CN114605238A - Preparation method of p-diacetylbenzene - Google Patents
Preparation method of p-diacetylbenzene Download PDFInfo
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- CN114605238A CN114605238A CN202011430261.9A CN202011430261A CN114605238A CN 114605238 A CN114605238 A CN 114605238A CN 202011430261 A CN202011430261 A CN 202011430261A CN 114605238 A CN114605238 A CN 114605238A
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- diethylbenzene
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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Abstract
The invention provides a preparation method of p-diacetylbenzene, which takes p-diacetylbenzene as a raw material, air as an oxidant and one or two of cobalt naphthenate and manganese naphthenate as a catalyst to prepare the p-diacetylbenzene. The method adopts air as the oxidant, is cheap and easy to obtain, and uses a large amount of residual nitrogen after the reaction as a part of tail gas, and can quickly remove reaction heat, thereby easily realizing low-energy-consumption continuous production; the method does not use a solvent, so that the reaction product is easy to separate; the catalyst adopted by the invention has the advantages of simple structure, small dosage and high activity, and the reaction time is shortened; the preparation method of p-diacetylbenzene has wide industrial application prospect.
Description
Technical Field
The invention relates to a preparation method of p-diacetylbenzene, in particular to a method for preparing p-diacetylbenzene by liquid-phase air oxidation of p-diacetylbenzene.
Background
P-diacetylbenzene is an important organic synthesis intermediate and is widely applied to the fields of synthetic medicines, pesticides, dyes and the like. The method for preparing p-diacetylbenzene by directly oxidizing p-diethylbenzene has wide market prospect and great economic value because the p-diacetylbenzene mainly depends on import and no large-scale production device is available in China.
Patent CN107286005A discloses a method for preparing a catalyst from p-diethylbenzene and Fe (NO)3)3 •9H2O、NiCl2•6H2O、MnSO4•H2O、Co(CH3COO)2•4H2O、Cu(NO3)2•3H2O、CuSO4•5H2O、Co(NO3)2•6H2The method for preparing p-diethylbenzene comprises the steps of taking one or more soluble metal salts in O as a catalyst, taking the molar ratio of the catalyst to p-diethylbenzene as 0.05-0.5: 1, taking any one of oxygen, hydrogen peroxide or tert-butyl hydroperoxide as an oxidant, taking any one or two of potassium bromide, potassium chloride or sodium iodide as an auxiliary agent, taking one of glacial acetic acid, DMF or acetonitrile as a solvent, and carrying out homogeneous oxidation reaction for 2-6 h at the reaction temperature of 50-100 ℃ to prepare p-diethylbenzene. The method uses the solvent, and a solvent separation process is necessary in the follow-up process, so that the production cost is increased; and the halide is used as an auxiliary agent, which causes the problems of equipment corrosion and the like. The patent application with the publication number of CN101759541B discloses a method for preparing p-diacetylbenzene by using p-diethylbenzene as a raw material, selecting a metalloporphyrin biomimetic catalyst and oxygen as an oxidant under the conditions of normal pressure and no solvent, and performing an oxidation reaction at an initiation temperature of 140-170 ℃ and a reaction temperature of 80-130 ℃. The method adopts metalloporphyrin catalyst, and is expensive; the method has the advantages of optimal reaction time of 16-18 h, overlong reaction time and high energy consumption.
In order to solve the above problems, we have always sought an ideal technical solution.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a method for preparing p-diacetylbenzene, which has the advantages of short reaction time, low cost, simple process and no subsequent solvent treatment link.
A process for preparing p-diacetylbenzene from p-diacetylbenzene, air as oxidant and one or two of cobalt naphthenate and manganese naphthenate as catalyst. Air is used as an oxidant in the reaction, the price is low, a large amount of nitrogen left after the reaction is used as tail gas, a large amount of reaction heat can be taken away, the forward reaction process is promoted, the product conversion rate is improved, and continuous production is realized.
As a further improvement of the technical scheme, in order to promote the forward reaction process, reduce the reaction time and control the equipment cost, the reaction pressure of the method is 0.1-1.0 MPa.
As a further improvement of the technical scheme, in order to enable the reaction to be sufficient and enable tail gas to take away reaction heat, the flow speed of oxidant air in the method is 100-500L/h.
