JPH0735350B2 - 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 (USP 3,148,222,
USP 2,988,573), copper-containing zirconium phosphate (Japanese Patent Publication No. 51-6108), rare earth metal phosphates and their copper-containing products (JP-A-47-27936) are known.

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

(Means for Solving the Problems) As a result of intensive studies to develop a highly active catalyst, the inventors of the present invention have shown the following in an anhydrous state containing a metal of Group IB and / or Group VIII on the periodic table. It was found that the crystalline iron silicate having the above composition has a high activity, and the present invention has been completed.

That is, the present invention is an anhydride containing a metal of Group IB and / or Group VIII of the periodic table as a catalyst when an aryl halide is hydrolyzed in the gas phase in the presence of water to be converted into an aryl hydroxide. In this state, a crystalline iron silicate having the following composition is used, and the present invention relates to a method for producing an aryl hydroxide.

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

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

M ² / nO · xSiO ₂ · yAl ₂ O ₃ · zFe ₂ O ₃ (where M represents at least one cation having an n valency, y + z = 1, y ≧ 0, z> 0, and x is 10 to 1000. X shown here is 10 to 1000, but 20 is preferable.
~ 500, more preferably 30-200.

The crystalline iron silicate used in the present invention always contains an iron atom, but the amount thereof is preferably 0.2 in the value of z in the formula.
To 1.0, and more preferably 0.3 to 1.0.

As such crystalline iron silicate, zeolite ZSM-
5 Similar iron silicate (Japanese Patent Laid-Open No. 56-22623) and crystalline iron silicate AZ-4 (Japanese Patent Application No. 61-997) previously filed by the applicant.
No. 2) and the like.

The crystalline iron silicate 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 iron silicate may be any state of cation, oxide, salt such as halide, and reduced metal, but the state of cation is preferable.

The content of these metals is not particularly limited, but if it is too low, the activity is low, and if it is too high, the selectivity is low. Therefore, normally 0.005 to 50 wt% with respect to the crystalline iron silicate,
Preferably 0.01 to 20 wt%, more preferably 0.1 to 1
It is in the range of 0 wt%.

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

The aryl halide in the present invention includes, for example, chlorobenzene, brombenzene, iodobenzene, dichlorobenzene, dibromobenzene, diiodobenzene,
Examples thereof include chlorotoluene, bromotoluene, iodotoluene, chlorxylene, bromoxylene, and iodoxylene.

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

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 in the range of 250 to 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.

(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
62.2wt%) 300g to which 10wt% tetrapropylammonium hydroxide aqueous solution 200g was added.
O ₃₎ was added to ₃ · 9H ₂ O solution of 29.0g was obtained a homogeneous solution. Furthermore, nitric acid was added dropwise with stirring to adjust the pH to about 11, and a homogeneous gel was obtained. 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 a crystalline iron silicate similar to zeolite ZSM-5. After ion exchange with 1N nitric acid,
The compositional formula of this crystalline silicate in a dry state obtained by fluorescent X-ray analysis in a dry state was H ₂ O.40SiO ₂ .0.08Al ₂ O ₃ .0.92Fe ₂ O ₃ .

The obtained crystalline iron silicate was subjected to ion exchange in a 20 wt% CuCl ₂ · 2H ₂ O aqueous solution at room temperature for one day, filtered, washed, and
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 a fluorescent X-ray, it was 0.60 wt% with respect to the original crystalline iron silicate.

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 atmospheric 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.

After 1 to 2 hours from the start of the reaction, the chlorobenzene conversion rate was 30.0%, the phenol selectivity was 96.8%, and the benzene selectivity was 3.2%.

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

Under the reaction conditions, water / brominebenzene molar ratio = 4.0, WHSV
(Brombenzene standard) = 1.0 hr ^-1 , reaction temperature: 450 ° C,
I went under normal pressure.

After 1 to 2 hours from the start of the reaction, the bromobenzene conversion rate was 12.0%, the phenol selectivity was 90.0%, and the benzene selectivity was 4.0%.

Example 4 The crystalline iron silicate obtained in Example 1 was used on the periodic table.
Hydrolysis reaction of chlorobenzene was carried out under the following conditions using a catalyst ion-exchanged with various metals of Group IB and Group VIII.

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 iron silicate AZ-4 was synthesized by the following procedure.

1,8-diamino-4-aminomethyloctane 10 g, Fe (N
_{O 3) 3 · 9H 2 O} 0.8g, sodium hydroxide 0.5g was dissolved in water 15 g, to obtain a homogeneous solution by addition of further silica sol (30% SiO ₂₎ 20g. 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 filtered, washed and dried at 120 ° C. for 4 hours, 550
It was calcined in air for 4 hours. This product was identified as AZ-4 by X-ray diffraction analysis.

Also, after ion exchange in 1N hydrochloric acid, it was dried at 120 ° C for 4 hours, and the composition obtained by fluorescent X-ray analysis was H ₂ O ・ 100SiO ₂・ 0.08Al ₂ O ₃・ 0.92Fe _{It was 2} O ₃ .

This AZ-4 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-4. Cu measured by fluorescent X-ray of this catalyst
The content rate was 3.0 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 28.0%, 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 and _{Fe (NO 3) 3 · 9H} 2 O2. A solution in which 0 g was dissolved 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 crystalline iron silicate similar to zeolite ZSM-5 by X-ray diffraction analysis.

The composition in an anhydrous state, which was obtained by fluorescent X-ray analysis after being ion-exchanged in 1N hydrochloric acid and dried at 120 ° C, was H ₂ O ・ 25SiO ₂・ 0.4Al ₂ O ₃・ 0.6Fe. _{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, filtered, washed, and dried at 120 ° C for 4 hours.
The operation of firing at 00 ° C. for 5 hours was performed twice. Cu of this catalyst
The content rate measured by fluorescent X-ray analysis is 0.75
It was wt%.

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.

1-2 hours after the start of the reaction, chlorobenzene conversion rate = 29.0%, phenol yield = 27.8%, phenol selectivity =
It was 96.0% and the benzene selectivity = 4.0%.

Comparative Example 1 Copper-containing LaPO ₄ was prepared according to JP-A-47-27936.

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

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 was 3.5%.

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

ZrOCl ₂・ 8H ₂ O ＝ 24g is dissolved in 10g of water, then CuCl ₂・ 2H ₂ O
= 0.6g was melted. This solution, NaOH = 8.0 g and 85% H ₃ PO
₄ = 14.8g was added to the solution which melt | dissolved in 100g of water, and stirring was continued at room temperature for 44 hours. After filtering and washing the obtained slurry,
It was dried at 110 ° C. for 4 hours and baked at 400 ° C. for 3 hours in air 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. A crystalline iron silicate having the following composition in an anhydrous state, when a halogenated benzene is hydrolyzed in the gas phase in the presence of water to be converted into hydroxylated benzene,
A method for producing benzene hydroxide, which comprises using a catalyst containing copper and / or a Group VIII metal of the periodic table. M _{2 / n} O · xSiO ₂ · yAl ₂ O ₃ · zFe 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. )