JPH0616582A - Production of aryl hydroxide - Google Patents
Production of aryl hydroxideInfo
- Publication number
- JPH0616582A JPH0616582A JP5016178A JP1617893A JPH0616582A JP H0616582 A JPH0616582 A JP H0616582A JP 5016178 A JP5016178 A JP 5016178A JP 1617893 A JP1617893 A JP 1617893A JP H0616582 A JPH0616582 A JP H0616582A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- chlorobenzene
- hours
- aryl
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、各種ポリマー原料とし
て有用なフェノール類の製造法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing phenols useful as various polymer raw materials.
【０００２】[0002]
【従来の技術】アリールハロゲン化物を水の存在下、気
相において加水分解してアリール水酸化物に転化する方
法は、古くからフェノール合成に於けるラシヒ法の後段
反応として知られている。このアリールハロゲン化物の
加水分解の触媒としては、銅を含むリン酸カルシウムア
パタイト（米国特許第３１４８２２２号明細書、米国特
許第２９８８５７３号明細書）、銅を含むリン酸ジルコ
ニウム（特公昭５１ー６１０８号公報）、希土類金属リ
ン酸塩及び銅を含んだ希土類金属リン酸塩（特開昭４７
ー２７９３６号公報）等が知られている。2. Description of the Related 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-reaction of the Raschig method in phenol synthesis. As a catalyst for the hydrolysis of the aryl halide, calcium phosphate apatite containing copper (US Pat. No. 3,148,222, US Pat. No. 2,988,573) and zirconium phosphate containing copper (Japanese Patent Publication No. 51-6108). , Rare earth metal phosphates and rare earth metal phosphates containing copper
No. 27936) is known.
【０００３】これまでの触媒は、活性が低いため高転化
率を得るためには、５００℃以上の高温で反応をさせる
か、叉は非常に低い空間速度で反応させる必要があっ
た。さらに、これらの触媒は、反応中の活性低下が著し
く、触媒の再生も困難であった。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】[0004]
【発明が解決しようとする課題】本発明は、高活性でか
つ活性低下が少なく、再生の容易な触媒を用いるアリー
ル水酸化物の製造方法を提供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing an aryl hydroxide which uses a catalyst which is highly active, has a small decrease in activity, and is easily regenerated.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記目的
を達成すべく鋭意検討した結果、周期律表上のＩＢ族の
金属を含有する結晶性アルミノシリケートＡＺ−１が高
活性かつ活性低下が少なく、触媒再生が容易であること
を見い出し、本発明を完成するに至った。すなわち、本
発明は以下のとおりである。 １．アリールハロゲン化物を水の存在下、気相において
加水分解してアリール水酸化物に転化する際に、触媒と
して周期律表ＩＢ族の金属を含有する結晶性アルミノシ
リケートＡＺ−１を用いることを特徴とするアリール水
酸化物の製造方法。 ２．周期律表ＩＢ族の金属が、銅であることを特徴とす
る上記１に記載のアリール水酸化物の製造方法。 本発明に用いられる結晶性アルミノシリケートとは、Ｓ
i Ｏ4 とＡｌＯ4 とが酸素原子を介して交さ結合してい
る剛性の三次元構造を有する無機結晶体である。この中
のアルミニウム原子とケイ素原子の和と酸素原子との比
は、１：２であり、またアルミニウムを含有する四面体
の電子価は、結晶内に種々のカチオンを含有する事によ
って平衡が保たれている。この結晶性アルミノシリケー
トはこれまでに多くのものが知られているが、本発明に
用いられるのは結晶性アルミノシリケートＡＺ−１であ
る。このＡＺ−１とは、特開昭５９−１２８２１０号公
報及び米国特許第３８３２４４９号明細書に記載されて
いる本研究者らが開発した新規な結晶性アルミノシリケ
ートである。Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that crystalline aluminosilicate AZ-1 containing a metal of Group IB on the periodic table has high activity and activity. The inventors have found that the reduction is small and catalyst regeneration is easy, and completed the present invention. That is, the present invention is as follows. 1. A crystalline aluminosilicate AZ-1 containing a metal of Group IB of the periodic table is used 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. And a method for producing an aryl hydroxide. 2. The method for producing an aryl hydroxide according to the above 1, wherein the metal of Group IB of the periodic table is copper. The crystalline aluminosilicate used in the present invention is S
It is an inorganic crystal body having a rigid three-dimensional structure in which i O 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 is a novel crystalline aluminosilicate developed by the present inventors, which is described in JP-A-59-128210 and US Pat. No. 3,832,449.
