JPH059141A - Production of hydroxy aromatic compound - Google Patents

Abstract

PURPOSE:To stably produce a hydroxyaromatic compound such as phenol in a high selectively by hydrolyzing an aromatic halide in a gaseous phase. CONSTITUTION:An aromatic halide is hydrolyzed in the presence of a crystalline aluminosilicate (e.g. ZSM-5) containing a combination of cobalt with one kind or more of silver, copper and lead as a catalyst in a gaseous phase to produce a hydroxy aromatic compound. The catalyst can repeatedly be regenerated and used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a hydroxy aromatic compound. More specifically, a method for producing a hydroxyaromatic compound by hydrolyzing an aromatic halide using a crystalline aluminosilicate containing a cobalt component and any one component selected from silver, copper and lead as a catalyst. Regarding

[0002]

2. Description of the Related Art As a method for producing a hydroxy aromatic compound such as phenol by hydrolyzing a halogenated aromatic compound in a gas phase, a method using copper-supported calcium phosphate apatite as a catalyst (US Pat. 2,9
88,573), a method using copper-supported zirconium phosphate as a catalyst (JP-B-51-6108), and a method using copper-supported rare earth metal phosphate as a catalyst (JP-A-47-27936). JP-A-62-192330, JP-A-62-2.
No. 81834), a method using a crystalline borosilicate as a catalyst (JP-A-62-240635), and a method using a crystalline iron silicate as a catalyst (JP-A-62-24063).
No. 6), and a method using a crystalline chromosilicate as a catalyst (JP-A-62-240634).

[0003]

The catalysts such as calcium phosphate apatite, zirconium phosphate, and rare earth phosphates have low activity, and it is necessary to react at a high temperature of 500 ° C. or higher and at a low space velocity. Further, the crystalline metallosilicate-based catalyst has a relatively high activity, but in any of these catalysts, the copper component, which is the most effective active component, is scattered and lost as copper halide during the reaction. It has a problem that it deteriorates in activity over time, and it is not industrially satisfactory.

[0004]

Means for Solving the Problems The inventors of the present invention have made earnest studies on a method for producing a hydroxyaromatic compound by hydrolyzing an aromatic halide, and as a result, have found that a cobalt component and a silver, copper and lead component as a hydrolysis catalyst. It was found that phenols can be stably produced in high yield by using a crystalline aluminosilicate catalyst containing any one or more selected from the above. Especially in use including repeated regeneration of the catalyst,
The catalyst stabilizing effect of the present invention is remarkable.

The stability of the catalyst used in the present invention is determined by the fact that the reduction of cobalt as an active ingredient during the reaction hardly occurs, and by containing at least one of silver, copper and lead in combination. This is probably because these components interact with cobalt and have the effect of suppressing side reactions.

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.

As the aromatic halide, 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.

The catalyst used in the present invention is cobalt, silver,
Examples of the copper and lead components include halides, nitrates, sulfates, carbonates, organic acid salts, hydroxides and oxides. Specifically, cobalt compounds such as cobalt chloride, cobalt nitrate, cobalt sulfate and cobalt carbonate, silver compounds such as silver nitrate, silver chloride, silver sulfate and silver carbonate, and copper compounds such as copper nitrate and chloride. Copper, copper sulfate, copper carbonate, etc. are used as lead compounds such as lead nitrate, lead chloride,
Lead sulfate, lead carbonate, etc. can be used. The content of cobalt is 0.05 to 10% by weight, preferably 0.1 to 5% by weight as a metal, and the content of silver or lead is 0.
001 to 2.0% by weight, preferably 0.01 to 1.0% by weight, and the content of copper is 0.001 to 0.5% by weight,
It is preferably 0.01 to 0.4% by weight.

As a method of adding these metal components, a generally used impregnation method, ion exchange method, blending method or the like can be used. These metal components may be added at the same time, but it is preferable to add the silver, copper and lead components by the ion exchange method before adding the cobalt component. The crystalline aluminosilicate used in the present invention is 200 to 7 in the presence of steam.
Treat at a temperature of 00 ° C or 600 without steam
What was heat-treated at a temperature of up to 850 ° C. is preferably used from the viewpoint of phenol selectivity and catalyst stability.

