the method can be used for production of adipic acid.
Description
Technical Field
The invention relates to a method for producing adipic acid, in particular to a method for producing adipic acid by directly oxidizing cyclohexane.
Background
Adipic acid (adipic acid), also known as adipic acid, is an important organic diacid, and is an important raw material for preparing polyurethane and nylon 66. The international application field of adipic acid in nylon 66 is over 70 percent, and the international application field of adipic acid in polyurethane is 78 percent. At present, the world has four methods for producing adipic acid, namely a phenol method, a cyclohexane method, a cyclohexene method, a butadiene method and the like. Before the fifty years, the production of adipic acid mainly uses phenol as a raw material, and the production of adipic acid by using a phenol method is a more classical method. But the phenol resource is limited, the price is high, the product cost is high, and the phenol is basically eliminated at present. The modern industrial production mainly adopts a cyclohexane method, the yield of which accounts for about 93 percent of the total yield, and the method mainly comprises two steps of adipic acid synthesis. The first step of oxidation of cyclohexane to give cyclohexanol and cyclohexanone (KA oil), followed by separation of the reaction mixture, recycling of unreacted cyclohexane, and the second step of oxidation of KA oil to adipic acid with nitric acid. The method has the advantages that: the process is mature, the process is dominant in the production of adipic acid, byproducts are mainly succinic acid and glutaric acid, the separation is easy, and the product is relatively pure. Has the following defects: in the process of synthesizing KA oil, the conversion per pass is low, the conversion rate is generally 5% -12%, and a large amount of strong acid and strong alkali solution is needed, so that equipment is corroded, and the environment is polluted; in the second step, in the process of preparing adipic acid by oxidizing KA oil, the used oxidant is nitric acid, 68 percent of nitric acid is consumed for producing 1t of adipic acid product, the corrosion to equipment is serious, and a large amount of nitrogen oxide compounds which seriously pollute the environment can be generated.
In order to solve the problem, researchers explore a more environment-friendly and simple process route for synthesizing adipic acid by taking cyclohexane as a raw material and air or oxygen as an oxidant, wherein most researches adopt biomimetic catalysis and free radical oxidation modes to convert cyclohexane into adipic acid with high conversion rate and high selectivity
For example, chinese invention patents CN 1247501C (title of the invention: cyclohexane catalytic oxidation process), CN 1218922C (title of the invention: method for preparing adipic acid by air oxidation of hexacyclic carbon ring compound) and CN 1231449C (title of the invention: method for preparing adipic acid by biomimetic catalytic oxygen oxidation of cyclohexane) disclose methods for preparing adipic acid by air oxidation of cyclohexane using metalloporphyrin as a catalyst.
For example, the document Organic Process Research&Development 1998,2,255-260 (article title: direct Conversion of cyclic hexane in o additive Acid with Molecular Oxygen catalyst by N-Hydroxyphthamide composite with Mn (acac) 2 and Co(OAc) 2 ) In Ishii et al, cyclohexane is directly oxidized to adipic acid with oxygen using a free radical catalyst, N-hydroxyphthalimide (NHPI for short), and a small amount of a transition metal promoter. The reaction was carried out in acetic acid solvent with NHPI (10 mol%) and manganese acetylacetonate (1 mol%) as catalysts at 100 ℃ for 20 hours, with a cyclohexane conversion of 73% and an adipic acid yield of 53%.
The cases realize the high-efficiency conversion of cyclohexane to adipic acid, but because side reactions are more in the oxidation process, a plurality of formed byproducts and catalysts cannot be effectively separated from adipic acid, and the byproducts and the catalysts can be coprecipitated with adipic acid in the crystallization process of adipic acid after the reaction is finished, so that the quality of adipic acid products is influenced, and the production of high-quality adipic acid is difficult.
