JPH0570391A - Method for producing aromatic hydroxide - Google Patents

Abstract

PURPOSE:To produce a phenol in high selectivity and in high yield by hydrolyzing an aromatic halide in a vapor phase. CONSTITUTION:An aromatic halide is hydrolyzed in a vapor phase by using a mixture (e.g. CuO+Na-ZSM-5) prepared by blending a copper compound with a substantially nonacidic crystalline aluminosilicate as a catalyst to produce a phenol.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an aromatic hydroxide. More specifically, it relates to a method for producing an aromatic hydroxide by hydrolyzing an aromatic halide in a gas phase using a mixed catalyst of a copper-containing compound and a substantially acid-free crystalline aluminosilicate.

[0002]

2. Description of the Related Art As a method for producing phenols by hydrolyzing a halogenated aromatic compound in a gas phase, a method using copper-supported calcium phosphate apatite as a catalyst (US Pat. No. 2,988,573) is used. No.), a method using zirconium phosphate supporting copper as a catalyst (Japanese Patent Publication No. 51-6108), and a method using a rare earth metal phosphate supporting copper as a catalyst (Japanese Patent Laid-Open No. 47-279).
No. 36), a method using a crystalline aluminosilicate containing a metal component as a catalyst recently (JP-A-62-1923).
30 and JP-A-62-281834), a method using a crystalline borosilicate as a catalyst (JP-A-62-24).
No. 0635), a method using a crystalline iron silicate as a catalyst (JP-A-62-240636), and a method using a crystalline chromosilicate as a catalyst (JP-A-62-2406).
No. 34) is proposed.

[0003]

However, as a hydrolysis catalyst for aromatic halides, calcium phosphate apatite, zirconium phosphate, and rare earth phosphate catalysts have low activity, and high temperature reaction at 500 ° C. or higher and low It is necessary to react at space velocity. Further, the crystalline metallosilicate-based catalyst has relatively high activity, but the selectivity is not sufficient. In particular, there is a problem that the selectivity is poor at high conversion. In addition, there is a problem that activity deterioration with time due to caulking is large, which is not industrially satisfactory.

[0004]

Means for Solving the Problems As a result of intensive studies on the method for producing phenols by hydrolysis of aromatic halides, the present inventors have found that a copper-containing compound and a substantially acid-free crystal as a hydrolysis catalyst. By using a mixed catalyst with a water-soluble aluminosilicate, it was found that phenols can be produced stably with a high selectivity, a high yield, and a decrease in the activity over time due to coking, and the present invention has been completed. ..

As the crystalline aluminosilicate used in the present invention, a high silica crystalline aluminosilicate is preferable. For example, ZSM-5, ZSM-11, AZ
-1 (Japanese Patent Laid-Open No. 59-128210) Those having a similar structure are preferable. Silica / alumina ratio is 1
It is preferably 0 or more and 100 or less. Exchange cations of these crystalline aluminosilicates are alkali metal cations such as sodium, potassium and cesium, which are substantially non-acidic. In order to make it substantially non-acidic, an alkali metal that neutralizes the acidity may be added to the crystalline aluminosilicate by ion exchange or the like.
Usually, the amount of alkali metal corresponds to the aluminum atom in the crystalline aluminosilicate skeleton, and the atomic ratio is 0.9.
A quantitative ratio of 5 to 1.05 is preferable.

In the present invention, the crystalline aluminosilicate is treated at a temperature of 200 to 700 ° C. in the presence of steam or heat-treated at a temperature of 600 to 850 ° C. in the absence of steam to obtain the selectivity and the catalytic property. It is preferably used because of its stability. As the aromatic halide, a chlorine atom,
Any one or more of bromine atoms directly substituted with an aromatic nucleus, for example, halogen-substituted benzene such as chlorobenzene, dichlorobenzene, bromobenzene, dibromobenzene, chlorotoluene, bromotoluene, chloroxylene, bromoxylene, etc. And halogen-substituted naphthalenes such as chloronaphthalene and bromonaphthalene.

Examples of the copper-containing compound used for preparing the catalyst of the present invention include copper oxide, copper hydroxide, copper nitrate, copper chloride and copper acetate. Copper oxide and copper hydroxide are preferred. The content of copper in the catalyst is 0.0 as a metal.
It is 5 to 10% by weight, preferably 0.1 to 5% by weight.

As the catalyst of the present invention, a copper-containing compound powder and a substantially acid-free crystalline aluminosilicate are uniformly mixed, and if necessary, an inorganic binder such as alumina, silica, or a viscosity is added and molded. .. As the inorganic binder, it is preferable to use one having a low acidity. Usually, the inorganic binder can be selected in the range of 10 to 90% by weight of the molded catalyst. Examples of the catalyst molding method include extrusion granulation method, compression molding granulation method, tumbling granulation method, in-oil molding granulation method, and spray granulation method. It can be granulated into any shape and size depending on the state of use. The method of the present invention comprises a fixed bed,
It can be carried out by any method such as a moving bed or a fluidized bed.

The reaction conditions of the method of the present invention differ depending on the halogenated aromatic compound as the raw material, but usually 250 to 6
A temperature of 00 ° C., preferably 300 to 550 ° C., more preferably 350 to 500 ° C. is used as a molar ratio of water to the halogenated aromatic compound of 0.5 to
100, preferably 1-50, more preferably 1.5
~ 20 are used. The feed rate of the raw material halogenated aroma is 0.05-hour by weight hourly space velocity (WHSV).
20Hr ⁻¹ , preferably 0.1 to 10Hr ⁻¹ is used.

