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Reaction method for preparing corresponding lactone, hydroxy acid and dicarboxylic acid through cyclic ketone oxidation

A technology of dicarboxylic acid and hydroxy acid, which is applied in the preparation of carboxylic acid by oxidation, chemical instruments and methods, preparation of organic compounds, etc., can solve the problems of poor atom economy, low selectivity, easy to fly temperature, etc. The effect of stable control, increasing hydrogen peroxide concentration and improving selectivity

Active Publication Date: 2013-10-30
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, the industrialized production of ε-caprolactone mainly adopts the Baeyer-Villiger oxidation process of cyclohexanone and peroxycarboxylic acid, but peroxyacid oxidants also have relatively large disadvantages: (1) after the reaction, a large amount of organic Carboxylic acid (salt) waste has a greater impact on the environment, and it is more difficult to recycle or process; (2) the separation and purification of reaction products are more difficult, the selectivity is low, the atom economy is poor, and it does not meet the basic principles of green chemistry; (3) ) Organic peroxyacids need to use high-concentration hydrogen peroxide in the production process, which is unstable in nature, high in production costs, and dangerous in transportation, storage and operation, thus limiting its application in industrial production
However, this kind of reaction has a large heat release. If the heat is not obtained in time, it is easy to overheat and increase the ineffective decomposition of hydrogen peroxide. In order to effectively control the reaction temperature and improve the utilization efficiency of hydrogen peroxide, the development of chemical reaction engineering technology must be paid attention to.
The present invention is based on nano-beta molecular sieve and its metal-modified nano-beta molecular sieve as a catalyst, and optimizes the best process conditions by selecting new and efficient reaction engineering technology, which is beneficial to realize industrialized large-scale production, and there is no literature report on related research

Method used

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  • Reaction method for preparing corresponding lactone, hydroxy acid and dicarboxylic acid through cyclic ketone oxidation
  • Reaction method for preparing corresponding lactone, hydroxy acid and dicarboxylic acid through cyclic ketone oxidation
  • Reaction method for preparing corresponding lactone, hydroxy acid and dicarboxylic acid through cyclic ketone oxidation

Examples

Experimental program
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Effect test

Embodiment 1

[0036] This example illustrates the direct catalytic oxidation of cyclohexanone to produce ε-caprolactone, 6-hydroxycaproic acid and adipic acid.

[0037] The reactor is a slurry bed reactor, the catalyst used is nano-beta molecular sieve, and the particle diameter distribution of the catalyst is 1-200 μm; the reaction raw materials are 30% hydrogen peroxide and more than 99.9% cyclohexanone; the entrainer is ethyl acetate. Prepare the ethyl acetate slurry with a catalyst concentration of 5% in the catalyst storage tank, and fully stir and disperse it for later use. Use ethyl acetate to test run the device under the set conditions. After the device is stable, mix the catalyst slurry, hydrogen peroxide The raw material cyclohexanone is added to the reaction section in the tower. The absolute pressure is 0.1MPa, the reaction setting temperature is 75°C, the azeotropic temperature in the reactor is 74°C, the molar ratio of cyclohexanone to ethyl acetate in the reaction section is...

Embodiment 2

[0039] This example illustrates the direct catalytic oxidation of cyclohexanone to produce ε-caprolactone, 6-hydroxycaproic acid and adipic acid.

[0040] Weigh 20g of nano-beta molecular sieve and put it into 50ml of dilute sulfuric acid solution with a concentration of 25%, stir continuously at 70°C for 2 hours, filter, dry and roast in a muffle furnace at 550°C for 3 hours, and take it out to get an alumina content of 2.3 wt% of acid-eluted aluminum nano-beta molecular sieves. Weigh 1.36g of zinc chloride solid and fully dissolve it in 10ml of water, add 10g of the prepared acid-eluted aluminum nano-beta molecular sieve and impregnate it in equal volume at room temperature for 6 hours, then put it in an oven at 110°C for 3 hours, and then place it at 550 ℃ in a muffle furnace for 3 hours, and the ZnO / acid-eluted aluminum nano-beta molecular sieve with a zinc oxide content of 8.14 wt% was obtained after taking it out.

[0041]The test was operated according to the diagram, ...

Embodiment 3

[0043] This example illustrates the catalytic oxidation of cyclopentanone to δ-valerolactone, 5-hydroxyvaleric acid and glutaric acid. Weigh 30g of nano-beta molecular sieve and put it into 50ml of HCl solution with a concentration of 15%, stir continuously at 90°C for 2 hours, filter, dry and roast in a muffle furnace at 550°C for 3 hours, and take it out to get an alumina content of 2.9wt % of acid-eluted aluminum nano-beta molecular sieves. Weigh 3.55g of tin tetrachloride pentahydrate solid and fully dissolve it in 15ml of water, add 20g of the prepared acid-eluted aluminum nano-beta molecular sieve, impregnate in equal volume at room temperature for 6 hours, and then put it in an oven at 110°C for 3 hours. Then bake in a muffle furnace at 550°C for 3 hours, and take it out to obtain SnO with a zinc oxide content of 7.51wt%. 2 / Acid-eluted aluminum nano-beta molecular sieve.

[0044] The test was operated according to Figure 1, the reactor was a slurry bed reactor, and t...

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Abstract

The invention relates to a reaction method for preparing corresponding lactone, hydroxy acid and dicarboxylic acid through cyclic ketone oxidation. The reaction method is characterized by comprising the following steps of: enabling reaction materials which include cyclic ketone, hydrogen peroxide, an entrainer and water to contact under the condition of oxidation reaction in the presence of a catalyst to obtain a product; and continuously adding and extracting the reaction materials and the product in a reaction device, wherein the entrainer generates azeotropism with the water, an azeotrope formed under a reaction condition is continuously removed and separated, the reaction materials and the entrainer are recycled, and the catalyst is a nano beta molecular sieve and / or a metal modified nano beta molecular sieve.

Description

technical field [0001] The invention relates to a reaction method for preparing corresponding lactones, hydroxy acids and dibasic carboxylic acids by oxidizing cyclic ketones. Background technique [0002] ε-caprolactone, colorless oily liquid, with aromatic odor, density 1.0693, boiling point 98-99°C, melting point about 5°C, refractive index 1.4611, soluble in water, ethanol, benzene, insoluble in petroleum ether, heat changes into dimers or polymer polyesters. ε-caprolactone has the advantages of low viscosity, easy processing, and low VOC content. Used as oligomers and denaturants in processes such as , can improve functionalities such as toughness, low temperature characteristics and reactivity. [0003] ε-caprolactone was successfully synthesized in the laboratory as early as the 1930s. The synthesis methods of ε-caprolactone that appeared successively thereafter mainly include Baeyer-Villiger oxidation method; 1,6-hexanediol catalytic dehydrogenation method; 6-hydr...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D313/04C07D309/30C07C59/01C07C51/31C07C55/14C07C55/12C07C51/285
CPCY02P20/584
Inventor 林民夏长久朱斌龙立华彭欣欣舒兴田邹飞艳汝迎春
Owner CHINA PETROLEUM & CHEM CORP
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