As a further improvement of the technical scheme, in order to ensure that the reaction is sufficient, the method is used for reacting under the stirring condition, and the stirring speed is 200-800 r/min.
As a further improvement of the technical proposal, in order to improve the catalytic effect, the molar ratio of the catalyst to the p-diethylbenzene is (0.001-0.05): 1.
As a further improvement of the technical proposal, in order to improve the catalytic effect, the molar ratio of the catalyst to the p-diethylbenzene is (0.005-0.03): 1.
As a further improvement of the technical scheme, in order to improve the reaction rate, improve the conversion rate of p-diethylbenzene and reduce energy consumption, the reaction temperature of the method is 60-160 ℃, and the reaction time is 1-6 h.
As a further improvement of the technical scheme, in order to reduce energy consumption and reduce the generation of byproducts, the reaction time of the method is 3-5 h.
As a further improvement of the technical scheme, in order to improve the conversion rate of the p-diethylbenzene, the reaction temperature of the method is 90-130 ℃.
Compared with the prior art for preparing p-diacetylbenzene by oxidizing p-diethylbenzene, the method has the beneficial effects that:
firstly, the catalyst used in the invention has the advantages of solubility in raw materials, low price, high catalytic activity and reaction time reduction.
Air is used as an oxidant, so that the air is cheap and easy to obtain, and the cost is saved; and the tail gas of the reaction contains a large amount of nitrogen, so that the reaction heat can be quickly removed, and the continuous production with low energy consumption is easy to realize.
The reaction time of the invention is 1-6 h, and the invention has the advantages of short reaction time and low energy consumption.
And fourthly, the method does not use a solvent, adopts direct oxidation of p-diethylbenzene, reduces the subsequent solvent separation link compared with the process using the solvent, and can greatly reduce energy consumption and production cost.
Detailed Description
The technical solution of the present invention is further described in detail by the following embodiments.
The preparation method of each example adopts a 1000ml stainless steel high-pressure reaction kettle, a magnetic stirrer and an automatic temperature controller.
Example 1
406.7g of p-diethylbenzene with the purity of 99.0 percent and cobalt naphthenate are added into a reaction kettle, the molar ratio of the cobalt naphthenate to the p-diethylbenzene is 0.001:1, air is introduced for reaction at the reaction temperature of 60 ℃ and the reaction pressure of 0.1Mpa, wherein the flow rate of the air is 100L/h, and the rotating speed of a stirrer is 200 r/min. After 6 hours of reaction, 445.5g of a product is obtained, wherein the mass fraction of p-diacetylbenzene in the reaction product is 14.3 percent, the conversion rate of the p-diacetylbenzene is 27.5 percent, and the selectivity of the p-diacetylbenzene is 47.4 percent, which are measured by a gas chromatograph.
Example 2
406.7g of p-diethylbenzene with the purity of 99.0 percent and cobalt naphthenate are added into a reaction kettle, the molar ratio of the cobalt naphthenate to the p-diethylbenzene is 0.01:1, air is introduced for reaction at the reaction temperature of 110 ℃ and the reaction pressure of 0.6Mpa, the flow rate of the air is 240L/h, the rotating speed of a stirrer is 600r/min, and 540.1g of product is prepared after reaction for 3h, wherein the mass fraction of the p-diethylbenzene in the reaction product is measured by a gas chromatograph to be 38.2 percent, the conversion rate of the p-diethylbenzene is 85.6 percent, and the selectivity of the p-diethylbenzene is 49.8 percent.
Example 3
406.7g of p-diethylbenzene with the purity of 99.0 percent and cobalt naphthenate are added into a reaction kettle, the molar ratio of the cobalt naphthenate to the p-diethylbenzene is 0.05:1, air is introduced for reaction at the reaction temperature of 130 ℃ and the reaction pressure of 0.8Mpa, the flow rate of the air is 360L/h, the rotating speed of a stirrer is 700r/min, and a product 612.3g is prepared after the reaction is carried out for 2h, wherein the mass fraction of the p-diethylbenzene in the reaction product is 44.3 percent, the conversion rate of the p-diethylbenzene is 95.8 percent, and the selectivity of the p-diethylbenzene is 58.3 percent through gas chromatograph.
