JPS61251633A - Production of highly pure p-tert-butylphenol - Google Patents
Production of highly pure p-tert-butylphenolInfo
- Publication number
- JPS61251633A JPS61251633A JP60070445A JP7044585A JPS61251633A JP S61251633 A JPS61251633 A JP S61251633A JP 60070445 A JP60070445 A JP 60070445A JP 7044585 A JP7044585 A JP 7044585A JP S61251633 A JPS61251633 A JP S61251633A
- Authority
- JP
- Japan
- Prior art keywords
- mixed gas
- reaction
- activated clay
- butylphenol
- inert gas
- 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.)
- Pending
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
【発明の詳細な説明】
芝！土！
本発明は、高純度のｐ −ｔｅｒｔ−ブチルフェノール
（以下ＰＴＢＰと略記することがある）の製造方法に関
するものである。[Detailed description of the invention] Shiba! soil! The present invention relates to a method for producing highly pure p-tert-butylphenol (hereinafter sometimes abbreviated as PTBP).
本発明の方法によれば安価なイソブチレンおよびｎ−ブ
テン類を主成分とする混合ガスを原料として、工業的に
簡便にしかも分離・精製の困難な副生物であるｐ−５ｅ
ｅ−ブチルフェノール（以下ＰＳＢＰと略記することが
ある）及びｏ −ｓｅａ −ブチルフェノール（以下０
８ＢＰと略記することがある）の生成を抑制して、目的
とする高純度のｐ −ｔｅｒｔ−ブチルフェノールを高
選択率で収率よく製造することができる。According to the method of the present invention, p-5e, which is a by-product that is difficult to separate and purify, can be produced industrially easily using an inexpensive mixed gas containing isobutylene and n-butenes as the main components.
e-butylphenol (hereinafter sometimes abbreviated as PSBP) and o-sea-butylphenol (hereinafter 0
(sometimes abbreviated as 8BP) can be suppressed, and the desired high-purity p-tert-butylphenol can be produced with high selectivity and good yield.
ｐ −ｔｅｒｔ−ブチルフェノールは、可塑剤、樹脂、
香料、重合禁止剤、酸化防止剤、分子量調整剤等の原料
となるなど有用な物質である。p-tert-butylphenol is used as a plasticizer, resin,
It is a useful substance as a raw material for fragrances, polymerization inhibitors, antioxidants, molecular weight regulators, etc.
先行技術
イソブチレンとフェノールを触媒の存在下反応させてＰ
ＴＢＰを製造することけ公知である。一方、イソブチレ
ンは高価な原料であるので安価なナフサ分解の際に得ら
れるＣ４炭化水素留分からブタジェンを除去したイソブ
チレンおよびｎ−ブテン類を主成分とする混合ガスを原
料として用いる方法も知られている（英国特許第１，０
６２，２９８号明細書及び特開昭５４−１４９３３号公
報参照）。Prior Art Isobutylene and phenol are reacted in the presence of a catalyst to produce P.
It is known to produce TBP. On the other hand, since isobutylene is an expensive raw material, it is also known that a mixed gas containing n-butenes and isobutylene, obtained by removing butadiene from the inexpensive C4 hydrocarbon fraction obtained during naphtha cracking, is used as a raw material. (British Patent Nos. 1 and 0)
(See specification No. 62,298 and Japanese Unexamined Patent Publication No. 14933/1983).
しかしながら、上記安価な原料であるイソブチレンおよ
びｎ−ブテン類を主成分とする混合ガスを用いる方法は
、触媒の調製、触媒の除去が複雑である又は分離・、精
製困難な０８ＢＰやＰＳＢＰの副生が多い等の問題点を
有するものであった。However, the method using a mixed gas mainly composed of isobutylene and n-butenes, which are inexpensive raw materials, requires complicated preparation and removal of the catalyst, or produces by-products of 08BP and PSBP that are difficult to separate and purify. This method had many problems, such as a large number of
この欠点を改良する方法として、活性白土および電子供
与体の存在下に上記の安価な混合ガスとフェノールとを
反応させ、次いで転位反応させて目的とするＰＴＢＰを
、ＰＳＢＰや０８ＢＰの副生を抑制して製造する方法が
提案された（特開昭５８−５２２３４号公報）。As a method to improve this drawback, the above-mentioned inexpensive mixed gas is reacted with phenol in the presence of activated clay and an electron donor, and then a rearrangement reaction is carried out to produce the desired PTBP while suppressing the by-products of PSBP and 08BP. A manufacturing method was proposed (Japanese Unexamined Patent Publication No. 58-52234).
しかしながら、この方法においても転位反応時に０８Ｂ
Ｐ及びＰＳＢＰが副生し、これら不純物を含むＰＴＢＰ
はその使用時において着色、固結等を起こし最終製品の
特性及び純度を低下させるなどの問題を有し、高純度Ｐ
ＴＢＰを製造するには未だ不充分と言わざるを得なかっ
た。However, even in this method, 08B
P and PSBP are produced as by-products, and PTBP contains these impurities.
When used, high-purity P has problems such as coloration, caking, etc., which reduces the properties and purity of the final product.
It had to be said that it was still insufficient for producing TBP.
