JPH06234683A - Production of beta-naphthol - Google Patents
Production of beta-naphtholInfo
- Publication number
- JPH06234683A JPH06234683A JP5024103A JP2410393A JPH06234683A JP H06234683 A JPH06234683 A JP H06234683A JP 5024103 A JP5024103 A JP 5024103A JP 2410393 A JP2410393 A JP 2410393A JP H06234683 A JPH06234683 A JP H06234683A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- naphthol
- catalyst
- butenylphenol
- beta
- 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.)
- Granted
Links
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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、β−ナフトールの製造
方法に関するものである。更に詳しくは、本発明は、ｐ
−ブテニルフェノールを出発原料とするβ−ナフトール
の製造方法に関するものである。β−ナフトールは、医
薬、農薬、香料、ゴム用添加剤、選鉱剤などの製造原料
として使用される。FIELD OF THE INVENTION The present invention relates to a method for producing β-naphthol. More specifically, the present invention provides p
-It relates to a method for producing β-naphthol starting from butenylphenol. β-naphthol is used as a raw material for manufacturing pharmaceuticals, agricultural chemicals, fragrances, additives for rubbers, mineral processing agents and the like.
【０００２】[0002]
【従来の技術】β−ナフトールの製造方法として、ナフ
タレンスルホン酸をアルカリ溶融に付す技術は公知であ
る（たとえば、特開昭６１−１１５０３９号公報参
照）。しかしながらこの方法には、腐食性物質である強
酸や強アルカリを多量に使用する必要があり、高価な耐
蝕性の装置材料を用いるなければならないこと、及び副
生物として大量に発生する（亜）硫酸ナトリウムを処理
する必要があり、そのための設備及び処理工程を用いな
ければならないといった問題を有しており、かかる問題
の存在は、特に産業的実施の観点からは、極めて不都合
なものであった。2. Description of the Related Art As a method for producing β-naphthol, a technique of subjecting naphthalenesulfonic acid to alkali melting is known (see, for example, JP-A-61-115039). However, this method requires the use of a large amount of corrosive substances such as strong acid and strong alkali, requires the use of expensive corrosion-resistant equipment materials, and produces a large amount of by-product (sulfurous acid). There is a problem that it is necessary to treat sodium, and equipment and a treatment process therefor must be used, and the existence of such a problem is extremely inconvenient particularly from the viewpoint of industrial implementation.
【０００３】[0003]
【発明が解決しようとする課題】かかる状況に鑑み、本
発明が解決しようとする課題は、従来の技術の問題点を
解消し、多量の腐食性物質を用いることなく、しかも大
量の副生物の発生を伴わない、新規で効率的なβ−ナフ
トールの製造方法を提供する点に存する。In view of the above situation, the problem to be solved by the present invention is to solve the problems of the prior art, to use a large amount of by-products without using a large amount of corrosive substances. It is intended to provide a novel and efficient method for producing β-naphthol that does not occur.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記の課
題を解決すべく鋭意検討の結果、本発明に到達した。す
なわち、本発明は、ｐ−ブテニルフェノールを環化脱水
素反応に付すβ−ナフトールの製造方法に係るものであ
る。The present inventors have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention relates to a method for producing β-naphthol by subjecting p-butenylphenol to a cyclodehydrogenation reaction.
【０００５】以下、詳細に説明する。本発明のｐ−ブテ
ニルフェノールにおけるブテニル基としては、１−ブテ
ニル基、２−ブテニル基又は３−ブテニル基のいずれで
もよく、これらブテニル基を有するｐ−ブテニルフェノ
ールの二種以上を混合して用いてもよい。好ましいｐ−
ブテニルフェノールは、ｐ−（２−ブテニル）フェノー
ルである。The details will be described below. The butenyl group in the p-butenylphenol of the present invention may be any of a 1-butenyl group, a 2-butenyl group and a 3-butenyl group, and two or more kinds of p-butenylphenols having these butenyl groups are mixed. You may use it. Preferred p-
Butenylphenol is p- (2-butenyl) phenol.
