Method of producing 3,4-epoxy-1-butylene

A technology of butene and epoxy, applied in the direction of organic chemistry, etc., can solve the problems of low conversion rate of raw materials, wasteful product yield, etc.

Active Publication Date: 2016-02-10

CHINA PETROLEUM & CHEM CORP +1

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AI-Extracted Technical Summary

Problems solved by technology

[0006] The technical problem to be solved by the present invention is that the prior art has the problems of low raw mat...

Abstract

The invention relates to a method of producing 3,4-epoxy-1-butylene and mainly solves the problem that a method in the prior art is low in raw material conversion rate, is serious in waste and is low in production yield. The synthetic method includes the following steps: a) performing a reaction to isopropyl benzene and air to obtain a hydrogen peroxide isopropyl benzene oxidized liquid; b) controlling the weight percentage ratio of organic acid to be not more than 0.3%, the weight percentage ratio of alkali metal ions or alkali earth metal ions to be not more than 0.1% and the weight percentage ratio of water to be not more than 0.5% in the hydrogen peroxide isopropyl benzene oxidized liquid; c) performing an epoxidation reaction to the hydrogen peroxide isopropyl benzene oxidized liquid with 1,3-butadiene to generate the 3,4-epoxy-1-butylene and [alpha],[alpha]-dimethyl benzyl alcohol; and d) performing a reaction between the [alpha],[alpha]-dimethyl benzyl alcohol and hydrogen to generate isopropyl benzene, and feeding the isopropyl benzene back to the step a) as the raw material for producing the hydrogen peroxide isopropyl benzene. The method can solves technical problems and can be used in industrial production of the 3,4-epoxy-1-butylene.

Application Domain

Organic chemistry

Technology Topic

IonOrganic acid +10

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Examples

Experimental program(6)
Comparison scheme(4)

Example Embodiment

[0034] [Example 1]

[0035] At 105° C., 0.4 MPa, and the tail oxygen volume content is controlled to be less than 5%, the cumene and air undergo oxidation reaction to obtain cumene hydrogen peroxide (CHP) oxidation solution with a weight concentration of 20-24%.

[0036] The cumene hydrogen peroxide oxidation solution is washed with an aqueous solution with a NaOH weight content of 2%, wherein the volume ratio of the oxidation solution to the lye is 3:1, and the organic acid is removed. Then wash the oxidizing solution with deionized water to remove the residual Na due to alkaline washing + , Where the volume ratio of oxidizing solution to deionized water is 3:1. According to the needs of the epoxidation reaction, it is concentrated in a vacuum at a concentration temperature of 75°C to obtain an oxidizing solution with a concentration of 50% by weight of cumene hydrogen peroxide. At the same time as the concentration is concentrated, the residual water due to washing is also to a certain extent. Was removed. After treatment, the weight content of organic acid in cumene hydrogen peroxide oxidation solution is 90ppm, H 2 The weight content of O is 200ppm, Na + The weight content is 55ppm.

[0037] The above cumene hydrogen peroxide oxidation solution (CHP concentration is 50% by weight) in the presence of Ti-HMS catalyst (Ti content is 1.6% by weight) in a fixed bed reactor and 1,3-butane The olefin undergoes selective redox reaction to generate 3,4-epoxy-1-butene and α,α-dimethylbenzyl alcohol. Among them, 1,3-butadiene/CHP=5:1 (mole), the weight space velocity of CHP=4 hours -1 , The reaction temperature is 100°C, and the reaction pressure is 3.0MPa.

[0038] The reaction mixture is passed into the butadiene recovery tower to recover excess 1,3-butadiene for recycling. The butadiene recovery tower is operated under normal pressure, the top temperature is -4.5°C, and the bottom temperature is 150°C. Pressure. The tower kettle contains 3,4-epoxy-1-butene, α,α-dimethylbenzyl alcohol, cumene and other materials into the 3,4-epoxy-1-butene separation tower, which is at atmospheric pressure The temperature at the top of the tower is 66°C and the temperature at the bottom of the tower is 160°C.

[0039] The 3,4-epoxy-1-butene separation tower still contains materials such as α,α-dimethylbenzyl alcohol and cumene into the benzyl alcohol hydrogenolysis reactor. α,α-Dimethylbenzyl alcohol in 0.5%Pd/Al 2 O 3 In the presence of a catalyst, hydrogenolysis produces cumene. The reaction temperature is 160℃, the reaction pressure is 2.0MPa, H 2 The molar ratio of /α,α-dimethylbenzyl alcohol is 3:1, and the weight space velocity of α,α-dimethylbenzyl alcohol is 1.0 hour -1. The produced cumene is recycled to the oxidation step as a raw material for preparing cumene hydroperoxide. The results of the reaction are shown in Table 1.