Disclosure of Invention
The invention aims to solve the technical problem that in the prior art, a plurality of carboxylic acid byproducts, such as succinic acid, glutaric acid, 6-hydroxycaproic acid and the like, are generated in the reaction process of preparing adipic acid by directly oxidizing cyclohexane, and after the reaction is finished, the carboxylic acid byproducts are difficult to separate from adipic acid products and are coprecipitated along with the crystallization of the adipic acid product, so that the purity of the adipic acid product is reduced, and the production of high-purity adipic acid is difficult to realize.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a process for producing adipic acid comprising reacting cyclohexane with an oxygen-containing gas in the presence of a catalyst selected from at least one of fourth period transition metal salts, an initiator, a solvent, and an additive to produce adipic acid; the initiator is selected from at least one of small molecular organic aldehyde or ketone, the solvent is selected from at least one of polar protic solvents, and the additive is an organic acid with pKa less than or equal to 1.
By adding the additive, the generation of carboxylic acid by-products is inhibited, the selectivity of adipic acid is improved, and higher purity adipic acid products are obtained when the products are separated by crystallization.
In the above technical solution, when the acid as the additive is a dibasic acid or an acid having more than two elements, pKa refers to pKa of first-order ionization, that is, pKa1.
In the above technical solution, preferably, the fourth phase transition metal includes at least one selected from copper, cobalt, and manganese.
In the above-described aspect, the transition metal salt preferably includes at least one selected from the group consisting of a carboxylate, an organic complex, and a halide.
In the above-mentioned embodiment, the aldehyde is preferably an aldehyde having 10 or less carbon atoms in the molecule, for example, but not limited to acetaldehyde or the like.
In the above aspect, the ketone is preferably a ketone having 10 or less carbon atoms in the molecule. Such as but not limited to acetone, cyclohexanone, and the like.
In the above-mentioned aspect, the polar protic solvent is preferably an organic polar protic solvent having 6 or less carbon atoms in a molecule. For example, but not limited to, the number of carbons in the polar protic solvent molecule may be 6, 5, 4, 2, and so forth.
In the above technical scheme, it is preferable that the polar solvent includes a neutral compound, and the neutral compound is preferably a tertiary alcohol, such as but not limited to tertiary butanol, as a non-limiting example.
In the above technical solution, the polar solvent preferably includes an acidic compound, and more preferably, the pKa of the acidic compound is greater than or equal to 3. By way of non-limiting examples of specific compounds, there may be mentioned, but are not limited to, glacial acetic acid, propionic acid and the like.
In the above-mentioned embodiment, the additive is preferably an organic acid having 10 or less carbon atoms in its molecule, for example, an organic acid having 10, 9, 8, 7, 6, 5, 4, 3, or 2 carbon atoms. Non-limiting classes of such organic acids are exemplified by, but not limited to, organic sulfonic acids, halogenated acetic acids. The additive is p-toluenesulfonic acid, trifluoromethanesulfonic acid and trifluoroacetic acid.
In the above technical solutions, the molar ratio of the catalyst to the additive is preferably 0.001 to 1, for example, but not limited to, the molar ratio of the catalyst to the additive is 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, and the like.
In the above technical solution, the molar ratio of the initiator to the additive is preferably 0.01 to 10, for example, but not limited to, the molar ratio of the initiator to the additive is 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, and the like.
In the above-mentioned embodiment, the oxygen-containing gas is preferably selected from gases having an oxygen content of 5 to 100% by volume, for example, but not limited to, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, etc. in the oxygen-containing gas. Thus, the oxygen-containing gas may be embodied in, but not limited to, air, pure oxygen, oxygen-enriched or oxygen-depleted.
The pressures stated in the present invention are gauge pressures.
The selectivity of the product adipic acid is detected by liquid phase HPLC. And (3) electromagnetically stirring and dissolving a solid-liquid mixed product obtained by the reaction of preparing adipic acid by oxidizing cyclohexane by using water-methanol =90 (V/V), and filtering and diluting the solution into a high-performance liquid phase for detection. Chromatographic analysis conditions: the chromatography column model is ZORBAX SAX 4.6mm X250mm 5 μm, and the mobile phase is methanol: 50mmol/L KH 2 PO 4 Aqueous solution =5, column temperature 25 ℃, flow rate 1.0mL/min, sample size 20 μ L, detection wavelength 210nm.
