JPH07110824B2 - Phenol manufacturing method - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a process for producing phenol useful as a raw material for various polymers.

[0002]

2. Description of the Related Art A method in which halogenated benzene is hydrolyzed in the gas phase in the presence of water to be converted into phenol has long been known as a post-stage reaction of the Raschig method in phenol synthesis. As a catalyst for the hydrolysis of the halogenated benzene , calcium phosphate apatite containing copper (US Pat. No. 3,148,222, US Pat. No. 29) is used.
88573), zirconium phosphate containing copper (JP-B-51-6108), rare earth metal phosphate and copper-containing rare earth metal phosphate (JP-A-47-27).
No. 936) is known.

Since the activity of conventional catalysts is low, it has been necessary to react at a high temperature of 500 ° C. or higher or at a very low space velocity in order to obtain a high conversion rate. Furthermore, the activity of these catalysts was significantly reduced during the reaction, and it was difficult to regenerate the catalysts.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a phenotype which uses a catalyst which is highly active, has a small decrease in activity, and is easily regenerated.
It is an object of the present invention to provide a method for manufacturing a package .

[0005]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the present inventors have found that a crystalline aluminosilicate AZ-1 containing copper has high activity and little activity decrease, and catalyst regeneration is easy. Therefore, the present invention has been completed. That is, the present invention relates to halogenated benzene.
Zen is hydrolyzed in the gas phase in the presence of water to pheno
Fe which when converted to le, characterized by using a crystalline aluminosilicate AZ-1 containing copper as a catalyst
It is a manufacturing method of a knot . The crystalline aluminosilicate used in the present invention is an inorganic crystal body having a rigid three-dimensional structure in which SiO ₄ and AlO ₄ are cross-bonded through oxygen atoms. The ratio of the sum of aluminum atoms and silicon atoms to oxygen atoms in this is 1: 2, and the electron valence of the tetrahedron containing aluminum is balanced by the inclusion of various cations in the crystal. Is dripping Although many crystalline aluminosilicates are known so far, the crystalline aluminosilicate AZ-1 is used in the present invention. This AZ-1 refers to JP-A-59-128210 and US Pat. No. 38324.
It is a novel crystalline aluminosilicate developed by the present inventors described in Japanese Patent No. 49.

The crystalline aluminosilicate AZ-1 used in the present invention must contain copper . The state of this metal contained in the crystalline aluminosilicate AZ-1 may be any of a cation, an oxide, a salt such as a halide, and a reduced metal, but a cation state is preferable.

The content of this metal is not particularly limited,
If it is too small, the activity will be low, and if it is too large, the selectivity will be low. Therefore, it is usually 0.005 to 50 wt%, preferably 0.01 to 2 with respect to the crystalline aluminosilicate AZ-1.
It is 0 wt%, and more preferably 0.1 to 10 wt%. As a method for incorporating the metal into the crystalline aluminosilicate AZ-1, a usual ion exchange method, an impregnation method or the like is used.

The halogenated benzene in the present invention is
Examples thereof include chlorobenzene, bromobenzene, iodobenzene and the like. Water and halogenated benzene in the present invention
The zen ratio is usually 0.5 to 100, preferably 1 to 50, and more preferably 2 to 20 in terms of water / halogenated benzene (molar ratio).

The reaction temperature in the present invention is usually 250 to
The temperature is 600 ° C, preferably 300 to 550 ° C, more preferably 350 to 500 ° C.

The pressure in the present invention may be any of reduced pressure, normal pressure and increased pressure.

[0011]

EXAMPLES The present invention will be described below with reference to examples. The conversion rate, yield, and selectivity in the following examples and comparative examples were determined based on the analysis values by a usual gas chromatograph method.

[0012]

Example 1 Zeolite AZ-1 was synthesized by the following procedure according to the description of JP-A-59-128210.
10 g of 1,8-diamino-4-aminomethyloctane,
Aluminum sulfate _{(Al 2 (SO 4) 3} · 18H 2 O)
0.5 g and 0.5 g of sodium hydroxide were dissolved in 15 g of water, and 20 g of silica sol (30% SiO ₂ ) was further added to obtain a homogeneous solution. 20% while stirring in this solution
Sulfuric acid was added dropwise to adjust the pH to 12 to obtain a homogeneous gel.
Furthermore, this gel is put in a mixer, and it is 1 at 1000 rpm.
Mix for 0 minutes to promote gelation. This gel was placed in a Teflon test tube and placed in a stainless steel pressure vessel at 170 ° C for 4
Crystallization was carried out by standing still for 8 hours.

The obtained product was filtered, washed, dried at 120 ° C. for 4 hours, and calcined in air at 550 ° C. for 4 hours. This product was identified as AZ-1 by X-ray diffraction analysis. or,
The SiO ₂ / Al ₂ O ₃ (molar ratio) determined by fluorescent X-ray analysis was 120. 10 wt% Cu of this AZ-1
After immersing in Cl ₂ · 2H ₂ O aqueous solution, evaporate to dryness, and further calcination in air at 450 ° C for 3 hours, Cu supporting AZ
-1 was prepared. Cu measured by fluorescent X-ray of this catalyst
The content rate was 1.5 wt%. Using this catalyst, chlorobenzene was hydrolyzed under the following reaction conditions. [Reaction conditions] Water / chlorobenzene (molar ratio) = 3.
0, WHSV (based on chlorobenzene) = 0.8 hr ^-1 ,
Reaction temperature = 460 ° C., normal pressure. The results after 3 to 4 hours from the start of the reaction were chlorobenzene conversion rate = 16%, phenol selectivity = 97%, and benzene selectivity = 3%.

