JPH0735349B2 - Method for producing aryl hydroxide - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing phenols useful as various polymer raw materials.

(Prior Art) A method of hydrolyzing an aryl halide in the gas phase in the presence of water to convert it into an aryl hydroxide has long been known as a post-stage reaction of the Raschig method in the phenol synthesis.

As a catalyst for the hydrolysis of this aryl halide,
Calcium phosphate apatite containing copper (USP3,148,222, U
SP2,988,573), zirconium phosphate containing copper (JP-B-5
1-6108), rare earth metal phosphates and their copper-containing products (Japanese Patent Laid-Open No. 47-27936) and the like.

(Problems to be solved by the invention) Since the conventional catalysts have low activity, it is necessary to react them at a high temperature of 500 ° C or higher or to react them at an extremely low SV in order to obtain a high conversion rate. It was

(Means for Solving the Problem) As a result of intensive studies to develop a highly active catalyst, the present inventors have shown the following in an anhydrous state containing a Group IB and / or a Group VIII metal on the periodic table. The inventors have found that crystalline borosilicate having a composition is highly active, and completed the present invention.

That is, the present invention is an anhydrous halide containing a metal of Group IB and / or Group VIII of the periodic table as a catalyst when the aryl halide is hydrolyzed in the gas phase in the presence of water to be converted into an aryl hydroxide. The present invention relates to a method for producing an aryl hydroxide, which comprises using crystalline borosilicate having the following composition in a state.

The crystalline borosilicate used in the present invention is an inorganic crystal body having a three-dimensional structure with rigidity similar to that of crystalline aluminosilicate generally called zeolite. In this crystalline borosilicate, SiO ₄ and BO ₄ or AlO ₄ are cross-bonded through an oxygen atom, and the ratio of the sum of boron atom, aluminum atom, silicon atom and oxygen atom is 1: 2. Also, the electron valence of tetrahedra containing boron or aluminum is balanced by the inclusion of various cations within the crystallinity.

The crystalline borosilicate used in the present invention is represented by the following composition formula in an anhydrous state.

_{M 2 / n O · xSiO 2} · yAl 2 O 3 · zB 2 O 3 ( however, M represents at least one cation of valence n, y + z = 1, y ≧ 0, z> 0, x is 10 to 1000 X shown here is 10 to 1000, but preferred is
20-500 More preferred is the range of 30-200.

The crystalline borosilicate used in the present invention always contains a boron atom, but the amount thereof is preferably 0 in the value of z in the formula.
The range is 2 to 1.0, and more preferably 0.3 to 1.0.

Zeolite ZSM- is one of the crystalline borosilicates.
5 Similar borosilicates (JP-A-55-7598), crystalline borosilicate AZ-2 (JP-A-60-231410), and the like.

The crystalline borosilicate used in the present invention needs to contain a metal of Group IB and / or Group VIII on the periodic table.
Group IB on the Periodic Table is copper, silver and gold, and Group VIII is nickel, palladium, platinum, cobalt, rhodium, iridium, iron, ruthenium and osmium. , Copper, nickel, cobalt and palladium, with copper being particularly preferred.

The state of these metals contained in the crystalline borosilicate may be any of a cation, an oxide, a salt such as a halide, and a reduced metal, but the cation state is preferable.

The content of these metals is not particularly limited, but if it is too small, the activity is low, and if it is too much, the selectivity is low. Therefore, normally 0.005 to 50 wt% with respect to the crystalline borosilicate,
Preferably 0.01 to 20 wt%, more preferably 0.1 to 10 wt%
% Range.

As a method of incorporating these metals into the crystalline borosilicate, a usual ion exchange method, an impregnation method or the like is used.

The aryl halide in the present invention, for example, chlorobenzene, brombenzene, iodobenzene, dichlorobenzene, dibromobenzene diiodobenzene, chlorotoluene, bromotoluene, iodotoluene, chlorxylene, bromoxylene, iodoxylene and the like. Can be mentioned.

The ratio of water to aryl halide in the present invention is usually
The water / aryl halide molar ratio is in the range of 0.5 to 100, preferably 1 to 50, more preferably 2 to 20.

The aryl hydroxide in the present invention is a corresponding hydroxybenzene when the raw material is a monohalogenated benzene, and is monohydroxybenzene and / or dihydroxybenzene when the raw material is a dihalide.

The reaction temperature in the present invention is usually 250 to 600 ° C., preferably
It is in the range of 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.

(Effects of the Invention) The catalyst of the present invention has higher activity than conventional catalysts. This is very advantageous for industrial use.

(Example) Next, this invention is demonstrated using an Example.

Example 1 Q brand silicate aqueous solution (Na ₂ O 8.9 wt%, SiO ₂ 28.9 wt%, H ₂ O
200 g of 10 wt% tetrapropylammonium hydroxide aqueous solution was added to 300 g of 62.2 wt%), and a solution of 6.0 g of boric acid (H ₃ BO ₃ ) in 100 g of water was added to obtain a homogeneous solution. Furthermore, nitric acid was added dropwise with stirring to adjust the pH to about 11 to obtain a homogeneous gel. This gel was placed in a Teflon-lined autoclave and crystallized at 180 ° C. for 24 hours while stirring.