【０００６】本発明は、ｐ−ブテニルフェノールを環化
脱水素反応に付すことにより行われる。環化脱水素反応
にあたっては固体酸触媒、固体塩基触媒、金属酸化物触
媒又は貴金属触媒を用いることが好ましく、このことに
より目的の環化脱水素反応を効率的に推進させることが
できる。ここで、触媒の具体例としては、シリカ、アル
ミナ、シリカ−アルミナ、ボリア、ジルコニア、チタニ
ア、カルシア、マグネシア、酸化亜鉛、酸化鉄、酸化ク
ロム、酸化銅などの金属酸化物及びこれらの複合酸化
物；モレキュラーシーブ１３Ｘ、モレキュラーシーブ１
３Ｙ、モルデナイトなどの結晶性アルミノケイ酸塩及び
これらを各種の金属カチオンでイオン交換したもの；ロ
ジウム、白金、パラジウムなどの貴金属を活性炭、シリ
カ、アルミナなどの担体に担持させたもの；並びにこれ
らの混合物をあげることができる。なかでも、収率の観
点から、アルミナ、シリカ−アルミナ、ジルコニア、マ
グネシア及び酸化亜鉛が好ましい。The present invention is carried out by subjecting p-butenylphenol to a cyclodehydrogenation reaction. In the cyclization dehydrogenation reaction, it is preferable to use a solid acid catalyst, a solid base catalyst, a metal oxide catalyst or a noble metal catalyst, whereby the desired cyclization dehydrogenation reaction can be efficiently promoted. Here, specific examples of the catalyst include metal oxides such as silica, alumina, silica-alumina, boria, zirconia, titania, calcia, magnesia, zinc oxide, iron oxide, chromium oxide, and copper oxide, and composite oxides thereof. ; Molecular sieve 13X, molecular sieve 1
Crystalline aluminosilicates such as 3Y and mordenite, and those ion-exchanged with various metal cations; Noble metals such as rhodium, platinum and palladium supported on carriers such as activated carbon, silica and alumina; and mixtures thereof. Can be raised. Among them, alumina, silica-alumina, zirconia, magnesia and zinc oxide are preferable from the viewpoint of yield.
【０００７】環化脱水素反応の反応温度は３００〜７０
０℃が好ましく、更に好ましくは４００〜６００℃であ
る。反応温度が低すぎる場合には目的の環化脱水素反応
の進行が十分ではなく、一方反応温度が高すぎる場合に
は好ましくない副反応が増加することがある。環化脱水
素反応の反応圧力は２０気圧以下が好ましく、更に好ま
しくは１０気圧以下である。反応圧力が高すぎる場合に
はｐ−ブテニルフェノールの側鎖に水素添加反応が生じ
ることがある。なお、反応は気相下に実施することが、
反応の進行上、好ましい。反応原料であるｐ−ブテニル
フェノールの供給速度としては、液空塔速度（すなわ
ち、触媒１リットルあたり、１時間あたりの原料供給速
度であり、ｈｒ-1単位で表される）で０．０１〜１０ｈ
ｒ-1が好ましい。反応原料であるｐ−ブテニルフェノー
ルは予熱器で気化された後反応容器に送られるが、この
とき窒素、アルゴンなどの不活性ガス及び／又はベンゼ
ン、フェノールなどの芳香族炭化水素、脂環族炭化水
素、脂肪族炭化水素などの有機溶媒でｐ−ブテニルフェ
ノールを希釈した後反応容器に供給してもよい。環化脱
水素反応により得られた反応混合物から目的のβ−ナフ
トールを回収するには、たとえば通常の蒸留、晶析など
の方法を用いればよい。The reaction temperature of the cyclodehydrogenation reaction is 300 to 70.