[0014]

[Comparative Example 1] Na-Y type zeolite (Linde Devijo
SK-40, SiO₂/ Al ₂O₃(Molar ratio) =
4.6) 15 wt% CuCl₂・ 2H₂In O water solution
Ion exchange was performed for 1 day. After filtration and washing, 120 ° C at 4:00
After being dried for a while, it is baked at 450 ° C for 3 hours to form Cu-Y type
A zeolite was obtained. Cu measured by fluorescent X-ray analysis
Was 1.5 wt%. With this catalyst
The hydrolysis reaction of chlorobenzene was performed under the above reaction conditions. [Reaction conditions] Water / chlorobenzene (molar ratio) = 3.
0, WHSV (based on chlorobenzene) = 3.0 hr^-1,
Reaction temperature = 450 ° C., normal pressure. 2-3 hours from the start of the reaction
The results are: chlorobenzene conversion = 1.2%, phenol
The selectivity was 99%.

[0015]

[Comparative Example 2] H-mordenite (Si produced by Toyo Soda Co., Ltd.
O ₂ / Al ₂ O ₃ (molar ratio) = 10) 20 wt% Cu
Ion exchange with Cl ₂ · 2H ₂ O aqueous solution for 1 day, filtration,
After washing, it was dried at 120 ° C. for 4 hours and calcined in air at 450 ° C. for 3 hours to obtain Cu-mordenite. The Cu content determined by fluorescent X-ray analysis was 1.0 wt%. Using this catalyst, hydrolysis reaction of chlorobenzene was performed under the following reaction conditions. [Reaction conditions] Water / chlorobenzene (molar ratio) = 4.
0, WHSV (based on chlorobenzene) = 1.0 hr ^-1 ,
Reaction temperature = 450 ° C., normal pressure. The results after 3 to 4 hours from the start of the reaction were chlorobenzene conversion rate = 2.1% and phenol selectivity = 99%.

[0016]

[Comparative Example 3] As described in JP-A-47-27936.
Copper containing LaPO_FourWas prepared. That is, La (N
O₃)₃・ 6H₂O = 28.8 g dissolved in 200 cc of water
To the solution (NH_Four)₂HPO_Four= 17.6 g water 1
Add the solution in 00 cc with vigorous stirring.
After that, adjust the pH to 6.0 with aqueous ammonia and filter.
After washing and cleaning, dry at 120 ℃ for 24 hours, at 500 ℃
White LaPO after firing in air for 16 hours_FourGot powder
It was This LaPO_Four= 10 g of Cu (NO₃)₂・ 3H
₂Evaporate by immersing in 20cc of 0.2wt% aqueous solution of O
After drying to dryness, it was baked in air at 450 ° C. for 5 hours. this
Cu-containing LaPO_FourCu content in 0.05 wt%
there were. This Cu-containing LaPO_FourUsing as a catalyst,
The hydrolysis reaction of chlorobenzene was carried out under the reaction conditions of. [Reaction conditions] Water / chlorobenzene (molar ratio) = 3.
0, WHSV (chlorobenzene standard) = 0.8 hr^-1,
Reaction temperature = 460 ° C., normal pressure.

2-3 hours after the start of the reaction, the chlorobenzene conversion rate was 9.2% and the phenol selectivity was 9
It was 6.0% and the benzene selectivity = 4.0%. Comparison of this result with Example 1 shows that the activity of this catalyst is low.

[0018]

[Comparative Example 4] Zirconium phosphate containing copper was prepared according to the description in JP-B-51-6108. That is, Z
rOCl ₂ · 8H ₂ O = 24 g was dissolved in 100 g of water,
Further, CuCl ₂ .2H ₂ O = 0.6 g was melted. This solution was added with NaOH = 8.0 g and 85% H ₃ PO ₄ = 1.
4.8g was added to the solution which melt | dissolved in 100g of water, and stirring was continued at room temperature for 44 hours. The obtained slurry was filtered, washed, dried at 110 ° C. for 4 hours, and calcined in air at 400 ° C. for 3 hours to obtain copper-containing zirconium phosphate.

Using this copper-containing zirconium phosphate as a catalyst, a hydrolysis reaction of chlorobenzene was carried out under the same conditions as in Comparative Example 3. 2 to 3 hours after the start of the reaction, the chlorobenzene conversion rate was 7.0% and the phenol selectivity was 9%.
It was 7.0% and benzene selectivity = 3.0%. Comparing this result with the example shows that the activity of this catalyst is low.

[0020]

EFFECT OF THE INVENTION The catalyst of the present invention has a higher activity than that of the conventional catalyst and has a small decrease in activity, which facilitates catalyst regeneration. This is very advantageous for industrial use.

Claims (1)

[Claims] 1. A crystalline aluminosilicate AZ-1 containing copper as a catalyst when a halogenated benzene is hydrolyzed in the gas phase in the presence of water to be converted into phenol.
A method for producing phenol , which comprises using