Example Embodiment

[0040] [Example 2]

[0041] Under the condition of controlling the volume content of tail oxygen to be lower than 5% at 100°C and 0.3MPa, cumene and air undergo oxidation reaction to obtain cumene hydrogen peroxide (CHP) oxidation solution with a weight concentration of 20-24%.

[0042] Adopt Na 2 CO 3 The 5% by weight aqueous solution washes the cumene hydrogen peroxide oxidation solution, wherein the volume ratio of the oxidation solution to the lye is 4:1, and the organic acid is removed. Then wash the oxidizing solution with deionized water to remove the residual Na due to alkaline washing + , Where the volume ratio of oxidizing solution to deionized water is 4:1. According to the needs of the epoxidation reaction, it is concentrated in a vacuum at a concentration temperature of 70°C to obtain an oxidizing solution with a concentration of 40% by weight of cumene hydrogen peroxide. At the same time as the concentration is concentrated, the residual water due to washing is also to a certain extent. Was removed. After treatment, the weight content of organic acid in the cumene hydrogen peroxide oxidation solution is 100ppm, H 2 The weight content of O is 250ppm, Na + The weight content is 40ppm.

[0043] The above cumene hydrogen peroxide oxidation solution (CHP concentration is 40% by weight) in the presence of Ti-MCM-41 catalyst (Ti content is 2.0% by weight) in a fixed bed reactor to neutralize 1,3- Butadiene undergoes selective redox reaction to generate 3,4-epoxy-1-butene and α,α-dimethylbenzyl alcohol. Among them, 1,3-butadiene/CHP=5:1 (mole), and the weight space velocity of CHP=4.5 hours -1 , The reaction temperature is 98°C, and the reaction pressure is 2.8MPa.

[0044] The process of butadiene recovery and product separation is the same as [Example 1].

[0045] The 3,4-epoxy-1-butene separation tower still contains materials such as α,α-dimethylbenzyl alcohol and cumene into the benzyl alcohol hydrogenolysis reactor. α,α-Dimethylbenzyl alcohol is hydrogenolyzed to produce cumene in the presence of 0.2% Pd/C catalyst. The reaction temperature is 150℃, the reaction pressure is 2.0MPa, H 2 The molar ratio of /α,α-dimethylbenzyl alcohol is 3:1, and the weight space velocity of α,α-dimethylbenzyl alcohol is 1.0 hour -1. The produced cumene is recycled to the oxidation step as a raw material for preparing cumene hydroperoxide. The results of the reaction are shown in Table 1.

Example Embodiment

[0046] [Example 3]

[0047] Under the condition of controlling the volume content of tail oxygen to be less than 5% at 98°C and 0.3MPa, the cumene reacts with air to obtain cumene hydrogen peroxide (CHP) oxidation solution with a weight concentration of 20-24%.

[0048] The cumene hydrogen peroxide oxidation solution is washed with an aqueous solution with a NaOH weight content of 2%, wherein the volume ratio of the oxidation solution to the lye is 3:1, and the organic acid is removed. Then wash the oxidizing solution with deionized water to remove the residual Na due to alkaline washing + , Where the volume ratio of oxidizing solution to deionized water is 4:1. According to the needs of the epoxidation reaction, it is concentrated in a vacuum at a concentration temperature of 80°C to obtain an oxidizing solution with a concentration of cumene hydroperoxide of 60% by weight. While the concentration is concentrated, the water remaining due to washing is also to a certain extent. Was removed. After treatment, the weight content of organic acid in the cumene hydrogen peroxide oxidation solution is 70ppm, H 2 The weight content of O is 100ppm, Na + The weight content of 30ppm.

[0049] The above cumene hydrogen peroxide oxidation solution (CHP concentration is 60% by weight) in the presence of Ti-TUD-1 catalyst (Ti content is 1.5% by weight) in a fixed bed reactor to neutralize 1,3- Butadiene undergoes selective redox reaction to generate 3,4-epoxy-1-butene and α,α-dimethylbenzyl alcohol. Among them, 1,3-butadiene/CHP=6:1 (mole), the weight space velocity of CHP=4 hours -1 , The reaction temperature is 100°C, and the reaction pressure is 3.5MPa.

[0050] The process of butadiene recovery and product separation is the same as [Example 1].

[0051] The 3,4-epoxy-1-butene separation tower still contains materials such as α,α-dimethylbenzyl alcohol and cumene into the benzyl alcohol hydrogenolysis reactor. α,α-Dimethylbenzyl alcohol is hydrogenolyzed to produce cumene in the presence of 0.2% Pd/C catalyst. The reaction temperature is 165℃, the reaction pressure is 2.4MPa, H 2 The molar ratio of /α,α-dimethylbenzyl alcohol is 2:1, and the weight space velocity of α,α-dimethylbenzyl alcohol is 1.0 hour -1. The produced cumene is recycled to the oxidation step as a raw material for preparing cumene hydroperoxide. The results of the reaction are shown in Table 1.

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