【０００６】本発明に用いられる結晶性アルミノシリケ
ートＡＺ−１は、周期律表のＩＢ族の金属を含有する必
要がある。周期律表上のＩＢ族とは、銅、銀、金である
が、これらの中で好ましいのは銅、銀であり、特に好ま
しいのは銅である。結晶性アルミノシリケートＡＺ−１
中に含まれるこれらの金属の状態は、カチオン、酸化
物、ハロゲン化物等の塩、還元金属のいずれの状態でも
構わないが、好ましいのはカチオンの状態である。The crystalline aluminosilicate AZ-1 used in the present invention must contain a metal of Group IB of the periodic table. Group IB on the periodic table is copper, silver and gold, of which copper and silver are preferable, and copper is particularly preferable. Crystalline aluminosilicate AZ-1
The state of these metals contained therein may be any of the states of cations, oxides, salts such as halides, and reduced metals, but the state of cations is preferred.
【０００７】これらの金属の含有量は、特に制限はない
が、あまり少ないと活性が低く、多すぎると選択性が低
くなるため、通常は結晶性アルミノシリケートＡＺ−１
に対して０．００５〜５０ｗｔ％、好ましくは０．０１
〜２０ｗｔ％、さらに好ましくは０．１〜１０ｗｔ％で
ある。結晶性アルミノシリケートＡＺ−１に、これらの
金属を含有させる方法としては、通常のイオン交換法、
含浸法等が用いられる。The content of these metals is not particularly limited, but if it is too small, the activity is low, and if it is too large, the selectivity is low. Therefore, crystalline aluminosilicate AZ-1 is usually used.
To 0.005 to 50 wt%, preferably 0.01
˜20 wt%, and more preferably 0.1 to 10 wt%. As a method of incorporating these metals into the crystalline aluminosilicate AZ-1, a usual ion exchange method,
An impregnation method or the like is used.
【０００８】本発明におけるアリールハロゲン化物と
は、例えばクロルベンゼン、ブロムベンゼン、ヨードベ
ンゼン、ジクロルベンゼン、ジブロムベンゼン、ジヨー
ドベンゼン、クロルトルエン、ブロムトルエン、ヨード
トルエン、クロルキシレン、ブロムキシレン、ヨードキ
シレン等が挙げられる。本発明における水とアリールハ
ロゲン化物の比は、通常水／アリールハロゲン化物（モ
ル比）で０．５〜１００、好ましくは１〜５０、さらに
好ましくは２〜２０である。The aryl halide in the present invention is, for example, chlorobenzene, bromobenzene, iodobenzene, dichlorobenzene, dibromobenzene, diiodobenzene, chlorotoluene, bromotoluene, iodotoluene, chlorxylene, bromoxylene, iodo. Xylene etc. are mentioned. The ratio of water to aryl halide in the present invention is usually water / aryl halide (molar ratio) of 0.5 to 100, preferably 1 to 50, more preferably 2 to 20.
【０００９】本発明におけるアリール水酸化物とは、原
料がモノハロゲン化ベンゼンの場合は、対応するヒドロ
キシベンゼンであり、原料がジハロゲン化物の場合はモ
ノヒドロキシベンゼン及び／又はジヒドロキシベンゼン
である。本発明における反応温度は、通常２５０〜６０
０℃、好ましくは３００〜５５０℃、さらに好ましくは
３５０〜５００℃である。The aryl hydroxide in the present invention is a corresponding hydroxybenzene when the raw material is a monohalogenated benzene, and monohydroxybenzene and / or dihydroxybenzene when the raw material is a dihalide. The reaction temperature in the present invention is usually 250 to 60.
The temperature is 0 ° C, preferably 300 to 550 ° C, more preferably 350 to 500 ° C.
【００１０】本発明における圧力は減圧、常圧、加圧い
ずれでも良い。The pressure in the present invention may be any of reduced pressure, normal pressure and increased pressure.
【００１１】[0011]
【実施例】以下、本発明を実施例を用いて説明する。な
お、以下の実施例、比較例における転化率、収率、選択
率は通常のガスクロマトグラフ法による分析値をもとに
求めた。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】[0012]
【実施例１】特開昭５９−１２８２１０号公報記載に従
って、ゼオライトＡＺ−１を下記の手順で合成した。
１，８ージアミノー４ーアミノメチルオクタン１０ｇ、
硫酸アルミニウム（Ａｌ2 （ＳＯ4 ）3 ・１８Ｈ2 Ｏ）
０．５ｇ、水酸化ナトリウム０．５ｇを水１５ｇにとか
し、さらにシリカゾル（３０％ＳｉＯ2 ）２０ｇを加え
て均質な溶液を得た。この溶液にかき混ぜながら２０％
硫酸を滴下してｐＨ１２に調整して均質なゲルを得た。
さらに、このゲルをミキサーに入れ１０００ｒｐｍで１
０分間混合しゲル化を促進した。このゲルをテフロン製
試験管に仕込みステンレス製耐圧容器中で１７０℃、４
８時間静置して結晶化を行った。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.
