CN115850143A - A method for removing light components from tert-butyl hydroperoxide - Google Patents

Abstract

The invention discloses a method for removing light components from tert-butyl hydroperoxide. High-purity tert-butyl peroxide can be obtained from the bottom of the tower by distillation. The present invention aims at the shortcomings of existing tert-butyl hydroperoxide preparation process that adopts acid-base washing to separate light components, which has complicated operation and produces a large amount of waste water, etc., and obtains more than 98% tert-butyl hydroperoxide product through rectification. After the tert-butyl hydroperoxide mixture containing di-tert-butyl peroxide, tert-butanol and water enters the rectification and separation, the light component mixture of di-tert-butyl peroxide, tert-butanol and water is obtained from the top of the tower , The liquid phase product in the tower kettle is a tert-butyl hydroperoxide product, and the separation process is environmentally friendly and efficient.

Description

A method for removing light components from tert-butyl hydroperoxide

technical field

The invention belongs to the technical field of tert-butyl hydroperoxide, in particular to a method for removing light components from tert-butyl hydroperoxide.

Background technique

Tert-butyl hydroperoxide (TBHP), also known as tert-butanol peroxide, is an important organic peroxide, mainly used as an initiator of polymerization, polymerization (such as polyvinyl chloride, polyacrylic emulsion polymerization unit Initiator for unsaturated polyester, emulsion polymerization, natural raw rubber vulcanization, paint industry, etc. It is also widely used as a raw material for the synthesis of other organic peroxides.

Tert-butyl hydroperoxide is the most basic kind of tert-butyl peroxide, and it is also the basic raw material for the synthesis of other organic peroxides. The common synthesis methods of tert-butyl hydroperoxide include: tert-butanol hydrogen peroxide method, isobutylene hydrogen peroxide method and Grignard reagent synthesis.

Among them, the tert-butanol oxidation method is the main production method in my country at present, and its production process is as follows:

First, tert-butanol was esterified with sulfuric acid to generate tert-butyl hydrogen sulfate, and then hydrogen peroxide was used to oxidize tert-butyl hydrogen sulfate to generate TBHP. The reaction process is as follows:

( CH ₃ ) ₃ C-OH+H ₂ SO ₄ →( CH ₃ ) ₃ C-OSO ₃ H + H ₂ O

( CH ₃ ) ₃ C-OSO ₃ H+H ₂ O ₂ →( CH ₃ ) ₃ CO-OH+ H ₂ SO ₄

Total reaction formula:

( CH ₃ ) ₃ C-OH+H ₂ O ₂ →( CH ₃ ) ₃ CO-OH+H ₂ O

Main side reaction generates di-tert-butyl hydroperoxide:

2( CH ₃ ) ₃ C-OH+H ₂ O ₂ →( CH ₃ ) ₃ COOC( CH ₃ ) ₃ +2H ₂ O

The production device investment cost of the method is low, the reaction is easy to control, and the operation is simple and convenient, and the reaction by-product di-tert-butyl peroxide is also an organic peroxide with a wide range of uses. The existing process uses liquid caustic soda synthesis, separates the by-product di-tert-butyl hydroperoxide, and then acidifies it with sulfuric acid. This process is complicated to operate, and a large amount of waste water is generated during the conversion process, which limits the economic scale of the product. Therefore, it is necessary to develop a simple, environmentally friendly and efficient separation method.

Contents of the invention

In order to improve the deficiencies in the prior art, the invention provides a method for removing light components from tert-butyl hydroperoxide, especially the method for the treatment of tert-butyl alcohol peroxidation reaction liquid, after the method is processed The tert-butyl hydroperoxide can reach more than 98%, and it can be sold directly as a product or as a solution.

The purpose of the present invention is achieved through the following technical solutions:

A method for removing light components from tert-butyl hydroperoxide, the tert-butyl hydroperoxide mixture containing di-tert-butyl peroxide, tert-butanol and water is removed from the bottom of the tower by rectification Obtain highly pure tert-butyl peroxide; comprise the steps:

After di-tert-butyl peroxide, tert-butyl hydroperoxide mixture of tert-butanol and water enters the rectification column from the feed port for separation, the gas phase product at the top of the tower is condensed by a condenser to obtain di-tert-butyl peroxide The mixture of tert-butanol and water enters the reflux tank, part of which returns to the top of the tower, and the other part is extracted as light components of di-tert-butyl peroxide, tert-butanol and water; the liquid phase product of the tower It is tert-butyl hydroperoxide, a part of which is returned to the tower kettle through a reboiler, and another part is extracted from the outlet of the rectifying tower as a tert-butyl hydroperoxide product.

The position of the feed plate where the feed inlet is located is the 6th to the 12th block. The temperature of the tower kettle is 38.3-69°C, and the pressure of the tower kettle is 4-16KPa. The molar ratio of the reflux is 2-6:1.

Beneficial effects of the present invention: the treated tert-butyl hydroperoxide can reach more than 98%, and it can be directly sold as a product or prepared as a solution. Through experimental research, we found that the mixture of tert-butyl alcohol-di-tert-butyl hydroperoxide-water can be obtained at the top of the column after rectification, so the method of rectification will contain di-tert-butyl hydroperoxide, tert-butyl alcohol, The so-called light components of water and tert-butyl hydroperoxide are effectively separated, and the tert-butyl hydroperoxide is obtained from the bottom of the tower, and the light components of di-tert-butyl hydroperoxide, tert-butanol and water are obtained from the top of the tower. The method has the characteristics of good separation effect, easy large-scale industrialization, no waste water, simple required equipment, etc., and has good prospects for large-scale industrial application.