0 degreeC is preferable, More preferably, it is 400-600 degreeC. If the reaction temperature is too low, the desired cyclodehydrogenation reaction does not proceed sufficiently, while if the reaction temperature is too high, undesirable side reactions may increase. The reaction pressure of the cyclodehydrogenation reaction is preferably 20 atm or less, more preferably 10 atm or less. If the reaction pressure is too high, a hydrogenation reaction may occur on the side chain of p-butenylphenol. In addition, the reaction may be carried out in the gas phase,
It is preferable for the progress of the reaction. The feed rate of p-butenylphenol, which is the reaction raw material, is 0.01 in terms of liquid superficial velocity (that is, the feed rate of the raw material per 1 liter of the catalyst per hour, which is expressed in hr −1 unit). -10h
r -1 is preferred. The reaction raw material, p-butenylphenol, is vaporized by a preheater and then sent to a reaction vessel. At this time, an inert gas such as nitrogen or argon and / or an aromatic hydrocarbon such as benzene or phenol or an alicyclic group is used. The p-butenylphenol may be diluted with an organic solvent such as hydrocarbon or aliphatic hydrocarbon and then supplied to the reaction vessel. In order to recover the desired β-naphthol from the reaction mixture obtained by the cyclodehydrogenation reaction, for example, a usual method such as distillation or crystallization may be used.
【０００８】[0008]
【実施例】以下に本発明を実施例によって説明する。 実施例１ 酸化亜鉛触媒（１０〜２４メッシュ）１５．０ｇを縦型
石英製反応管（長さ４００ｍｍ、内径１２ｍｍ）に充填
し、昇温した。その後、反応管の上部から、ｐ−（２−
ブテニル）フェノールを２０重量％含有するトルエン溶
液を気化し、毎時３．５ｇで供給した。このとき、毎分
２０ｍｌの窒素ガスを同時に供給した。反応管出口ガス
を冷却して液を回収し、その成分をガスクロマトグラフ
により分析した結果、ｐ−（２−ブテニル）フェノール
転化率９８．４％（反応したｐ−（２−ブテニル）フェ
ノール／供給したｐ−（２−ブテニル）フェノール×１
００）、β−ナフトール選択率（生成したβ−ナフトー
ル（モル）／反応したｐ−（２−ブテニル）フェノール
（モル）×１００）７０．５％、低沸点物選択率（生成
した低沸点物（ｇ）／反応したｐ−（２−ブテニル）フ
ェノール（ｇ）×１００）５．５％及び高沸点物選択率
（生成した高沸点物（ｇ）／反応したｐ−（２−ブテニ
ル）フェノール（ｇ）×１００）２４．０％を得た。こ
こで、低沸点物とはフェノール、ｐ−クレゾール、ｐ−
エチルフェノールなどであり、高沸点物とは構造不明な
タール分や炭素質堆積物などである。EXAMPLES The present invention will be described below with reference to examples. Example 1 A vertical quartz reaction tube (length 400 mm, inner diameter 12 mm) was filled with 15.0 g of a zinc oxide catalyst (10 to 24 mesh), and the temperature was raised. After that, p- (2-
A toluene solution containing 20% by weight of butenyl) phenol was vaporized and fed at 3.5 g / h. At this time, 20 ml / minute of nitrogen gas was simultaneously supplied. The reaction tube outlet gas was cooled to collect the liquid, and its components were analyzed by gas chromatography. As a result, the p- (2-butenyl) phenol conversion rate was 98.4% (reacted p- (2-butenyl) phenol / supply P- (2-butenyl) phenol x 1
00), β-naphthol selectivity (produced β-naphthol (mol) / reacted p- (2-butenyl) phenol (mol) × 100) 70.5%, low boiling substance selectivity (produced low boiling substance) (G) / reacted p- (2-butenyl) phenol (g) × 100) 5.5% and high-boiling-point selectivity (generated high-boiling point (g) / reacted p- (2-butenyl) phenol (G) × 100) 24.0% was obtained. Here, the low boiling point substances are phenol, p-cresol, p-
Such as ethylphenol, high boiling point substances are tar and carbonaceous deposits of unknown structure.
【０００９】実施例２〜５ 表１の条件としたこと以外は実施例１と同様に行った。
結果を表１に示した。Examples 2 to 5 The same procedure as in Example 1 was carried out except that the conditions shown in Table 1 were used.
The results are shown in Table 1.