The product obtained is filtered, washed and dried at 120 ° C. for 4 hours, 500
It was calcined in air for 6 hours. This product was found by X-ray diffraction analysis to be crystalline borosilicate similar to zeolite ZSM-5. After ion exchange with IN nitric acid,
The compositional formula of this crystalline silicate in an anhydrous state obtained by fluorescent X-ray analysis in a dried state is H ₂ O · 30SiO ₂ · 0.05Al ₂
It was O ₃ · 0.95B ₂ O ₃ .

The obtained crystalline borosilicate was subjected to ion exchange in a 20 wt% CuCl ₂ · 2H ₂ O aqueous solution at room temperature for one day, and after rinsing and washing, 12
It was dried at 0 ° C. for 4 hours and calcined at 400 ° C. for 5 hours. Of this catalyst
As a result of measuring the Cu content using fluorescent X-ray, it was 0.45 wt% with respect to the original crystalline borosilicate.

Using this catalyst, chlorobenzene was hydrolyzed.

The reaction conditions were water / chlorobenzene molar ratio = 2.6 WHSV (chlorobenzene standard) = 3.0 hr ⁻¹ , reaction temperature: 450 ° C. and normal pressure.

The results of 1 to 2 hours after the start of the reaction are shown in Table 1.

Example 2 Using the catalyst obtained in Example 1, a hydrolysis reaction of chlorobenzene was carried out under the following conditions.

Water / chlorobenzene molar ratio = 6, WHSV (chlorobenzene standard) = 0.5 hr ⁻¹ , reaction temperature: 400 ° C. normal pressure 1-2 hours after the start of the reaction, the chlorobenzene conversion rate = 27.0%, phenol selection The ratio was 97.5% and the benzene selectivity was 2.5%.

Example 3 Using the catalyst obtained in Example 1, a hydrolysis reaction of bromobenzene was carried out under the following conditions.

The reaction conditions were water / brominebenzene molar ratio = 4.0 WHSV (brominebenzene standard) = 1.0 hr ⁻¹ , reactivity: 450 ° C., and atmospheric pressure.

After 1 to 2 hours from the start of the reaction, the bromobenzene conversion rate was 17.0%, the phenol selectivity was 91.0%, and the benzene selectivity was 6.0%.

Example 4 A hydrolysis reaction of chlorobenzene was carried out under the following conditions using a catalyst in which the crystalline borosilicate obtained in Example 1 was ion-exchanged with various metals of Group IB and Group VIII on the periodic table.

Water / chlorobenzene molar ratio = 2.6, WHSV (chlorobenzene standard) = 3.0 hr ⁻¹ , reaction temperature: 450 ° C., normal pressure.

The results of 1 to 2 hours after the start of the reaction are shown in Table 2.

Example 5 Crystalline borosilicate AZ-2 according to JP-A-60-231410
Was synthesized by the following procedure.

1,8-diamino-4-aminomethyloctane 10g, boric acid
0.21 g of (H ₃ BO ₃ ) and 0.5 g of sodium hydroxide were dissolved in 15 g of water, and 20 g of silica sol (30% SiO ₂ ) was added to obtain a homogeneous solution. While stirring this solution, 20% sulfuric acid was added dropwise to adjust the pH to about 11.5 to obtain a homogeneous gel. Further, this gel was put into a mixer and mixed at 5000 rpm for 10 minutes to promote gelation. This gel was placed in a Teflon test tube and allowed to stand in a stainless steel pressure vessel at 170 ° C. for 48 hours for crystallization.

The product obtained is overwashed and dried at 120 ° C for 4 hours, 550 ° C.
And baked in air for 4 hours. This product was identified as AZ-2 by X-ray diffraction analysis. Also, after ion exchange in IN hydrochloric acid, it was dried at 120 ° C for 4 hours, and the composition obtained by fluorescent X-ray analysis was H ₂ O ・ 60SiO ₂・ 0.03Al ₂ O ₃・ 0.97B in an anhydrous state.
_{It was 2} O ₃ .

This AZ-2 was immersed in a 10 wt% CuCl ₂ · 2H ₂ O aqueous solution, evaporated to dryness, and then calcined in air at 450 ° C. for 3 hours to prepare a Cu-supported AZ-2. Cu measured by fluorescent X-ray of this catalyst
The content rate was 1.5 wt%.

Using this catalyst, the hydrolysis reaction of chlorobenzene was carried out under the following conditions.

Water / chlorobenzene molar ratio = 3.0, WHSV (chlorobenzene standard) = 0.8 hr ⁻¹ , reaction temperature: 450 ° C., normal pressure.

