JP4207407B2 - Process for producing diisopropylbenzene hydroperoxides - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing diisopropylbenzene hydroperoxides. More specifically, the present invention relates to a method for producing diisopropylbenzene hydroperoxides by oxidizing diisopropylbenzene, wherein an active ingredient in an oxidation exhaust gas generated in this oxidation step is brought into contact with a low volatile substance. The present invention relates to a process for producing diisopropylbenzene hydroperoxides which are efficiently recovered and thus have economically superior characteristics. In addition, said active ingredient means a raw material and / or an intermediate body.
[0002]
[Prior art]
Methods are known for producing diisopropylbenzene hydroperoxides by oxidizing diisopropylbenzene with air or oxygen in the liquid phase. In this case, the oxidation exhaust gas generated when oxidizing the diisopropylbenzene contains active ingredients such as raw materials and / or intermediates. Then, although the method which cools oxidation exhaust gas using a heat exchanger and collect | recovers an active ingredient etc. is known, there existed a problem that an active ingredient cannot fully be collect | recovered.
[0003]
[Problems to be solved by the invention]
In such a situation, the problem to be solved by the present invention is a method for producing diisopropylbenzene hydroperoxides by oxidizing diisopropylbenzene, wherein the active ingredient in the oxidation exhaust gas generated in this oxidation step is reduced in volatility. The object of the present invention is to provide a method for producing diisopropylbenzene hydroperoxides which are efficiently recovered by contact with a substance and thus have economically excellent characteristics.
[0004]
[Means for Solving the Problems]
That is, the present invention relates to a method for producing diisopropylbenzene hydroperoxides by oxidizing diisopropylbenzene, and relates to a method for producing diisopropylbenzene hydroperoxides including the following steps.
1st process: The process which converts diisopropylbenzene into diisopropylbenzene hydroperoxide by oxidizing with air or oxygen in the liquid phase 2nd process: Diisopropylbenzene which is low volatile substance from oxidation exhaust gas generated in the 1st process is contacted with, step [0005] to trap the active ingredient in the oxidizing gas exhaust to the low volatility substance
DETAILED DESCRIPTION OF THE INVENTION
The present invention is a process for producing diisopropylbenzene hydroperoxides by oxidizing diisopropylbenzene. Examples of diisopropylbenzene include 1,3-diisopropylbenzene and 1,4-diisopropylbenzene. Examples of diisopropylbenzene hydroperoxides obtained by oxidizing diisopropylbenzene include di (2-hydroperoxy-2-propyl) benzene, (2-hydroxy-2-propyl)-(2-hydroperoxy-2- Propyl) benzene, (2-hydroperoxy-2-propyl) isopropylbenzene, and the like.
[0006]
Hereinafter, although the specific example which applies this invention is demonstrated using the process which obtains 1, 3- diisopropyl benzene, this invention is not limited to this process. Further, the process to be described is a representative example, and can be appropriately changed. The following steps in the process are also representative, and steps can be added and deleted as necessary.
[0007]
The first step of the present invention is a step of converting diisopropylbenzene into diisopropylbenzene hydroperoxide by oxidation with air or oxygen in the liquid phase.
[0008]
As specific conditions and methods of this step, the following can be exemplified. As normal oxidation conditions, a pressure of 0 to 1 MPaG, a temperature of 70 to 110 ° C., and a residence time of 0.1 to 50 hours can be exemplified. Examples of the apparatus that can be used in the oxidation step include a flow type, batch type reaction tank, and reaction tower. In the oxidation exhaust gas generated in this step, nitrogen is usually 0 to 99 vol%, oxygen is usually 0 to 15 vol%, diisopropylbenzene is usually 0 to 10 vol%, water is usually 5 to 50 vol%, and other active ingredients are usually 0. About 0.01 to 10 vol% is included. As other active ingredients, the extraction solvent in the following fifth step may be mixed into the first step through the fourth and sixth steps.
[0009]
The second step is a step of bringing the oxidized exhaust gas generated in the first step into contact with diisopropylbenzene, which is a low-volatile substance, and trapping active ingredients in the oxidized exhaust gas in the low-volatile substance.