Example 4
406.7g of p-diethylbenzene with the purity of 99.0 percent and cobalt naphthenate are added into a reaction kettle, the molar ratio of the cobalt naphthenate to the p-diethylbenzene is 0.03:1, and air is introduced for reaction at the reaction temperature of 160 ℃ and the reaction pressure of 1 Mpa. The flow rate of air is 500L/h, the rotating speed of the stirrer is 800r/min, 569.6g of product is obtained after 1h of reaction, wherein the mass fraction of p-diethylbenzene in the reaction product is 30.1%, the conversion rate of p-diethylbenzene is 97.1%, and the selectivity of p-diethylbenzene is 36.2% by gas chromatograph.
Example 5
406.7g of p-diethylbenzene with the purity of 99.0 percent and manganese naphthenate are added into a reaction kettle, the molar ratio of the manganese naphthenate to the p-diethylbenzene is 0.001:1, and air is introduced for reaction at the reaction temperature of 60 ℃ and the reaction pressure of 0.1 Mpa. The flow rate of air is 100L/h, the rotation speed of the stirrer is 200r/min, 436.2g of product is obtained after 6 hours of reaction, wherein the mass fraction of p-diethylbenzene in the reaction product is 12.4%, the conversion rate of p-diethylbenzene is 21.2%, and the selectivity of p-diethylbenzene is 52.3% by gas chromatograph.
Example 6
406.7g of p-diethylbenzene with the purity of 99.0 percent and manganese naphthenate are added into a reaction kettle, the molar ratio of the manganese naphthenate to the p-diethylbenzene is 0.01:1, air is introduced for reaction at the reaction temperature of 100 ℃ and the reaction pressure of 0.5Mpa, the flow rate of the air is 300L/h, the rotation speed of a stirrer is 200r/min, and 469.8g of product is prepared after 4h of reaction, wherein a gas chromatograph is used for measuring the mass fraction of p-diacetylbenzene in the reaction product to be 21.2 percent, the conversion rate of the p-diethylbenzene to be 35.7 percent and the selectivity of the p-diacetylbenzene to be 57.1 percent.
Example 7
406.7g of p-diethylbenzene with the purity of 99.0 percent and manganese naphthenate are added into a reaction kettle, the molar ratio of the manganese naphthenate to the p-diethylbenzene is 0.05:1, air is introduced for reaction at the reaction temperature of 140 ℃ and the reaction pressure of 0.9Mpa, the flow rate of the air is 400L/h, the rotation speed of a stirrer is 600r/min, and 528.4g of products are obtained after 2h of reaction, wherein a gas chromatograph is used for measuring the mass fraction of p-diacetylbenzene in the reaction products to be 24.1 percent, the conversion rate of the p-diethylbenzene to be 40.2 percent and the selectivity of the p-diacetylbenzene to be 64.8 percent.
Example 8
406.7g of p-diethylbenzene with the purity of 99.0 percent and manganese naphthenate are added into a reaction kettle, the molar ratio of the manganese naphthenate to the p-diethylbenzene is 0.02:1, air is introduced for reaction at the reaction temperature of 160 ℃ and the reaction pressure of 1Mpa, the flow rate of the air is 500L/h, the rotating speed of a stirrer is 800r/min, and 525.7g of a product is prepared after the reaction is carried out for 1h, wherein the mass fraction of the p-diethylbenzene in the reaction product is 23.9 percent, the conversion rate of the p-diethylbenzene is 73.3 percent, and the selectivity of the p-diethylbenzene is 35.4 percent through gas chromatograph.
Example 9
406.7g of p-diethylbenzene with the purity of 99.0 percent, cobalt naphthenate and manganese naphthenate are added into a reaction kettle, the molar ratio of the cobalt naphthenate to the manganese naphthenate is 2:1, the molar ratio of the sum of the cobalt naphthenate and the manganese naphthenate to the p-diethylbenzene is 0.005:1, air is introduced for reaction at the reaction temperature of 60 ℃ and the reaction pressure of 0.1Mpa, the flow rate of the air is 100L/h, the rotating speed of a stirrer is 200r/min, 448.3g of a product is obtained after the reaction is carried out for 6h, wherein the mass fraction of the p-diethylbenzene in the reaction product is 14.3 percent, the conversion rate of the p-diethylbenzene is 26.1 percent, and the selectivity of the p-diethylbenzene is 50.2 percent through gas chromatograph determination.
