JP2003171364A - Method for producing cumene hydroperoxide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing cumene hydroperoxide in high safety and efficiency by carrying out the hydrogenative decomposition of cumyl alcohol in the presence of a solid catalyst, supplying the produced cumene to an oxidation step and oxidizing the cumene to obtain cumene hydroperoxide. <P>SOLUTION: The production method contains the hydrogenative decomposition step to carry out the hydrogenative decomposition of cumyl alcohol in the presence of the solid catalyst and supply the produced cumene to the following oxidation step as the oxidation raw material and an oxidation step to oxidize the cumene to obtain cumene hydroperoxide. The production method further has a means for preventing the transfer of the solid catalyst component from the hydrogenative decomposition step to the oxidation step. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing cumene hydroperoxide. More specifically, the present invention provides cumene by hydrolyzing cumyl alcohol in the presence of a solid catalyst, supplying the cumene to an oxidation step, and oxidizing cumene in the oxidation step to form cumene hydroperoxide. A method for producing cumene hydroperoxide to obtain oxide, which prevents the problem that cumene hydroperoxide is degraded and decomposed by supplying the solid catalyst component used in the hydrocracking step to the oxidation step, and thus is safe. The present invention also relates to a method for producing cumene hydroperoxide, which has an excellent feature that cumene hydroperoxide can be efficiently obtained.

[0002]

Oxidation of propylene using ethylbenzene hydroperoxide as oxygen carrier,
The process of obtaining propylene oxide and styrene is known as the Halcon process. According to this method, styrene is inevitably produced as a by-product together with propylene oxide, which is unsatisfactory from the viewpoint of selectively obtaining only propylene oxide.

As a method of selectively obtaining only propylene oxide without co-producing styrene, cumene is oxidized to cumene hydroperoxide (oxidation step),
The cumene hydroperoxide is reacted with propylene to obtain propylene oxide and cumyl alcohol (epoxidation step), the cumyl alcohol is hydrolyzed back to cumene (hydrolysis step), and the cumene is again oxidized. There is a method of attaching to. However, in this case, there is a problem that a part of the components of the solid catalyst used in the hydrocracking step is mixed and supplied to the oxidizing step, and cumene hydroperoxide deteriorates and decomposes.

[0004]

Under the present circumstances,
The problem to be solved by the present invention is that in the presence of a solid catalyst,
A method for producing cumene hydroperoxide, wherein cumene is obtained by hydrolyzing cumyl alcohol, the cumene is supplied to an oxidation step, and cumene is obtained in the oxidation step to obtain cumene hydroperoxide. By supplying the solid catalyst component used in the hydrocracking step to the oxidation step, it is possible to prevent the problem that cumene hydroperoxide deteriorates and decomposes, and thus it is possible to obtain cumene hydroperoxide safely and efficiently. The object is to provide a method for producing cumene hydroperoxide having excellent characteristics.

[0005]

That is, the present invention is a method for producing cumene hydroperoxide which comprises the following steps, wherein a solid catalyst component used in a hydrocracking step is supplied to an oxidation step. The present invention relates to a method for producing cumene hydroperoxide having means for preventing it. Hydrocracking step: Cumene alcohol is hydrolyzed in the presence of a solid catalyst to obtain cumene, and the cumene is supplied to the oxidation step as a raw material for the following oxidation step. Oxidation step: By oxidizing cumene Process for obtaining cumene hydroperoxide

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the hydrocracking step of the present invention, cumene is obtained by hydrocracking cumyl alcohol in the presence of a solid catalyst, and the cumene is supplied to the oxidation step as a raw material for the following oxidation step. It is a process to do.

As the solid catalyst, any catalyst having a hydrogenating ability can be used, and examples thereof include Group 8A metal catalysts such as cobalt, nickel and palladium, copper,
The 1B group and 2B group metal catalysts such as zinc can be used, but from the viewpoint of suppressing by-products, it is preferable to use a copper catalyst. Examples of the copper-based catalyst include copper, Raney copper, copper-chromium, copper-zinc, copper-chromium-zinc, copper-silica, copper-alumina, and compounds containing these. The hydrocracking reaction can be advantageously carried out using a catalyst in the form of a slurry or fixed bed. The reaction can be performed by a batch method, a semi-continuous method or a continuous method.