【００１０】[0010]
【表１】 −−−−−−−−−−−−−−−−−−−−−−−−−−−−− 実 施 例 1 2 3 4 5 反応条件 触媒 *1 A B C D E 温度 ℃ 500 550 550 550 550 反応結果 転化率 % *2 98.4 99.9 99.9 99.9 99.8 選択率 % *3 β−ナフトール 70.5 36.9 52.0 59.1 56.7 低沸点物 5.5 24.3 14.7 14.7 20.4 高沸点物 24.0 38.8 33.3 26.2 23.9 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−[Table 1] −−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 1 2 3 4 5 Reaction conditions Catalyst * 1 ABCDE Temperature ℃ 500 550 550 550 550 Reaction results Conversion rate% * 2 98.4 99.9 99.9 99.9 99.8 Selectivity% * 3 β-naphthol 70.5 36.9 52.0 59.1 56.7 Low boiling point 5.5 24.3 14.7 14.7 20.4 High boiling point 24.0 38.8 33.3 26.2 23.9 −−−−− −−−−−−−−−−−−−−−−−−−−−−−−
【００１１】＊１ 触媒 Ａ：酸化亜鉛 Ｂ：マグネシア Ｃ：アルミナ Ｄ：ジルコニア Ｅ：ロジウム／アルミナ ＊２ 転化率：ｐ−（２−ブテニル）フェノール転化率 ＊３ 選択率 β−ナフトール：β−ナフトール選択率 低沸点物：低沸点物選択率 高沸点物：高沸点物選択率* 1 catalyst A: zinc oxide B: magnesia C: alumina D: zirconia E: rhodium / alumina * 2 conversion: p- (2-butenyl) phenol conversion * 3 selectivity β-naphthol: β-naphthol Selectivity Low boiling point: Low boiling point selectivity High boiling point: High boiling point selectivity
【００１２】[0012]
【発明の効果】以上説明したとおり、本発明により、多
量の腐食性物質を用いることなく、しかも大量の副生物
の発生を伴わない、新規で効果的なβ−ナフトールの製
造方法を提供することができた。As described above, the present invention provides a novel and effective method for producing β-naphthol, which does not use a large amount of corrosive substances and does not generate a large amount of by-products. I was able to.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 23/46 ３１１ Ｃ０７Ｃ 37/06 8930−4Ｈ // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location B01J 23/46 311 C07C 37/06 8930-4H // C07B 61/00 300
Claims (3)
応に付すβ−ナフトールの製造方法。1. A method for producing β-naphthol, which comprises subjecting p-butenylphenol to a cyclodehydrogenation reaction.
固体塩基触媒、金属酸化物触媒又は貴金属触媒を用いる
請求項１記載の方法。2. A solid acid catalyst in the cyclodehydrogenation reaction,
The method according to claim 1, wherein a solid base catalyst, a metal oxide catalyst or a noble metal catalyst is used.
温度３００〜７００℃であり、反応圧力２０気圧以下で
ある請求項１記載の方法。3. The method according to claim 1, wherein the conditions for the cyclodehydrogenation reaction are a reaction temperature of 300 to 700 ° C. under a gas phase and a reaction pressure of 20 atm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5024103A JP2830673B2 (en) | 1993-02-12 | 1993-02-12 | Method for producing β-naphthol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5024103A JP2830673B2 (en) | 1993-02-12 | 1993-02-12 | Method for producing β-naphthol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06234683A true JPH06234683A (en) | 1994-08-23 |
| JP2830673B2 JP2830673B2 (en) | 1998-12-02 |
Family
ID=12129023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5024103A Expired - Fee Related JP2830673B2 (en) | 1993-02-12 | 1993-02-12 | Method for producing β-naphthol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2830673B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9087476B2 (en) | 2000-01-17 | 2015-07-21 | Semiconductor Energy Laboratory Co., Ltd. | Display system and electrical appliance |
-
1993
- 1993-02-12 JP JP5024103A patent/JP2830673B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9087476B2 (en) | 2000-01-17 | 2015-07-21 | Semiconductor Energy Laboratory Co., Ltd. | Display system and electrical appliance |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2830673B2 (en) | 1998-12-02 |
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