The catalyst used in the present invention is usually used by molding using, as an inorganic binder, silicon, zirconia, titania, silica-magnesia, alumina, silica-beryria, silica-titania, germanium, kaolin, clay or the like. These refractory inorganic binders can be selected in the range of 10 to 90% by weight of the molded catalyst. The catalyst molding method includes extrusion granulation method, compression molding granulation method,
It is possible to granulate into any shape and size according to the state of use such as pellets, tablets, and spheres by a commonly used method such as rolling granulation method, in-oil molding granulation method, and spray granulation method. .. The method of the present invention can be carried out in any system such as fixed bed, moving bed and fluidized bed.

The reaction conditions for the method of the present invention will differ depending on the starting halogenated aromatic compound, but are 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 contact time is the weight hourly space velocity (WH
SV) 0.05 to 20 Hr ^-1 , preferably 0.1 to 1
0 Hr ^-1 is used.

[0012]

[Examples] Specific examples will be described below.
The present invention is not limited to this. Example 1 ZSM-5 by known methods _{(SiO 2 / Al 2 O 3} =
45) is hydrothermally synthesized, and then made into a sodium form by using a sodium chloride aqueous solution by a conventional method, followed by ion exchange using a silver nitrate aqueous solution, washing with water, and drying to obtain a zeolite powder containing 0.3% by weight of silver. Obtained. Anhydrous cobalt chloride powder was uniformly mixed with this in a mortar (containing 0.6% by weight of cobalt metal), then compression-molded, crushed, and sieved to 9-20 mesh for use.

For the reaction, one catalyst was placed in a 10 mm diameter quartz reaction tube.
It was filled with 0 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 0.28 Hr ⁻¹ , and nitrogen as a diluent at a nitrogen / chlorobenzene molar ratio of 1.2.

From the gas chromatographic analysis of the sampling liquid 2 to 3 hours after the start of the liquid passage, the conversion of chlorobenzene was 17%, the yield of phenol was 16.1 mol%, and most of the by-products were benzene. The total selectivity was 99.5 mol%. The reaction was further continued, and after 50 hours of reaction, the catalyst was taken out and the amount of cobalt and silver was measured by fluorescent X-ray analysis. As a result, no reduction was found in both cobalt and silver.

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, after exchanging silver as in Example 1,
According to the conventional method, impregnate with an aqueous solution of cobalt chloride,
C., dried for 2 hours, compression molded in the same manner as in Example 1 and used in the reaction (0.2% by weight of silver and 0.1% of cobalt.
It contained 6% by weight). This catalyst was used in the hydrolysis reaction of chlorobenzene as in Example 1. The reaction conditions were 450 ° C., WHSV = 0.25 Hr ⁻¹ , water / chlorobenzene molar ratio of 2, and nitrogen / chlorobenzene molar ratio of 10. As a result, the chlorobenzene conversion rate in the second to third hours was 13%, the phenol selectivity was 95 mol%, the chlorobenzene conversion rate in the 30th hour was 10%, and the phenol selectivity was 9%.
It showed 7 mol%. The catalyst used for the reaction for 50 hours was 500
Regenerated by air burning at ℃. Using a regenerated catalyst, chlorobenzene was hydrolyzed under the same conditions. As a result, the conversion of chlorobenzene was 12.5%, the phenol selectivity was 95 mol%, and the benzene selectivity was 4.5 mol%. The reaction is continued for 100 hours, and the chlorobenzene conversion rate is 7
% Of the catalyst was air-burned at 400 to 500 [deg.] C. and reacted in the same manner. As a result, the conversion of chlorobenzene was completely recovered to 13.2%.

Example 3 As Example 1, except that copper nitrate was used instead of silver nitrate, and 0.08% by weight of copper and cobalt were added to 0.6.
A catalyst containing wt% was prepared and used. Hydrolysis reaction of chlorobenzene was carried out in the same manner as in Example 1. The reaction conditions were 450 ° C., a water / chlorobenzene molar ratio of 6, a chlorobenzene supply amount WHSV of 0.28 Hr ⁻¹ , and a diluent of nitrogen gas of 1 mol amount of chlorobenzene. As a result, the chlorobenzene conversion rate after 2 to 3 hours was 18% and the phenol selectivity was 95%. The reaction was further advanced, and the conversion in 28 to 30 hours was 12% and the phenol selectivity was 97%. When the catalyst of the reaction solution was analyzed, almost no reduction was observed in both cobalt and copper.