Example 10
406.7g of p-diethylbenzene with the purity of 99.0 percent, cobalt naphthenate and manganese naphthenate are added into a reaction kettle, the molar ratio of the cobalt naphthenate to the manganese naphthenate is 1:1, the molar ratio of the sum of the cobalt naphthenate and the manganese naphthenate to the p-diethylbenzene is 0.01:1, air is introduced for reaction at the reaction temperature of 90 ℃ and the reaction pressure of 0.4Mpa, the flow rate of the air is 300L/h, the rotating speed of a stirrer is 600r/min, 500.7g of a product is obtained after the reaction is carried out for 3h, wherein the mass fraction of the p-diethylbenzene in the reaction product is 30.5 percent, the conversion rate of the p-diethylbenzene is 55.4 percent, and the selectivity of the p-diethylbenzene is 56.6 percent through gas chromatograph determination.
Example 11
406.7g of p-diethylbenzene with the purity of 99.0 percent, cobalt naphthenate and manganese naphthenate are added into a reaction kettle, the molar ratio of the cobalt naphthenate to the manganese naphthenate is 1:2, the molar ratio of the sum of the cobalt naphthenate and the manganese naphthenate to the p-diethylbenzene is 0.05:1, air is introduced for reaction at the reaction temperature of 120 ℃ and the reaction pressure of 0.7Mpa, the flow rate of the air is 250L/h, the rotating speed of a stirrer is 500r/min, 588.1g of a product is obtained after the reaction is carried out for 4h, wherein the mass fraction of the p-diethylbenzene in the reaction product is 40.7 percent, the conversion rate of the p-diethylbenzene is 77.3 percent, and the selectivity of the p-diethylbenzene is 63.7 percent through a gas chromatograph.
Example 12
406.7g of p-diethylbenzene with the purity of 99.0 percent, cobalt naphthenate and manganese naphthenate are added into a reaction kettle, the molar ratio of the cobalt naphthenate to the manganese naphthenate is 1:1, the molar ratio of the sum of the cobalt naphthenate and the manganese naphthenate to the p-diethylbenzene is 0.04:1, air is introduced for reaction at the reaction temperature of 160 ℃ and the reaction pressure of 1Mpa, the flow rate of the air is 500L/h, the rotating speed of a stirrer is 800r/min, and 587.2g of a product is obtained after the reaction is carried out for 1h, wherein the mass fraction of the p-diethylbenzene in the reaction product is 33.4 percent, the conversion rate of the p-diethylbenzene is 96.4 percent, and the selectivity of the p-diethylbenzene is 41.8 percent through gas chromatograph determination.
Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and not to limit the same; although the present invention has been described in detail with reference to preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; without departing from the spirit of the present invention, it is intended to cover all aspects of the invention as defined by the appended claims.
Claims (9)
1. The preparation method of p-diacetylbenzene is characterized by taking p-diacetylbenzene as a raw material, air as an oxidant and one or two of cobalt naphthenate and manganese naphthenate as a catalyst to prepare the p-diacetylbenzene.
2. The process for producing p-diacetophenone according to claim 1, wherein the reaction pressure is from 0.1 to 1.0 MPa.
3. The method of producing p-diacetoxybenzene as claimed in claim 1 or 2, wherein the flow rate of the oxidizing agent air is 100 to 500L/h.
4. The method for preparing p-diacetoxybenzene as claimed in claim 1, wherein the reaction is carried out under stirring at a rate of 200 to 800 r/min.
5. The process according to claim 1, wherein the molar ratio of the catalyst to p-diethylbenzene is (0.001-0.05): 1.
6. The process of claim 5, wherein the molar ratio of catalyst to p-diethylbenzene is (0.005-0.03): 1.
7. The method of claim 1, wherein the reaction temperature is 60-160 ℃ and the reaction time is 1-6 hours.
8. The method of claim 7, wherein the reaction time is 3 to 5 hours.
9. The method for producing p-diacetoxybenzene as claimed in claim 7, wherein the reaction temperature is 90 to 130 ℃.
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| CN202011430261.9A CN114605238A (en) | 2020-12-09 | 2020-12-09 | Preparation method of p-diacetylbenzene |
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