[0010]
The active ingredient is a raw material and / or an intermediate, and specific examples thereof include diisopropylbenzene and methyl isobutyl ketone, and the low volatile substance is diisopropylbenzene as an oxidation raw material. The following can be illustrated as a concrete method of this process. Usually, the temperature is 0 to 1 MPaG, the temperature is 0 to 80 ° C., more preferably 0 to 50 ° C. The equipment may be an oxidation exhaust gas and a low-volatile substance in contact with each other. For example, a countercurrent multistage equipment can be used. Low volatility substances from the top and oxidizing exhaust gas from the bottom can be used to absorb the active ingredients in the exhaust gas. In addition, before the oxidized exhaust gas is brought into contact with the low-volatile substance, the oxidized exhaust gas can be cooled by using a heat exchanger to recover the active ingredient to some extent. In the exhaust gas after the treatment in this second step, nitrogen is usually 0 to 99 vol%, oxygen is usually 0 to 15 vol%, diisopropylbenzene is usually 0 to 1 vol%, and other active ingredients are usually contained in an amount of 0 to 1 vol%. ing.
[0011]
In the present invention, the third step can be used. In the third step, the low-volatile substances trapped with the active ingredients obtained in the second step are subjected to distillation, and the classification containing the active ingredients is obtained from the low boiling side, and the classification containing the low volatile substances from the high boiling side. It is a process to obtain. Distillation can be carried out under conditions of -99 to 1000 KPaG, usually using simple distillation or a rectifying column. Further, the low-volatile substances generated in this step can be recycled to the third step or used in other steps.
[0012]
In the present invention, the fourth step can be used. In the fourth step, the oxidation reaction solution containing diisopropylbenzene hydroperoxides obtained in the first step is brought into contact with an alkaline aqueous solution to obtain an alkaline water layer containing diisopropylbenzene hydroperoxides and an oil layer containing unreacted diisopropylbenzene. It is a process. The weight ratio of the aqueous alkali solution to the oxidation reaction solution is usually 0.2-5. As the alkaline water, a sodium hydroxide aqueous solution is desirable from the viewpoint of cost. The alkali concentration in the aqueous alkali solution is usually 0.1 to 30% by weight. As normal extraction conditions, a temperature of 0 to 70 ° C. and a 1 to 10-stage countercurrent extraction can be mentioned. Examples of the apparatus include a mixer settler and an extraction tower.
[0013]
In the present invention, the fifth step can be used. The fifth step is a step in which the alkaline aqueous layer containing the diisopropylbenzene hydroperoxide obtained in the fourth step is brought into contact with an extraction solvent to obtain an oil layer containing the alkaline aqueous layer and the diisopropylbenzene hydroperoxide. Examples of the extraction solvent include methyl isobutyl ketone from the viewpoint of extraction efficiency. Examples of the apparatus, method and conditions for carrying out this step include the following. The weight ratio of the aqueous layer to the extraction solvent can usually be 0.2 to 10 and the temperature 20 to 80 ° C. Examples of the apparatus include a mixer settler and an extraction tower. The alkaline water layer used for extraction is generally recycled for the fourth step.
[0014]
In the present invention, the sixth step can be used. The sixth step is a step of recycling the oil layer containing unreacted diisopropylbenzene obtained in the fourth step to the first step. The following can be illustrated as conditions and a specific method of this process. The recycling to the first step is used in part or in whole, but usually 90 to 100% of the oil layer containing unreacted diisopropylbenzene obtained in the fourth step is used.
[0015]
【Example】
Example 1
First step: Using a reaction tower as an oxidation facility, a solution containing diisopropylbenzene hydroperoxides was obtained by oxidizing a solution containing diisopropylbenzene at 60 parts by weight per hour and in a liquid phase at 8000 parts by volume of air per hour. . The conditions were a pressure of 0.3 MPaG, a temperature of 90 ° C., and a residence time of 10 hours. The oxidation exhaust gas generated in this oxidation step contained 69 vol% nitrogen, 4 vol% oxygen, 0.6 vol% diisopropylbenzene, 26 vol% water, and 0.2 vol% methyl isobutyl ketone.
Second step: The oxidized exhaust gas to be treated was the oxidized exhaust gas generated in the first step, first cooled by using a heat exchanger and partially oxidized, and then used. Using a countercurrent multistage tower, the cooled oxidizing exhaust gas was introduced from the bottom of the tower, and 2.3 parts by weight of diisopropylbenzene cooled to 15 ° C. was introduced from the top of the tower to contact them. The conditions were 0.3 MPaG and a temperature of 15 ° C. The treated exhaust gas contains 94 vol% nitrogen, 5 vol% oxygen, 0.01 vol% diisopropylbenzene, and 0.01 vol% methyl isobutyl ketone. The diisopropylbenzene obtained from the bottom of the tower contains 3% methyl isobutyl ketone. It was included.