【００１３】得られた生成物を濾過、洗浄後１２０℃で
４時間乾燥、５５０℃で４時間空気中で焼成した。この
生成物はＸ線回折分析よりＡＺ−１と同定された。又、
ケイ光Ｘ線分析より求めたＳi Ｏ2 ／Ａｌ2 Ｏ3 （モル
比）は１２０であった。このＡＺ−１を１０ｗｔ％Ｃｕ
Ｃｌ2 ・２Ｈ2 Ｏ水溶液に浸漬した後、蒸発乾固し、さ
らに４５０℃で３時間空気中で焼成して、Ｃｕ担持ＡＺ
−１を調製した。この触媒のケイ光Ｘ線で測定したＣｕ
含有率は１．５ｗｔ％であった。この触媒を用い、下記
反応条件でクロルベンゼンの加水分解反応を行った。 〔反応条件〕 水／クロルベンゼン（モル比）＝３．
０、ＷＨＳＶ（クロルベンゼン基準）＝０．８ｈｒ-1、
反応温度＝４６０℃、常圧。反応開始から３〜４時間後
の結果はクロルベンゼン転化率＝１６％、フェノール選
択率＝９７％、ベンゼン選択率＝３％であった。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】[0014]
【比較例１】ＮａーＹ型ゼオライト（リンデ・デビジョ
ン社製ＳＫ−４０、Ｓi Ｏ2 ／Ａｌ 2 Ｏ3 （モル比）＝
４．６）を１５ｗｔ％ＣｕＣｌ2 ・２Ｈ2 Ｏ水溶液中で
１日イオン交換を行った。濾過、洗浄後１２０℃で４時
間乾燥したのち、４５０℃で３時間焼成してＣｕ−Ｙ型
ゼオライトを得た。ケイ光Ｘ線分析により測定したＣｕ
の含有率は１．５ｗｔ％であった。この触媒を用いて下
記反応条件でクロルベンゼンの加水分解反応を行った。 〔反応条件〕 水／クロルベンゼン（モル比）＝３．
０、ＷＨＳＶ（クロルベンゼン基準）＝３．０ｈｒ-1、
反応温度＝４５０℃、常圧。反応開始から２〜３時間の
結果は、クロルベンゼン転化率＝１．２％、フェノール
選択率＝９９％であった。[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】[0015]
【比較例２】Ｈ−モルデナイト（東洋曹達（株）製Ｓi
Ｏ2 ／Ａｌ2 Ｏ3 （モル比）＝１０）を２０ｗｔ％Ｃｕ
Ｃｌ2 ・２Ｈ2 Ｏ水溶液で１日イオン交換して、濾過、
洗浄後、１２０℃で４時間乾燥、４５０℃で３時間空気
中で焼成してＣｕーモルデナイトを得た。ケイ光Ｘ線分
析より求めたＣｕ含有量は１．０ｗｔ％であった。この
触媒を用い、下記の反応条件でクロルベンゼンの加水分
解反応を行った。 〔反応条件〕 水／クロルベンゼン（モル比）＝４．
０、ＷＨＳＶ（クロルベンゼン基準）＝１．０ｈｒー1、
反応温度＝４５０℃、常圧。反応開始から３〜４時間後
の結果は、クロルベンゼン転化率＝２．１％、フェノー
ル選択率＝９９％であった。[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】[0016]
【比較例３】特開昭４７−２７９３６号公報の記載に従
い、銅含有ＬａＰＯ4 を調製した。即ち、Ｌａ（Ｎ
Ｏ3 ）3 ・６Ｈ2 Ｏ＝２８．８ｇを水２００ｃｃに溶か
した溶液に、（ＮＨ4 ）2 ＨＰＯ4 ＝１７．６ｇを水１
００ｃｃに溶かした溶液を激しく撹拌しながら加える。
その後、アンモニア水でＰＨ＝６．０に調整して、濾
過、洗浄した後、１２０℃で２４時間乾燥、５００℃で
１６時間空気中で焼成して白色のＬａＰＯ4 粉末を得
た。このＬａＰＯ4 ＝１０ｇをＣｕ（ＮＯ3 ）2 ・３Ｈ
2 Ｏの０．２ｗｔ％水溶液２０ｃｃ中に浸漬して、蒸発
乾固した後、４５０℃で５時間空気中で焼成した。この
Ｃｕ含有ＬａＰＯ4 中のＣｕ含有率は０．０５ｗｔ％で
あった。このＣｕ含有ＬａＰＯ4 を触媒に用いて、下記
の反応条件でクロルベンゼンの加水分解反応を行った。 〔反応条件〕 水／クロルベンゼン（モル比）＝３．
０、ＷＨＳＶ（クロルベンゼン基準）＝０．８ｈｒ-1、
反応温度＝４６０℃、常圧。[Comparative Example 3] As described in JP-A-47-27936.
