Method of catalytic oxidization of cyclic ketone by using tin supported molecular sieve

A technology of catalytic oxidation and all-silicon molecular sieve, which is applied in the direction of molecular sieve catalysts, chemical instruments and methods, physical/chemical process catalysts, etc., can solve the problems that do not conform to the basic principles of green chemistry, the properties of heteropolyacid catalysts are unstable, and purification is difficult. , achieve catalytic oxidation activity and catalytic activity stability, high catalytic oxidation activity and activity stability, and overcome the complex production process

Active Publication Date: 2015-02-25
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] 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, heteropolyacid catalysts have shortcomings such as unstable properties, small specific surface area, easy deactivation, difficult recovery and short service life, so they have not been widely promoted at present.

Method used

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  • Method of catalytic oxidization of cyclic ketone by using tin supported molecular sieve
  • Method of catalytic oxidization of cyclic ketone by using tin supported molecular sieve
  • Method of catalytic oxidization of cyclic ketone by using tin supported molecular sieve

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] Weigh 2.3 grams of tin-loaded all-silicon molecular sieve SnO 2 / S-1(SnO 2 The massfraction is 2.3wt%) catalyzer is contained in the 100ml three-necked flask, then add magnetic stirrer, 19.63 gram cyclohexanone, 3.6 gram water and 46ml concentration successively and be 30% hydrogen peroxide, now cyclohexanone and peroxide The molar ratio of hydrogen is 1:2. The three-necked flask is placed on a temperature-controlled magnetic stirrer, and the upper part of the three-necked flask is condensed and refluxed with a condenser, and the magnetic stirrer and heating device are started to start the reaction. The reaction temperature was controlled at about 80°C. After 8 hours of reaction, the conversion rate of cyclohexanone was 40.65%, the selectivity of generating ε-caprolactone was 26.45%, the selectivity of 6-hydroxycaproic acid was 31.68%, and the Acid selectivity was 24.12%.

Embodiment 2

[0044] Weigh 2.44 grams of tin-loaded all-silicon molecular sieve SnO 2 / S-1 catalyst (SnO 2 The mass fraction is 1.9wt%) is installed in the 100ml three-neck flask, then add magnetic stirrer, 19.63 grams of cyclohexanone, 23 grams of acetone and 23ml concentration successively and be 30% hydrogen peroxide, now cyclohexanone and hydrogen peroxide The molar ratio is 1:1. The three-necked flask is placed on a temperature-controlled magnetic stirrer, and the upper part of the three-necked flask is condensed and refluxed with a condenser, and the magnetic stirrer and heating device are started to start the reaction. The reaction temperature was controlled at about 60°C. After 3 hours of reaction, the conversion rate of cyclohexanone was 37.82%, the selectivity of ε-caprolactone was 89.45%, the selectivity of 6-hydroxycaproic acid was 3.29%, and the selectivity of adipic acid was 37.82%. The selectivity is 0.41%.

Embodiment 3

[0046] Weigh 2.65 grams of tin-loaded all-silicon molecular sieve SnO 2 / S-1 catalyst (SnO 2 The mass fraction is 3.3wt%) to be installed in the 100ml three-necked flask, then add magnetic stirrer, 19.63 gram cyclohexanone, 18 gram dioxane and 46ml concentration successively and be 30% hydrogen peroxide, now cyclohexanone and The molar ratio of hydrogen peroxide is 1:2. The three-necked flask is placed on a temperature-controlled magnetic stirrer, and the upper part of the three-necked flask is condensed and refluxed with a condenser, and the magnetic stirrer and heating device are started to start the reaction. The reaction temperature was controlled at about 93°C. After 6 hours of reaction, the conversion rate of cyclohexanone was 89.57%, the selectivity of ε-caprolactone was 95.45%, the selectivity of 6-hydroxycaproic acid was 2.37%, and the selectivity of adipic acid The selectivity is 1.18%.

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Abstract

The invention provides a method of catalytic oxidization of cyclic ketone by using a tin supported molecular sieve. The method is characterized in that cyclic ketone, a solvent and hydrogen peroxide react in the presence of a catalyst at the temperature of 5-200 DEG C at the reaction pressure of 0.1-3.0MPa in a molar ratio of cyclic ketone to solvent to hydrogen peroxide being 1: (0-50): (0.2-20), and products are collected, wherein the catalyst is a tin supported full-silica molecular sieve (SnO2 / S-1).

Description

technical field [0001] The invention relates to a method for catalytically oxidizing cyclic ketones, in particular to a method for oxidizing cyclic ketones with hydrogen peroxide in the presence of a catalyst. Background technique [0002] ε-caprolactone has the advantages of low viscosity, easy processing, and low VOC content. It is used as oligomer and denaturant in the process, which can improve the toughness, low temperature characteristics and reactivity and other functionalities; in terms of coatings, it is used as an improvement in solvents and latex coatings for automotive primers, surface coatings and various building materials. It can improve the toughness of the coating film, improve the low-temperature characteristics, reactivity, and increase the crosslinking density; in terms of adhesives, it can be used to improve the bonding properties of hot-melt adhesives and solvent-based adhesives; in resin modification On the one hand, it can be used to improve softness...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/00C07D313/04C07C51/245C07C55/14C07C53/126
Inventor 夏长久朱斌林民龙立华邹飞艳舒兴田汝迎春
Owner CHINA PETROLEUM & CHEM CORP
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