Third step: Diisopropylbenzene containing methyl isobutyl ketone obtained in the second step is subjected to rectification at -80 KpaG, and 0.1 part by weight of the section containing methyl isobutyl ketone from the low boiling side, diisopropylbenzene from the high boiling side 2.3 parts by weight of the section containing was obtained.
Fourth step: 60 parts by weight of the oxidation reaction solution containing diisopropylbenzene hydroperoxides obtained in the first step is brought into contact with a 7% aqueous sodium hydroxide solution, an alkaline aqueous layer containing diisopropylbenzene hydroperoxides and unreacted diisopropyl. An oil layer containing benzene was obtained. The weight ratio of the alkaline aqueous solution to the oxidation reaction solution was 0.6, the temperature was 40 ° C., and the mixer was used.
Fifth step: Using an extraction tower, the alkaline aqueous layer containing diisopropylbenzene hydroperoxides obtained in the fourth step was brought into contact with methyl isobutyl ketone to obtain an alkaline aqueous layer and an oil layer containing diisopropylbenzene hydroperoxides. The weight ratio of the aqueous alkali solution to the extraction solvent is 0.6-5. The temperature was 20 to 60 ° C. The alkaline water layer was almost recycled in the fourth step.
Sixth step: 99.6% of the oil layer containing unreacted diisopropylbenzene obtained in the fourth step was recycled to the first step.
[0016]
【The invention's effect】
As described above, according to the present invention, a method for producing diisopropylbenzene hydroperoxides by oxidizing diisopropylbenzene, wherein an active ingredient in an oxidation exhaust gas generated in this oxidation step is brought into contact with a low-volatile substance. It was possible to provide a process for producing diisopropylbenzene hydroperoxides that are more efficiently recovered and thus have economically superior characteristics.
[Brief description of the drawings]
FIG. 1 is an example of a flow of the present invention.
[Explanation of symbols]
1 1st process 2 2nd process 3 3rd process 4 4th process 5 5th process 6 6th process 7 Diisopropylbenzene 8 Air or oxygen 9 Oxidation exhaust gas
10 Low volatile substances
11 Low volatile substances containing active ingredients
12 Active ingredients
13 Low volatile substances
14 Oxidation reaction solution containing diisopropylbenzene hydroperoxides
15 Alkaline aqueous solution
16 Alkaline water layer containing diisopropylbenzene hydroperoxides
17 Oil reservoir containing unreacted diisopropylbenzene
18 Extraction solvent
19 Oil layer containing diisopropylbenzene hydroperoxides

Claims (6)

A method for producing diisopropylbenzene hydroperoxides by oxidizing diisopropylbenzene, which comprises the following steps.
1st process: The process which converts diisopropylbenzene into diisopropylbenzene hydroperoxide by oxidizing with air or oxygen in the liquid phase 2nd process: Diisopropylbenzene which is low volatile substance from oxidation exhaust gas generated in the 1st process To trap active ingredients in oxidation exhaust gas in low volatile substances. The manufacturing method of Claim 1 including the following process.
Third step: Distill the low-volatile substance trapping the active ingredient obtained in the second step, and obtain the category containing the active ingredient from the low boiling side and the category containing the low-volatile substance from the high boiling side. Process The manufacturing method of Claim 1 including the following process.
Fourth step: A step of contacting the oxidation reaction solution containing diisopropylbenzene hydroperoxides obtained in the first step with an alkaline aqueous solution to obtain an alkaline water layer containing diisopropylbenzene hydroperoxides and an oil layer containing unreacted diisopropylbenzene. Fifth step: a step of contacting the alkaline aqueous layer containing the diisopropylbenzene hydroperoxides obtained in the fourth step with an extraction solvent to obtain an oil layer containing the alkaline aqueous layer and the diisopropylbenzene hydroperoxides Sixth step: the fourth step Recycling the oil layer containing unreacted diisopropylbenzene obtained in step 1 to the first step   The process according to claim 1, wherein the active ingredient is methyl isobutyl ketone.   The process according to claim 3, wherein the extraction solvent is methyl isobutyl ketone.   The production method according to claim 1, wherein the diisopropylbenzene is 1,3-diisopropylbenzene and at least one of the hydroperoxides is 1,3-di- (2-hydroperoxy-2-propyl) benzene.

Images