Copper containing LaPOFourWas prepared. That is, La (N
O3)3・ 6H2O = 28.8 g dissolved in 200 cc of water
To the solution (NHFour)2HPOFour= 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 hoursFourGot powder
It was This LaPOFour= 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 LaPOFourCu content in 0.05 wt%
there were. This Cu-containing LaPOFourUsing 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.
【００１７】反応開始から２〜３時間後の成績は、クロ
ルベンゼン転化率＝９．２％、フェノール選択率＝９
６．０％、ベンゼン選択率＝４．０％であった。この結
果と実施例１とを比較すると、この触媒の活性が低いこ
とが判る。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】[0018]
【比較例４】特公昭５１ー６１０８号公報の記載に従っ
て、銅を含むリン酸ジルコニウムを調製した。即ち、Ｚ
ｒＯＣｌ2 ・８Ｈ2 Ｏ＝２４ｇを水１００ｇに溶かし、
さらにＣｕＣｌ2 ・２Ｈ2 Ｏ＝０．６ｇを溶かした。こ
の溶液をＮａＯＨ＝８．０ｇと８５％Ｈ3 ＰＯ4 ＝１
４．８ｇを水１００ｇに溶かした溶液に加え４４時間室
温で撹拌を続けた。得られたスラリーを濾過、洗浄した
後、１１０℃で４時間乾燥、４００℃で３時間空気中で
焼成を行い銅含有リン酸ジルコニウムを得た。[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.
【００１９】この銅含有リン酸ジルコニウムを触媒に用
い、比較例３と同じ条件でクロルベンゼンの加水分解反
応を行った。反応開始から２〜３時間後の成績は、クロ
ルベンゼン転化率＝７．０％、フェノール選択率＝９
７．０％、ベンゼン選択率＝３．０％であった。この結
果と実施例とを比較すると、この触媒の活性が低いこと
が判る。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】[0020]
【発明の効果】本発明における触媒は、従来の触媒に比
べて活性が高く、かつ活性低下が小さく触媒再生が容易
である。この事は工業的に行う上で非常に有利となる。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 (2)
相において加水分解してアリール水酸化物に転化する際
に、触媒として周期律表ＩＢ族の金属を含有する結晶性
アルミノシリケートＡＺ−１を用いることを特徴とする
アリール水酸化物の製造方法。1. A crystalline aluminosilicate AZ-1 containing a metal of Group IB 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. A method for producing an aryl hydroxide, comprising:
を特徴とする請求項１記載のアリール水酸化物の製造方
法。2. The method for producing an aryl hydroxide according to claim 1, wherein the metal of Group IB of the periodic table is copper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5016178A JPH07110824B2 (en) | 1993-02-03 | 1993-02-03 | Phenol manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5016178A JPH07110824B2 (en) | 1993-02-03 | 1993-02-03 | Phenol manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0616582A true JPH0616582A (en) | 1994-01-25 |
| JPH07110824B2 JPH07110824B2 (en) | 1995-11-29 |
Family
ID=11909261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5016178A Expired - Lifetime JPH07110824B2 (en) | 1993-02-03 | 1993-02-03 | Phenol manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07110824B2 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62192330A (en) * | 1986-02-20 | 1987-08-22 | Asahi Chem Ind Co Ltd | Production of aryl hydroxide |
| JPH047039A (en) * | 1990-04-23 | 1992-01-10 | Res Assoc Util Of Light Oil | Production of catalyst |
| JPH04117338A (en) * | 1990-09-06 | 1992-04-17 | Res Assoc Util Of Light Oil | Production of aromatic hydroxide |
| JPH04117339A (en) * | 1990-09-06 | 1992-04-17 | Res Assoc Util Of Light Oil | Production of aromatic hydroxide |
| JPH04334333A (en) * | 1991-05-10 | 1992-11-20 | Res Assoc Util Of Light Oil | Production of phenols |
-
1993
- 1993-02-03 JP JP5016178A patent/JPH07110824B2/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62192330A (en) * | 1986-02-20 | 1987-08-22 | Asahi Chem Ind Co Ltd | Production of aryl hydroxide |
| JPH047039A (en) * | 1990-04-23 | 1992-01-10 | Res Assoc Util Of Light Oil | Production of catalyst |
| JPH04117338A (en) * | 1990-09-06 | 1992-04-17 | Res Assoc Util Of Light Oil | Production of aromatic hydroxide |
| JPH04117339A (en) * | 1990-09-06 | 1992-04-17 | Res Assoc Util Of Light Oil | Production of aromatic hydroxide |
| JPH04334333A (en) * | 1991-05-10 | 1992-11-20 | Res Assoc Util Of Light Oil | Production of phenols |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07110824B2 (en) | 1995-11-29 |
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| A01 | Written decision to grant a patent or to grant a registration (utility model) |
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