RU2801047C1 - Method for producing sec-butylbenzene hydroperoxide - Google Patents

Abstract

FIELD: chemical industry.

SUBSTANCE: invention relates to a method for producing sec-butylbenzene hydroperoxide. The proposed method consists in the liquid-phase oxidation of sec-butylbenzene with air oxygen at atmospheric pressure and a process temperature of 140-145°C for 30-60 min in the presence of a catalyst. As a catalyst, a mixture of N-hydroxyphthalimide and its derivative - potassium phthalimide is used, in the ratio of N-hydroxyphthalimide: potassium phthalimide 1:1, in a total amount of 2-4% of the mass.

EFFECT: reducing the reaction time to obtain a high content of hydroperoxide in the oxidation products and high selectivity of its formation.

1 cl, 4 ex

Description

The present invention relates to the petrochemical industry and can be used in the process of co-production of phenol and methyl ethyl ketone by the hydroperoxide method, which consists in the synthesis of sec-butylbenzene hydroperoxide subjected to acid decomposition into target products [G.D. Kharlampovich, Yu.V. Churkin. Phenols. - M.: Chemistry, 1974; S.V. Zavgorodny. Hydroperoxides of alkylaromatic hydrocarbons and their derivatives. - Advances in Chemistry, 1961].

Phenol and methyl ethyl ketone are valuable products of organic and petrochemical synthesis and are widely used in various branches of the chemical industry. So, phenol is used in the production of plastics and synthetic fibers, pesticides, dyes, and various explosives. In the oil refining industry, phenol, due to its high selectivity and efficiency in the removal of resinous substances, is widely used to purify oils in various process units. Recently, phenol has been actively used in the pharmaceutical industry as a preservative and antioxidant in the manufacture of medicines [B.D. Kruzhalov, B.I. Golovanenko. Joint production of phenol and acetone. - M: Gostoptekhizdat, 1963; Yu.A. Moskvichev, A.V. Tarasov, A.E. Meshechkin. History of chemical technology: a textbook for students of higher educational institutions studying in the direction of "Chemical technology". - Yaroslavl, 2015]. The main area of application of methyl ethyl ketone, due to its high dissolving power, is the production of paints and varnishes and polymeric materials and coatings, adhesives, printing inks. In fine organic synthesis, methyl ethyl ketone is known as a feedstock for the production of a number of compounds, for example, ethylacrylic, methylcrotonic acids, as well as 2,3-butadione, which are monomers in the production of organic glass [E.G. Zhizhin, V.F. Odyakov, A.L. Balashov, K.I. Matveev. Development of a new technology for the catalytic synthesis of methyl ethyl ketone by the oxidation of n-butylenes. - Catalysis in industry. 2005].

The main method for obtaining sec-butylbenzene hydroperoxide is liquid-phase aerobic oxidation of sec-butylbenzene. It is known from the literature that sec-butylbenzene can be oxidized to hydroperoxide in the presence of N-hydroxyphthalimide as a catalyst with a selectivity above 90% and a hydroperoxide accumulation rate of about 8-10% per hour. Thus, by oxidizing sec-butylbenzene with atmospheric oxygen at a temperature of 150°C, it is possible to achieve the formation of sec-butylbenzene hydroperoxide with a content of 39.8 wt% in the oxidate. [B.C. Kabanova. Development of an effective method for producing methyl ethyl ketone based on available petrochemical raw materials. Materials of the XXXII Mendeleev School-Conference of Young Scientists (May 11-13, 2022, Moscow) - M .: Pero Publishing House, 2022; Abstract of the dissertation for the degree of Doctor of Chemical Sciences Kurganova E.A. Liquid-phase oxidation of alkyl- and cyclohexylaromatic hydrocarbons to hydroperoxides in the presence of phthalimide catalysts - Moscow, 2013].

However, these works do not specifically disclose the amount of catalyst and the duration of the process in relation to the oxidation reaction of sec-butylbenzene.

Closest to the proposed method for producing sec-butylbenzene hydroperoxide is the liquid-phase oxidation of a technical mixture of isopropylbenzene and sec-butylbenzene with atmospheric oxygen at a temperature of 110-130°C in the absence of a catalyst. The methodology for carrying out the process of oxidation of sec-butylbenzene in the presence of isopropylbenzene is due to the fact that as a result of the process of oxidation of isopropylbenzene, its hydroperoxide-active initiator of chain reactions is formed, which can increase the rate of oxidation of sec-butylbenzene. However, despite this fact, the rate of oxidation of sec-butylbenzene in such a process is low (about 1.7% w/h); the conversion of the original hydrocarbon is about 15% with the selectivity of the formation of sec-butylbenzene hydroperoxide 64-70% (the content of sec-butylbenzene hydroperoxide is 13-14 wt%, during the contact time of 6 h) [Zakoshansky V.M. Phenol and acetone: Analysis of technologies, kinetics and mechanism of the main reactions. - St. Petersburg: KHIMIZDAT, 2009].