Detailed ways

The present invention will be further described in detail through specific embodiments below.

Example 1

Put the mixed material containing 80% tert-butyl hydroperoxide, 10% di-tert-butyl hydroperoxide, 2% tert-butanol, 7% water and about 1% hydrogen peroxide into the theoretical plate number 50 at 1000kg/kg. In the rectification tower on the feeder plate 6, the vapor phase at the top of the tower enters the reflux tank after being condensed by the condenser. Part of the material in the reflux tank is refluxed into the top of the rectification tower through the reflux pump, and the other part is extracted to obtain a product containing water, di-tert-butyl Mixed light components of hydrogen peroxide, tert-butanol, hydrogen peroxide. Part of the liquid in the bottom of the tower is heated by the reboiler and returned to the rectification tower, and the other part is taken out as a product and enters the product intermediate tank. The specific operating conditions are as follows:

The feed temperature is 30°C, the operating pressure of the tower is 6KPa, the temperature of the tower kettle is 49°C, and the reflux molar ratio is 2:1

Tower kettle obtains tert-butyl hydroperoxide product concentration and is 98.5%, and the recovery rate of basis is 99.6% by weight.

Example 2

Put the mixed material containing 85% tert-butyl hydroperoxide, 5% di-tert-butyl hydroperoxide, 2% tert-butanol, 7% water and about 1% hydrogen peroxide into the theoretical plate number 30 at 1000kg/kg. In the rectification tower on the material plate 6, after rectification, the gas phase at the top of the tower is condensed by the condenser and then enters the reflux tank. Part of the material in the reflux tank is refluxed into the top of the rectification tower through the reflux pump, and the other part is extracted to obtain Mixed light components of butyl hydroperoxide, tert-butanol, hydrogen peroxide. Part of the liquid in the bottom of the tower is heated by the reboiler and returned to the rectification tower, and the other part is taken out as a product and enters the product intermediate tank. The operating conditions are as follows:

The feed temperature is 18°C, the operating pressure of the tower kettle is 4KPa, the tower kettle temperature is 41°C, and the molar ratio of the reflux ratio is 4:1;

Tower kettle obtains tert-butyl hydroperoxide product concentration and is 98.8%, and the recovery rate of basis is 99.5% by weight.

Example 3

Put the mixed material containing 90% tert-butyl hydroperoxide, 4% di-tert-butyl hydroperoxide, 3% tert-butanol, 12% water and about 1% hydrogen peroxide into the theoretical plate number 22 at 1000kg/kg. In the rectification tower with the material plate 12, after rectification, the gas phase at the top of the tower is condensed by the condenser and then enters the reflux tank. Part of the material in the reflux tank is refluxed into the top of the rectification tower through the reflux pump, and the other part is extracted to obtain Mixed light components of butyl hydroperoxide, tert-butanol, hydrogen peroxide. Part of the liquid in the bottom of the tower is heated by the reboiler and returned to the rectification tower, and the other part is taken out as a product and enters the product intermediate tank. The specific operating conditions are as follows:

The feed temperature is 25°C, the operating pressure of the tower bottom is 15KPa, the temperature of the tower bottom is 69°C, and the reflux molar ratio is 6:1.

Tower kettle obtains tert-butyl hydroperoxide product concentration and is 98.6%, and the recovery rate of basis is 99.4% by weight.

By adopting the above method, the pickling and alkaline washing process in the production process of tert-butyl hydroperoxide can be omitted, thereby reducing pollution. The production cost is reduced, and it is suitable for large-scale production.

Claims (4)

1. a method for removing light component from tert-butyl hydroperoxide, is characterized in that: will contain di-tert-butyl peroxide, the tert-butyl hydroperoxide mixed solution of tert-butyl alcohol and water is passed through The rectification method obtains high-purity tert-butyl peroxide from the bottom of the tower; comprises the following steps: After di-tert-butyl peroxide, tert-butyl hydroperoxide mixture of tert-butanol and water enters the rectification column from the feed port for separation, the gas phase product at the top of the tower is condensed by a condenser to obtain di-tert-butyl peroxide The mixture of tert-butanol and water enters the reflux tank, part of which returns to the top of the tower, and the other part is extracted as light components of di-tert-butyl peroxide, tert-butanol and water; the liquid phase product of the tower It is tert-butyl hydroperoxide, a part of which is returned to the tower kettle through a reboiler, and another part is extracted from the outlet of the rectifying tower as a tert-butyl hydroperoxide product. 2. the method for removing light components from tert-butyl hydroperoxide as claimed in claim 1, is characterized in that: the theoretical plate number of described rectifying tower is 20～50, and feed inlet is located The position of the feeding plate is the 6th to 12th. 3. the method for removing light component from tert-butyl hydroperoxide as claimed in claim 1, is characterized in that: described tower still temperature 38.3～69 ℃, tower still pressure is 4～16KPa. 4. the method for removing light component from tert-butyl hydroperoxide as claimed in claim 1, is characterized in that: the mol ratio of described reflux is 2～6:1.