The present invention will be described in detail below with reference to examples and comparative examples.
Detailed Description
[ example 1]
10mol of glacial acetic acid, 2mol of cyclohexane and 0.001mol of CoAc 2 、0.001mol MnAc 2 、0.001mol CuAc 2 Adding 0.05mol of cyclohexanone and 0.05mol of p-toluenesulfonic acid into a 2-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 110 ℃, continuously introducing air at 5 liters/min, controlling the pressure in the kettle to be kept at 1.5MPa all the time, reacting for 3 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion 15.2% (cyclohexane conversion = (molar amount of cyclohexane reacted/total molar amount of cyclohexane) × 100%), adipic acid selectivity 88.6% (adipic acid selectivity = (molar amount of adipic acid formed by reaction/molar amount of cyclohexane consumed) × 100%).
And slowly cooling the reaction solution after the reaction to 5 ℃, keeping cooling for 1h, and filtering to obtain 35.8g of crude adipic acid product with the purity of 99.8 percent.
For comparison, the main experimental conditions and experimental results are shown in table 1.
[ example 2]
10mol of glacial acetic acid, 2mol of cyclohexane and 0.001mol of CoAc 2 、0.001mol MnAc 2 、0.001mol CuAc 2 Adding 0.05mol of cyclohexanone and 0.05mol of trifluoromethanesulfonic acid into a 2-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 110 ℃, continuously introducing air at 5 liters/min, controlling the pressure in the kettle to be kept at 1.5MPa all the time, reacting for 3 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion 16.4% and adipic acid selectivity 87.1%.
And slowly cooling the reaction solution after the reaction to 5 ℃, keeping cooling for 1h, and filtering to obtain 36.5g of crude adipic acid product with the purity of 99.6 percent.
For comparison, the main experimental conditions and experimental results are shown in table 1.
[ example 3]
10mol of propionic acid, 2mol of cyclohexane and 0.001mol of CoAc 2 、0.001mol MnAc 2 、0.001mol CuAc 2 Adding 0.05mol of cyclohexanone and 0.05mol of trifluoroacetic acid into a 2-step pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 110 ℃, continuously introducing air at 5 liters/min, controlling the pressure in the kettle to be kept at 1.5MPa all the time, reacting for 3 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion 14.8% and adipic acid selectivity 87.5%.
And slowly cooling the reaction solution after the reaction to 5 ℃, keeping cooling for 1h, and filtering to obtain 32.3g of crude adipic acid product with the purity of 99.5 percent.
For comparison, the main experimental conditions and experimental results are listed in table 1.
[ example 4]
10mol of glacial acetic acid, 2mol of cyclohexane and 0.001mol of acetylCobalt acetone Co (acac) 2 0.001mol manganese acetylacetonate Mn (acac) 2 、0.001mol CuCl 2 Adding 0.05mol of acetone and 0.05mol of trifluoroacetic acid into a 2-step pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 110 ℃, continuously introducing air at 5 liters/min, controlling the pressure in the kettle to be kept at 1.5MPa all the time, reacting for 3 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 15.5% and adipic acid selectivity was 86.8%.
And slowly cooling the reaction solution after the reaction to 5 ℃, keeping cooling for 1h, and filtering to obtain 33.6g of crude adipic acid product with the purity of 99.6 percent.
For comparison, the main experimental conditions and experimental results are shown in table 1.
[ example 5]
10mol of tert-butanol, 2mol of cyclohexane and 0.001mol of CoAc 2 、0.001mol MnAc 2 、0.001mol CuAc 2 Adding 0.05mol of cyclohexanone and 0.05mol of trifluoroacetic acid into a 2-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 110 ℃, continuously introducing air at 5 liters/min, controlling the pressure in the kettle to be kept at 1.5MPa all the time, reacting for 3 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 13.9% and adipic acid selectivity was 87.2%.