During oxidation under these conditions, the oxidation rate is not high enough from a technological point of view and up to 40% of by-products are formed.

To increase the speed of the process, catalysts are used - manganese resinate, sodium stearate and alkaline additives such as NaOH and CaO. However, in the case of using such compounds, additional purification of the oxidation products from inorganic spent catalysts is required.

The objective of the present invention is to eliminate the above disadvantages: increasing the rate of oxidation of sec-butylbenzene, increasing the selectivity of the formation of sec-butylbenzene hydroperoxide, as well as reducing the content of by-products in the oxidate.

This problem is solved using a method for producing sec-butylbenzene hydroperoxide by liquid-phase oxidation of sec-butylbenzene without adding isopropylbenzene with air oxygen at atmospheric pressure at a temperature of 140-145 ° C in the presence of a mixture of N-hydroxyphthalimide and its derivative, potassium phthalimide, as a catalyst, in the ratio N -hydroxyphthalimide: potassium phthalimide 1:1 in a total amount of 2-4% of the mass, for 30-60 minutes.

Under these conditions, it is possible to achieve a conversion of sec-butylbenzene up to 30% with a selectivity for the formation of sec-butylbenzene hydroperoxide up to 95%.

Characteristic features of the oxidation process under such conditions are: the use of N-hydroxyphthalimide and its derivative, potassium phthalimide, as a catalyst, which has a lower cost, availability and relatively simple technology for its production.

The present invention is illustrated by the following examples:

Example 1

In a glass reactor with a capacity of 10 cm ³ was loaded with 3 cm ³ sec-butylbenzene and a mixture of N-hydroxyphthalimide, in the amount of 1% of the mass, from the loading of the hydrocarbon, and potassium phthalimide, in the same amount; served oxygen at atmospheric pressure, at a temperature of 140°C for 60 minutes with continuous stirring.

The content of sec-butylbenzene hydroperoxide was 22 wt%, with a selectivity of its formation of 91%. The oxidate was analyzed for hydroperoxide content by iodometric analysis.

Example 2

In a glass reactor with a capacity of 10 cm ³ was loaded with 3 cm ³ sec-butylbenzene and a mixture of N-hydroxyphthalimide, in the amount of 1% of the mass, from the loading of the hydrocarbon, and potassium phthalimide, in the same amount; served oxygen at atmospheric pressure, at a temperature of 145°C for 30 minutes with continuous stirring.

The content of sec-butylbenzene hydroperoxide was 17 wt%, with a selectivity of its formation of 92%. The oxidate was analyzed for the content of hydroperoxide by the iodometric method of analysis.

Example 3

In a glass reactor with a capacity of 10 cm ³ was loaded with 3 cm ³ of sec-butylbenzene and a mixture of N-hydroxyphthalimide, in the amount of 2% of the mass, from the loading of the hydrocarbon, and potassium phthalimide, in the same amount; served oxygen at atmospheric pressure, at a temperature of 145°C for 30 minutes with continuous stirring.

The content of sec-butylbenzene hydroperoxide was 17% by weight, with a selectivity of its formation of 92%. The oxidate was analyzed for hydroperoxide content by iodometric analysis.

Example 4

In a glass reactor with a capacity of 10 cm ³ was loaded with 3 cm ³ sec-butylbenzene and a mixture of N-hydroxyphthalimide, in the amount of 1% of the mass, from the loading of the hydrocarbon, and potassium phthalimide, in the same amount; served oxygen at atmospheric pressure, at a temperature of 145°C for 60 minutes with continuous stirring.

The content of sec-butylbenzene hydroperoxide was 26 wt%, with a selectivity of its formation of 90%. The oxidate was analyzed for hydroperoxide content by iodometric analysis.

Claims (1)

A method for producing sec-butylbenzene hydroperoxide by liquid-phase oxidation of sec-butylbenzene with air oxygen at atmospheric pressure, characterized in that the process is carried out in the presence of a catalyst: a mixture of N-hydroxyphthalimide and its derivative - potassium phthalimide, in the ratio of N-hydroxyphthalimide : potassium phthalimide 1: 1, in a total amount of 2-4% wt., at a temperature of 140-145°C for 30-60 minutes.