Example 4 As in Example 1, except that lead chloride was used in place of silver nitrate for ion exchange, followed by impregnation with a cobalt chloride aqueous solution according to a conventional method, and 0.4% by weight of lead and cobalt. Then, 0.7% by weight of zeolite was molded in the same manner as in Example 1 and subjected to the hydrolysis reaction of chlorobenzene in the same manner as in Example 1. The reaction conditions were 450 ° C., a water / chlorobenzene molar ratio of 2, a chlorobenzene supply amount WHSV of 0.28 Hr ⁻¹ , and a nitrogen gas of 10 mol of chlorobenzene as a diluent were supplied for reaction.

The chlorobenzene conversion rate after 2 to 3 hours is 1
6%, and the phenol selectivity was 94 mol%. 20-2
Conversion in the second hour is 13%, phenol selectivity 95 mol
%showed that. After continuing the reaction for 50 hours, regeneration was carried out by air burning at 500 ° C., and the reaction was carried out under the same conditions. As a result, the conversion of chlorobenzene was 16.4% and the selectivity of phenol was 94 mol%. It was confirmed that the activity was almost completely restored by the regeneration. Most of the by-products were benzene.

Comparative Example 1 As in Example 1, but using a silver-free catalyst,
The hydrolysis reaction of chlorobenzene was carried out under the same conditions.
As a result, the initial chlorobenzene conversion rate was 16%, the phenol yield was 14.4 mol%, and the phenol yield at 50 hours was 8 mol%. The phenol selectivity at the initial stage of the reaction was 90%, and the phenol selectivity at the 70th hour was 88%, showing a decreasing tendency. After reacting for 70 hours, it was regenerated and used in the same manner as in Example 2. The yield of phenol was 12.7 mol%.
At 30 hours, the phenol yield was 6.5 mol%. It was recognized that the phenol yield tended to decrease due to the reaction regeneration.

Comparative Example 2 As in Example 2, but with steamed Na
A hydrolysis test of chlorobenzene was conducted under the same formulation and conditions except that ZSM-5 ion-exchanged with copper at 0.1% by weight was used. The conversion rate of chlorobenzene after 2 to 3 hours of reaction was 20%, the yield of phenol was 19.7 mol%, and the combined selectivity of benzene and phenol was 99 mol%. The reaction was further continued, and after 30 hours, the catalyst was taken out and the amount of copper as an active ingredient was measured. As a result, a decrease of 25% was recognized.

When the copper content of the same catalyst and the catalyst after the reaction under the same conditions for 50 hours was measured, the copper content showed a decrease of 50%.
The catalyst after the reaction was regenerated by air burning and again subjected to hydrolysis of chlorobenzene under the same conditions. as a result,
The conversion rate of chlorobenzene was 14%.

Comparative Example 3 As in Example 1, a catalyst containing only silver and no cobalt was used in the hydrolysis reaction of chlorobenzene under the same conditions and conditions as in Example 1. As a result, the conversion rate of chlorobenzene was 2.1%.

Comparative Example 4 The hydrolysis reaction of chlorobenzene was conducted under the same conditions as in Example 4, except that a catalyst containing no cobalt was used. As a result, the conversion rate of chlorobenzene is 2.3%
And showed a low value.

[0024]

According to the method of the present invention, an aromatic halide can be hydrolyzed to produce a hydroxyaromatic compound such as phenol with high selectivity, high yield and stably. The catalyst has a great industrial significance such that it can be regenerated by air burning and can be repeatedly used.

Claims (1)

Claim: What is claimed is: 1. A method for producing a hydroxyaromatic compound by hydrolyzing an aromatic halide in a gas phase,
A process for producing a hydroxyaromatic compound, which comprises using a crystalline aluminosilicate containing a cobalt component and one or more components selected from silver, copper and lead as a catalyst.