And slowly cooling the reaction solution after the reaction to 5 ℃, keeping cooling for 1h, and filtering to obtain 32.1g of crude adipic acid product with the purity of 99.5 percent.
For comparison, the main experimental conditions and experimental results are shown in table 1.
[ example 6]
10mol of tert-amyl alcohol, 2mol of cyclohexane and 0.001mol of CoAc 2 、0.001mol MnAc 2 、0.001mol CuAc 2 Adding 0.05mol of cyclohexanone and 0.05mol of trifluoroacetic acid into a 2-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 110 ℃, and keeping the temperature at 5 litersContinuously introducing air per minute, controlling the pressure in the kettle to be kept at 1.5MPa all the time, cooling to room temperature after reacting for 3 hours, taking out the reaction mixture for analysis, and obtaining an analysis result: cyclohexane conversion was 13.6% and adipic acid selectivity was 86.3%.
And slowly cooling the reaction solution after the reaction to 5 ℃, keeping cooling for 1h, and filtering to obtain 31.8g of crude adipic acid product with the purity of 99.4 percent.
For comparison, the main experimental conditions and experimental results are listed in table 1.
[ example 7]
10mol of glacial acetic acid, 2mol of cyclohexane and 0.000033mol of CoAc 2 、0.000033mol MnAc 2 、0.000033mol CuAc 2 Adding 0.1mol of cyclohexanone and 0.1mol of trifluoroacetic acid into a 2-step pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 110 ℃, continuously introducing air at 5 liters/min, controlling the pressure in the kettle to be kept at 1.5MPa all the time, reacting for 3 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion 10.6%, adipic acid selectivity 84.8%.
And slowly cooling the reacted reaction solution to 5 ℃, keeping cooling for 1h, and filtering to obtain 25.2g of crude adipic acid product with the purity of 99.4%.
For comparison, the main experimental conditions and experimental results are shown in table 1.
[ example 8]
10mol of glacial acetic acid, 2mol of cyclohexane and 0.02mol of CoAc 2 、0.015mol MnAc 2 、0.015mol CuAc 2 Adding 0.05mol of cyclohexanone and 0.05mol of trifluoroacetic acid into a 2-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 110 ℃, continuously introducing air at 5 liters/min, controlling the pressure in the kettle to be kept at 1.5MPa all the time, reacting for 3 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 18.9% and adipic acid selectivity was 88.2%.
And slowly cooling the reaction solution after the reaction to 5 ℃, keeping cooling for 1h, and filtering to obtain 42.7g of crude adipic acid product with the purity of 99.7 percent.
For comparison, the main experimental conditions and experimental results are shown in table 1.
[ example 9]
10mol of glacial acetic acid, 2mol of cyclohexane and 0.0033mol of CoAc 2 、0.0033mol MnAc 2 、0.0033mol CuAc 2 Adding 0.01mol of cyclohexanone and 1mol of trifluoroacetic acid into a 2-step pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 110 ℃, continuously introducing air at 5 liters/min, controlling the pressure in the kettle to be kept at 1.5MPa all the time, reacting for 3 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion 13.5%, adipic acid selectivity 86.9%.
And slowly cooling the reaction solution after the reaction to 5 ℃, keeping cooling for 1h, and filtering to obtain 28.6g of crude adipic acid product with the purity of 99.6 percent.
For comparison, the main experimental conditions and experimental results are shown in table 1.
[ example 10]
10mol of glacial acetic acid, 2mol of cyclohexane and 0.001mol of CoAc 2 、0.001mol MnAc 2 、0.001mol CuAc 2 Adding 0.05mol of cyclohexanone and 0.05mol of trifluoroacetic acid into a 2-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealing and stirring, heating to 100 ℃, continuously introducing air at 5 liters/min, controlling the pressure in the kettle to be kept at 1.0MPa all the time, reacting for 3 hours, cooling to room temperature, taking out a reaction mixture for analysis, and analyzing the result: cyclohexane conversion was 12.8% and adipic acid selectivity was 85.6%.