[0010]

[Examples] Specific examples will be described below.
The present invention is not limited to this. Example 1 According to a known method, ZSM-5 (SiO ₂ / AL ₂ O ₃ =
45) was hydrothermally synthesized, and then sodium exchange was carried out using a sodium chloride aqueous solution by a conventional method. After washing with water and drying, copper oxide powder was added and uniformly mixed in a mortar to contain 0.6% by weight of copper. The product was compression-molded and made into a mesh of 8 to 20 and subjected to a reaction.

The reaction is carried out by adding a catalyst to a quartz reaction tube of 10 mm in diameter.
The mixture was charged with g, heated to a predetermined temperature in a heating furnace, and a predetermined amount of chlorobenzene and water were supplied by a metering pump to carry out the hydrolysis reaction. The reaction conditions were 450 ° C., a water / chlorobenzene molar ratio of 6, a chlorobenzene supply amount WHSV of 0.3 Hr ⁻¹ , and nitrogen as a diluent at a nitrogen / chlorobenzene molar ratio of 1.1. From the gas chromatographic analysis of the sampling liquid 2 to 3 hours after the start of liquid passage, the conversion of chlorobenzene was 35% and the selectivity of phenol was 99.2mo.
It was l% and the benzene selectivity was 0.7 mol%.

Comparative Example 1 ZSM-5 used in Example 1 was copper-exchanged with an aqueous solution of cupric chloride according to a conventional method, and 0.6% by weight of copper was contained in the same manner as in Example 1. It was molded and subjected to a hydrolysis reaction of chlorobenzene. The reaction conditions were the same as in Example 1. As a result, the conversion rate of chlorobenzene was 37
%, Phenol selectivity 93 mol%, benzene selectivity 5
Mol% and others were high-boiling substances, and the main component was naphthalene. The reaction conditions were changed from WHSV to 1.0 Hr ⁻¹ . Chlorobenzene conversion 18%, phenol selectivity 9
8%.

Comparative Example 2 As in Example 1, except that an ammonium chloride aqueous solution was used instead of sodium exchange, and ammonium exchange was performed.
After drying, it was calcined at 500 ° C. to obtain a proton type. Copper oxide powder was uniformly mixed with this product and then compression molded to obtain a catalyst containing 0.8% by weight of copper. This catalyst was subjected to a hydrolysis reaction of chlorobenzene in the same manner as in Example 1. As a result of carrying out the reaction under the same reaction conditions as in Example 1,
Chlorobenzene conversion 38%, phenol selectivity 92
The mol% and the benzene selectivity were 5 mol%.

Comparative Example 3 The ZSM-5 zeolite of Example 1 was exchanged with ammonium using an ammonium chloride aqueous solution according to a conventional method, dried, and then calcined in the air at 500 ° C. for 5 hours to obtain a proton type. In the same manner as in Comparative Example 1, an aqueous cupric chloride solution was used for ion exchange, followed by washing with water, drying, firing in air at 500 ° C. for 5 hours, and compression molding to obtain a catalyst containing 1.0% by weight of copper. This catalyst was used in the hydrolysis reaction of chlorobenzene as in Example 1. As a result of carrying out under the same conditions as in Example 1, the chlorobenzene conversion rate was 36% and the phenol selectivity was 88 mol%. The reaction condition WHSV is 1.0
Was carried out in the same manner, but the conversion of chlorobenzene was 18% and the selectivity of phenol was 98%.

Example 2 As in Example 1, except that Na-type ZSM-5 was heat-treated at a temperature of 450 ° C. for 20 hours in an 80 vol% steam / nitrogen atmosphere. Then, copper oxide was added as copper at 1.0% by weight and silica sol was added as a binder (30% by weight as silica), kneading, extrusion molding, drying, 500
The pellets were baked at 0 ° C. to give pellets of 1 mmφ × 3 mm, which were subjected to a hydrolysis reaction of chlorobenzene. The reaction conditions are 450 ° C, W
HSV = 0.2 Hr ^-1 , water / chlorobenzene molar ratio 2,
It was carried out at a nitrogen / chlorobenzene molar ratio of 8. as a result,
Chlorobenzene conversion rate of 2 to 3 hours is 42%, phenol selectivity is 99.0 mol%, chlorobenzene conversion rate of 20 hours is 35%, phenol selectivity is 99.3 mol%.
showed that.

Example 3 Similar to Example 1, except that copper chloride was used in place of copper oxide, blended with Na-type ZSM-5, and contained 0.6% by weight of copper as in Example 1. Using the molded body as a catalyst, hydrolysis reaction of chlorobenzene was carried out in the same manner as in Example 1. As a result, the chlorobenzene conversion rate was 47% and the phenol selectivity was 97 mol%.

Example 4 As in Example 1, except that copper hydroxide was mixed with Na-type ZSM-5 instead of copper oxide, and 0.6% by weight of copper was added to the catalyst, and a catalyst was used. Hydrolysis of chlorobenzene was performed as in Example 1. As a result, 1 to
The chlorobenzene conversion rate for 2 hours was 33%, the phenol selectivity was 98.2 mol% for the reaction, and the chlorobenzene conversion rate for 9 to 10 hours was 28% and the phenol selectivity was 9%.
It was 8.7 mol%.

[0018]

According to the method of the present invention, aromatic halides are hydrolyzed, phenols are converted at a high conversion rate, and
It can be manufactured with high selectivity and has very few industrial by-products, which has great industrial significance.

Claims (2)

[Claims] 1. A method for producing an aromatic hydroxide by hydrolyzing an aromatic halide in a gas phase, wherein a mixed catalyst of a copper-containing compound and a substantially acid-free crystalline aluminosilicate is used. A process for producing an aromatic hydroxide, characterized by: 2. The method according to claim 1, wherein the copper-containing compound is copper oxide or copper hydroxide, and the substantially acid-free crystalline aluminosilicate is an alkaline crystalline aluminosilicate.