After 1 to 2 hours from the start of the reaction, the chlorobenzene conversion rate was 35.0%, the phenol selectivity was 96.5%, and the benzene selectivity was 3.5%.

Example 6 Q brand silicate aqueous solution (Na ₂ O 8.9 wt%, SiO ₂ 28.9 wt%, H ₂ O
62.2wt%) to 10 wt% tetrapropylammonium hydroxide key side solution 200g was added to 300 g, further aluminum nitrate in water _{100g (Al (NO 3) 3} · 9H 2 O) 3g of boric acid (H ₃ BO ₃₎ 0.42g
Was added to obtain a homogeneous solution. Furthermore, nitric acid was added dropwise with stirring to adjust the pH to about 11 to obtain a homogeneous gel. This gel was placed in a Teflon-lined autoclave and crystallized at 180 ° C. for 36 hours while stirring.

The product obtained is filtered, washed and dried at 120 ° C. for 4 hours, 500
It was calcined in air for 6 hours. The product was identified as a crystalline borosilicate similar to zeolite ZSM-5 by X-ray diffraction analysis. The composition in an anhydrous state obtained by fluorescent X-ray analysis after ion exchange in hydrochloric acid of IN and drying at 120 ° C is H ₂ O ・ 30SiO ₂・ 0.5Al ₂ O ₃・ 0.5B _{It was 2} O ₃ .

Further, this catalyst was subjected to ion exchange in a 20 wt% CuCl ₂ · 2H ₂ O aqueous solution for one day, and then filtered, washed, and dried at 120 ° C for 4 hours.
The operation of baking at 5 ° C. for 5 hours was performed twice. The Cu content of this catalyst was measured by fluorescent X-ray analysis and found to be 0.75 wt.
It was in%.

Using this catalyst, hydrolysis reaction of chlorobenzene was carried out under the following conditions.

Water / chlorobenzene molar ratio = 5.5, WHSV (chlorobenzene standard) = 0.3 hr ⁻¹ , reaction temperature: 400 ° C., normal pressure.

After 1 to 2 hours from the start of the reaction, the chlorobenzene conversion rate was 32.0%, the phenol yield was 30.6%, the phenol selectivity was 95.5%, and the benzene selectivity was 4.5%.

Comparative Example 1 Copper PO containing LaPO ₄ was prepared in JP-A-47-27936.

La a _{(NO 3) 3 · 6H 2} O = 28.8g to a solution in water 200 cc., (N
H ₄ ) ₂ HPO ₄ = 17.6 g in 100 cc. Of water is added with vigorous stirring. After that, adjust the pH to 6.0 with aqueous ammonia, wash the excess, and then dry at 120 ° C for 24 hours, 500 ° C.
It was calcined in air for 16 hours to obtain white LaPO ₄ powder. The _{LaPO 4 = 10g, Cu (NO} 3) 2 · 3H 2 O of 0.2 wt% aqueous solution of 20 cc.
It was immersed in the solution, evaporated to dryness, and then baked at 450 ° C. for 5 hours in the air. The Cu content in this Cu-containing LaPO ₄ was 0.05 wt%.

Using this Cu-containing LaPO ₄ as a catalyst, a hydrolysis reaction of chlorobenzene was performed under the following conditions.

Water / chlorobenzene molar ratio = 2.6, WHSV (chlorobenzene standard) = 0.6 hr ⁻¹ , reaction temperature: 450 ° C., normal pressure.

After 1 to 2 hours from the start of the reaction, the chlorobenzene conversion rate was 13.0%, the phenol yield was 12.5%, the phenol selectivity was 96.5%, and the benzene conversion rate was 3.5%.

Comparative Example 2 A zirconium phosphate containing copper was prepared according to JP-B-51-6108.

ZrOCl ₂ · 8H ₂ O = 24 g is dissolved in 100 g of water, and CuCl ₂ O = 0.
6g was melted. This solution, 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. 110 ℃ after washing the resulting slurry
And dried in air at 400 ° C. for 3 hours to obtain copper-containing zirconium phosphate.

Comparative Example 1 using this copper-containing zirconium phosphate as a catalyst
The hydrolysis reaction of chlorobenzene was carried out under the same conditions as described above.

After 1 to 2 hours from the start of the reaction, the chlorobenzene conversion rate was 9.2%, the phenol yield was 8.9%, the phenol selectivity was 97.0%, and the benzene was 3.0%.

Claims (1)

[Claims] 1. When a halogenated benzene is hydrolyzed in the gas phase in the presence of water to be converted into hydroxylated benzene, crystalline borosilicate having the following composition in an anhydrous state is added to copper and / or the periodic table. A process for producing benzene hydroxide, which comprises using a catalyst containing a Group VIII metal in the table. M _{2 / n} O · xSiO ₂ · yAl ₂ O ₃ · zB ₂ O ₃ (where M represents at least one cation having an n-valence,
y + z = 1, y ≧ 0, z> 0, and x is 10 to 1000. )