The hydrocracking reaction is carried out by bringing cumyl alcohol and hydrogen into contact with a catalyst. The reaction can be carried out in a liquid phase or a gas phase using a solvent. The solvent must be substantially inert to the reactants and products. The solvent may consist of the substances present in the cumyl alcohol solution used. For example, when cumyl alcohol is a mixture consisting of the product cumene, it is possible to substitute the solvent without adding a solvent. Other useful solvents are alkanes (eg octane, decane, dodecane).
And aromatic monocyclic compounds (for example, benzene, ethylbenzene, toluene) and the like. The hydrogenolysis reaction temperature is generally 0 to 500 ° C, but 30 to 400 ° C.
Is preferred. Generally the pressure is 100-10000k
Pa is advantageous.

The oxidation step of the present invention is a step of oxidizing cumene to obtain cumene hydroperoxide.

The oxidation of cumene is usually carried out by autoxidation with an oxygen-containing gas such as air or oxygen-enriched air. This oxidation reaction may be carried out without using an additive, or an additive such as an alkali may be used. Normal reaction temperature is 50
˜200 ° C. and the reaction pressure is between atmospheric pressure and 5 MPa. In the case of the oxidation method using an additive, the alkaline reagent may be an alkali metal compound such as NaOH or KOH, an alkaline earth metal compound, Na ₂ CO ₃ , or NaH.
Alkali metal carbonates or ammonia and as _{CO 3 (NH 4) 2 CO} 3, alkali metal ammonium carbonate or the like is used.

The present invention has means for preventing the solid catalyst component used in the hydrocracking step from being supplied to the oxidation step. This solves the problem to be solved by the present invention.

As a preferable means for preventing the solid catalyst component used in the hydrocracking step from being supplied to the oxidation step, the following distillation step can be mentioned. Distillation step: a step in which cumene supplied from the hydrocracking step to the oxidation step is subjected to distillation, and cumene recovered from the top or side cut of the distillation column is supplied to the oxidation step. The distillation can be carried out either batchwise or continuously, but in the case of large-scale industrial operation, it is generally carried out continuously. A plate column, a packed column or the like can be used as the distillation column. The operating pressure is generally 100 kPa to 1000 kPa.

Further, another preferable means for preventing the solid catalyst component used in the hydrocracking step from being supplied to the oxidation step is the following filtration step. Filtration step: a step in which cumene supplied from the hydrocracking step to the oxidation step is subjected to filtration and the cumene after filtration is supplied to the oxidation step. Fibrous substances used as the filter medium
(Nonwoven fabric, filter paper, etc.), granular material (gravel gravel, etc.), porous material (sintered metal, other-porcelain porcelain, plastic, etc.), which can be implemented by any method.

Further, as another preferable means for preventing the solid catalyst component used in the hydrocracking step from being supplied to the oxidation step, the following washing step can be mentioned. Washing step: a step in which cumene supplied from the hydrocracking step to the oxidation step is washed with water or an aqueous alkaline solution, and the cumene after washing is supplied to the oxidation step. A mixer / settler type device is generally used for the washing operation.

The above-mentioned hydrocracking step and oxidation step can be steps in the method for producing propylene oxide including the following epoxidation step. Epoxidation step: a step of obtaining propylene oxide and cumyl alcohol by reacting cumene hydroperoxide obtained in the oxidation step with propylene

The epoxidation step is a step of obtaining propylene oxide and cumyl alcohol by reacting cumene hydroperoxide obtained in the oxidation step with propylene. The epoxidation step is usually carried out by reacting cumene hydroperoxide obtained in the oxidation step with an excess amount of propylene in the liquid phase in the presence of a solid catalyst.

As the catalyst, a catalyst composed of titanium-containing silicon oxide is preferable from the viewpoint of obtaining the desired product in high yield and high selectivity. These catalysts are preferably so-called Ti-silica catalysts containing Ti chemically bound to silicon oxide. Examples thereof include a Ti compound supported on a silica carrier, a compound compounded with silicon oxide by a coprecipitation method or a sol-gel method, or a zeolite compound containing Ti.

The cumene hydroperoxide used as a raw material in the epoxidation step may be a dilute or concentrated purified product or a non-purified product.

The epoxidation reaction is carried out by bringing propylene and cumene hydroperoxide into contact with a catalyst. The reaction is carried out in the liquid phase with a solvent. The solvent must be liquid under the temperature and pressure of the reaction and substantially inert to the reactants and products. The solvent may consist of the substances present in the hydroperoxide solution used. For example, when cumene hydroperoxide is a mixture consisting of cumene as the raw material, it is possible to substitute this solvent without adding a solvent. Other useful solvents include aromatic monocyclic compounds (eg, benzene, toluene, chlorobenzene, orthodichlorobenzene), alkanes (eg, octane, decane, dodecane) and the like.