And slowly cooling the reaction solution after the reaction to 5 ℃, keeping cooling for 1h, and filtering to obtain 29.8g of crude adipic acid product with the purity of 99.4 percent.
For comparison, the main experimental conditions and experimental results are shown in table 1.
Comparative example 1
10mol of glacial acetic acid and 2mol of cyclohexaneAlkane, 0.001mol of CoAc 2 、0.001mol MnAc 2 、0.001mol CuAc 2 And 0.05mol of cyclohexanone is added into a 2-step pressure-rising reaction kettle (provided with a reflux condensing device which is communicated with the atmosphere through a pressure-backup valve), sealed and stirred, heated to 110 ℃, continuously introduced with air at 5 l/min, the pressure in the kettle is controlled to be kept at 1.5MPa all the time, after the reaction is carried out for 3 hours, the kettle is cooled to the room temperature, and the reaction mixture is taken out for analysis, so that the analysis result is as follows: cyclohexane conversion 13.6% and adipic acid selectivity 83.5%.
And slowly cooling the reaction solution after the reaction to 5 ℃, keeping cooling for 1h, and filtering to obtain 27.9g of crude adipic acid product with the purity of 98.2%.
For comparison, the main experimental conditions and experimental results are shown in table 1.
Comparative example 2
10mol of glacial acetic acid, 2mol of cyclohexane and 0.001mol of CoAc 2 、0.001mol MnAc 2 、0.001mol CuAc 2 0.05mol of NHPI (N-hydroxyphthalimide) and 0.05mol of propionic acid are added into a 2-liter pressure-rising reaction kettle (provided with a reflux condensing device which is communicated with the atmosphere through a pressure-backup valve), sealed and stirred, heated to 110 ℃, continuously introduced with air at 5 liters/min, the pressure in the kettle is controlled to be kept at 1.5MPa all the time, and after 3 hours of reaction, the reaction mixture is cooled to the room temperature, taken out for analysis, and the analysis result is: cyclohexane conversion 14.3% and adipic acid selectivity 82.0%.
And slowly cooling the reaction solution after the reaction to 5 ℃, keeping cooling for 1h, and filtering to obtain 29.4g of crude adipic acid product with the purity of 97.6 percent.
For comparison, the main experimental conditions and experimental results are listed in table 1.
Comparative example 3
10mol of tert-butanol, 2mol of cyclohexane and 0.001mol of CoAc 2 、0.001mol MnAc 2 、0.001mol CuAc 2 0.05mol of cyclohexanone and 0.05mol of concentrated sulfuric acid are added into a 2-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealed and stirred, heated to 110 ℃, and continuously introduced into the reaction kettle at the speed of 5 liters/minuteAnd (3) controlling the pressure in the kettle to be kept at 1.5MPa all the time, cooling to room temperature after reacting for 3 hours, taking out the reaction mixture for analysis, and obtaining an analysis result: cyclohexane conversion was 16.9% and adipic acid selectivity was 78.4%.
And slowly cooling the reaction solution after the reaction to 5 ℃, keeping cooling for 1h, and filtering to obtain 36.4g of crude adipic acid product with the purity of 96.5 percent.
For comparison, the main experimental conditions and experimental results are shown in table 1.
Comparative example 4
10mol of glacial acetic acid, 2mol of cyclohexane and 0.0015mol of CoAc 2 、0.0015mol MnAc 2 0.05mol cyclohexanone and 0.05mol trifluoroacetic acid are added into a 2-liter pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealed and stirred, heated to 110 ℃, continuously introduced with air at 5 liters/min, the pressure in the kettle is controlled to be kept at 1.5MPa all the time, after reacting for 3 hours, cooled to room temperature, and the reaction mixture is taken out for analysis, and the analysis result is as follows: cyclohexane conversion 8.7% and adipic acid selectivity 81.0%.
And slowly cooling the reaction solution after the reaction to 5 ℃, keeping cooling for 1h, and filtering to obtain 15.8g of crude adipic acid product with the purity of 94.5%.