The epoxidation reaction temperature is generally 0 to 200 ° C.
However, a temperature of 25 to 200 ° C. is preferable. Pressure is
Sufficient pressure may be sufficient to keep the reaction mixture in the liquid state.
Generally, it is advantageous that the pressure is 100 to 10,000 kPa.

The solid catalyst can be advantageously implemented in the form of a slurry or a fixed bed. For large scale industrial operations it is preferred to use fixed beds. Also, batch method, semi-continuous method,
It can be carried out by a continuous method or the like. When the liquid containing the reactants is passed through the fixed bed, the liquid mixture exiting the reaction zone contains no or substantially no catalyst.

Propylene supplied to the epoxidation process /
The molar ratio of cumene hydroperoxide is 2/1 to 50
It is preferably / 1. If the ratio is too small, the reaction rate is reduced and the efficiency is poor. On the other hand, if the ratio is too large, the amount of propylene recycled is too large, and a large amount of energy is required in the recovery process.

[0023]

As described above, according to the present invention, cumene is obtained by hydrolyzing cumyl alcohol in the presence of a solid catalyst, the cumene is supplied to an oxidation step, and the cumene is oxidized in the oxidation step. A method for producing cumene hydroperoxide to obtain cumene hydroperoxide by carrying out the problem that cumene hydroperoxide is degraded and decomposed by supplying the solid catalyst component used in the hydrocracking step to the oxidation step. It was possible to provide a method for producing cumene hydroperoxide, which has an excellent feature that it is possible to prevent cumene hydroperoxide from being obtained safely and efficiently.

[Brief description of drawings]

FIG. 1 is an example of a flow of a method for producing cumene hydroperoxide according to the present invention.

[Explanation of symbols]

(1) Oxidation step (2) Epoxidation step (3) Propylene recovery step (4) Separation of propylene oxide and cumyl alcohol (5) Hydrocracking step (6) Separation of solid catalyst components <1> Cumene (fresh feed) ) <2> Oxygen source <3> Cumene hydroperoxide <4> Propylene (fresh feed) <5> Propylene (recycle) <6> Epoxidation process reaction liquid <7> Propylene oxide and cumyl alcohol <8> Propylene oxide <9> Cumyl alcohol <10> Hydrogen <11> Hydrolysis reaction liquid <12> Solid catalyst component <13> Cumene (recycle) The above <1>, <2>, <3> ... In Figure 1,
Corresponds to ...

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4C048 AA01 BB02 CC01 XX02                 4H006 AA02 AC13 AC40 AD11 BA05                       BA07 BA09 BA14 BA30 BA33                       BA61 BB11 BC10 BC11 BD84                       BE10 BE12                 4H039 CA19 CA63 CC40 CE40

Claims (5)

[Claims] 1. A method for producing cumene hydroperoxide, comprising the following steps, wherein cumene hydroperoxide having means for preventing the solid catalyst component used in the hydrocracking step from being supplied to the oxidation step: Production method. Hydrocracking step: Cumene alcohol is hydrolyzed in the presence of a solid catalyst to obtain cumene, and the cumene is supplied to the oxidation step as a raw material for the following oxidation step. Oxidation step: By oxidizing cumene Process for obtaining cumene hydroperoxide 2. The production method according to claim 1, wherein the means for preventing the solid catalyst component used in the hydrocracking step from being supplied to the oxidation step is the following distillation step. Distillation process: A process in which cumene supplied from the hydrocracking process to the oxidation process is subjected to distillation, and cumene recovered from the top or side cut of the distillation column is supplied to the oxidation process. 3. The production method according to claim 1, wherein the means for preventing the solid catalyst component used in the hydrocracking step from being supplied to the oxidation step is the following filtration step. Filtration step: a step of subjecting cumene supplied from the hydrocracking step to the oxidation step to filtration and supplying the cumene after filtration to the oxidation step 4. The production method according to claim 1, wherein the means for preventing the solid catalyst component used in the hydrocracking step from being supplied to the oxidation step is the following washing step. Washing step: a step of washing cumene supplied from the hydrocracking step to the oxidation step with water or an aqueous alkaline solution, and supplying the cumene after washing to the oxidation step 5. The production method according to claim 1, wherein the hydrocracking step and the oxidation step are steps in a method for producing propylene oxide including the following epoxidation step. Epoxidation step: a step of obtaining propylene oxide and cumyl alcohol by reacting cumene hydroperoxide obtained in the oxidation step with propylene