For comparison, the main experimental conditions and experimental results are shown in table 1.
Comparative example 5
10mol of glacial acetic acid, 2mol of cyclohexane and 0.001mol of CoAc 2 、0.001mol MnAc 2 、0.001mol CuAc 2 And 0.05mol of trifluoroacetic acid is added into a 2-step pressure-rising reaction kettle (provided with a reflux condensing device communicated with the atmosphere through a pressure-backup valve), sealed and stirred, heated to 110 ℃, continuously introduced with air at 5 liters/min, the pressure in the kettle is controlled to be kept at 1.5MPa all the time, after reacting for 3 hours, cooled to room temperature, and the reaction mixture is taken out for analysis, and the analysis result is as follows: cyclohexane conversion was 5.3% and adipic acid selectivity was 78.8%.
And slowly cooling the reaction solution after the reaction to 5 ℃, keeping cooling for 1h, and filtering to obtain 7.5g of crude adipic acid product with the purity of 95.8%.
For comparison, the main experimental conditions and experimental results are shown in table 1.
TABLE 1
Note: mn (acac) 2 Is manganese acetylacetonate, co (acac) 2 Cobalt acetylacetonate and NHPI is N-hydroxyphthalimide.
Claims (9)
1. A process for producing adipic acid comprising reacting cyclohexane with an oxygen-containing gas in the presence of a catalyst, an initiator, a solvent and an additive to produce adipic acid, said catalyst comprising a copper salt, a cobalt salt and a manganese salt; the initiator is selected from at least one of small molecular organic aldehyde or ketone, the solvent is selected from at least one of polar protic solvents, and the additive is an organic acid with pKa less than or equal to 1.
2. The method as set forth in claim 1, wherein the salt is at least one selected from the group consisting of a carboxylate, an organic complex and a halide.
3. The method according to claim 1, wherein the aldehyde is an aldehyde having 10 or less carbon atoms in the molecule; and/or the ketone is a ketone having 10 or less carbon atoms in the molecule.
4. The method according to claim 1, wherein the polar protic solvent is an organic polar protic solvent having 6 or less carbon atoms in a molecule.
5. The method as set forth in claim 1, characterized in that said polar solvent comprises an acidic compound.
6. The method according to claim 5, wherein the acidic compound has a pKa of 3 or more.
7. The method according to claim 1, wherein the additive is an organic acid having 10 or less carbon atoms in the molecule.
8. The process as claimed in claim 1, characterized in that the molar ratio of catalyst to additive is from 0.001 to 1; and/or the molar ratio of the initiator to the additive is 0.01 to 10.
9. The method as claimed in claim 1, wherein the oxygen-containing gas is selected from gases having an oxygen content of 5 to 100% by volume.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB956780A (en) * | 1960-08-22 | 1964-04-29 | Halcon International Inc | Improved production of adipic acid |
| CN1339021A (en) * | 1999-02-04 | 2002-03-06 | Rpc公司 | Oxidation of hydrocarbons to acids in the presence of fluoro compounds |
| CN101239899A (en) * | 2008-03-10 | 2008-08-13 | 华南理工大学 | Method for preparing adipic acid by using cyclohexane catalytic oxidation one-step method |
| JP2009184950A (en) * | 2008-02-05 | 2009-08-20 | Nagasaki Univ | Method for producing aliphatic dicarboxylic acid compound |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB956780A (en) * | 1960-08-22 | 1964-04-29 | Halcon International Inc | Improved production of adipic acid |
| CN1339021A (en) * | 1999-02-04 | 2002-03-06 | Rpc公司 | Oxidation of hydrocarbons to acids in the presence of fluoro compounds |
| JP2009184950A (en) * | 2008-02-05 | 2009-08-20 | Nagasaki Univ | Method for producing aliphatic dicarboxylic acid compound |
| CN101239899A (en) * | 2008-03-10 | 2008-08-13 | 华南理工大学 | Method for preparing adipic acid by using cyclohexane catalytic oxidation one-step method |
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| CN112521266A (en) | 2021-03-19 |
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