又里二且ｉ
本発明は、イソブチレンおよびｎ−ブテン類を主成分と
する混合ガスとフェノールを活性白土の存在下１０〜１
２０℃の温度範囲でアルキル化反応させ、次いで５０〜
２００℃の温度範囲で転位反応すせてｐ −ｔｅｒｔ−
ブチルフェノールを製造する方法において、アルキル化
反応後に反応系から該混合ガスを除去しかつ使用した触
媒を新しい活性白土に変えて転位反応させるか又は不活
性ガスを通じながらアルキル化反応後に反応系から該混
合ガスを除去し続いて不活性ガスを通じながら転位反応
させることを特徴とする高純度ｐ −ｔｅｒｔ −ブチ
ルフェノールの製造法を提供するものである。In the present invention, a mixed gas containing isobutylene and n-butenes as main components and phenol are mixed in the presence of activated clay at 10 to 1
Alkylation reaction is carried out in a temperature range of 20°C, then 50~
The rearrangement reaction is carried out in the temperature range of 200℃.
In the method for producing butylphenol, the mixed gas is removed from the reaction system after the alkylation reaction, and the used catalyst is changed to new activated clay to carry out the rearrangement reaction, or the mixed gas is removed from the reaction system after the alkylation reaction while passing an inert gas. The present invention provides a method for producing high-purity p-tert-butylphenol, which is characterized by removing gas and then carrying out a rearrangement reaction while passing an inert gas.
】５Ｖどケｉ
本発明の方法によれば、アルキル化反応後の転位反応に
おいて目的物からの分離・精製の困難な０８ＢＰ及びＰ
ＳＢＰの生成を極めて低く抑えてＰＴＢＰを高選択率で
収率よく製造できる。According to the method of the present invention, 08BP and P, which are difficult to separate and purify from the target products in the rearrangement reaction after the alkylation reaction.
PTBP can be produced with high selectivity and high yield by suppressing the production of SBP to an extremely low level.
本発明の上記効果は、アルキル化反応後に反応系小らイ
ソブチレンおよびｎ−ブテン類を主成分とする原料混合
ガスをただ単に除去しただけでは得られない。アルキル
化反応後に反応系から該混合ガスを除去しかつ使用した
触媒を新しい活性白土に変えて転位反応させるか、又は
不活性ガスを通じながらアルキル化反応後に反応系から
該混合ガスを除去し続いて不活性ガスを通じながら転位
反応させることにより初めて本発明の効果が生じ、この
様なことは公知技術から容易に想到するものではない全
く予想できないものである。The above-mentioned effects of the present invention cannot be obtained by simply removing the reactant mixed gas containing small isobutylene and n-butenes as main components after the alkylation reaction. Either the mixed gas is removed from the reaction system after the alkylation reaction and the used catalyst is replaced with fresh activated clay to carry out the rearrangement reaction, or the mixed gas is removed from the reaction system after the alkylation reaction while passing an inert gas. The effect of the present invention occurs only by carrying out a rearrangement reaction while passing an inert gas, and such a phenomenon is completely unexpected and cannot be easily conceived from known techniques.
発明の詳細な説明
（原料混合ガス）
本発明において使用される混合ガスは、イソブチレンお
よびｎ−ブテンを主成分とするものである。具体的には
ナフサのクラッキング工程より得られるＣ４炭化水素留
分からブタジェンを除いたイソブチレンおよびｎ−ブテ
ンで、イソブチレンを２０〜６０重量％含んでいるもの
である。イソブチレン以外の成分としては、ブタン、１
−ブテン、２−ブテン、ブタジェン等を含んでいる。上
記混合ガスの使用量は、原料の一つであるフェノール１
モルに対してイソブチレンが０．２〜３モル１好ましく
は０．５〜２モルである。Detailed Description of the Invention (Raw Material Mixed Gas) The mixed gas used in the present invention contains isobutylene and n-butene as main components. Specifically, it is isobutylene and n-butene obtained by removing butadiene from a C4 hydrocarbon fraction obtained from a naphtha cracking process, and contains 20 to 60% by weight of isobutylene. Components other than isobutylene include butane, 1
- Contains butene, 2-butene, butadiene, etc. The amount of the above mixed gas used is phenol 1, which is one of the raw materials.
The amount of isobutylene per mole is 0.2 to 3 moles, preferably 0.5 to 2 moles.
（活性白土）
触媒として使用する活性白土は、含水量が３〜４０ｗｔ
＊、好ましくは５〜２０ ｗｔ％かつＨｏ （酸強度）
が−８，２以上、好ましくは−８，２〜＋１．５のもの
である。ここでＨｏ （酸強度）とは、固体表面の酸点
の能力を示す値であり、田部浩三著「酸塩基触媒ｊｐ、
１６１（１９６６）産業図書に記載されているものであ
る。(Activated clay) The activated clay used as a catalyst has a water content of 3 to 40 wt.
*, preferably 5 to 20 wt% and Ho (acid strength)
is -8.2 or more, preferably -8.2 to +1.5. Here, Ho (acid strength) is a value indicating the ability of acid sites on the solid surface, and is a value that indicates the ability of acid sites on the solid surface.
161 (1966) Sangyo Tosho.
上記含水量より少い又は酸強度の低い活性臼゛土は、０
８ＢＰが副生するので好ましくない。Activated mortar with lower water content or lower acid strength than the above is 0.
This is not preferable because 8BP is produced as a by-product.
上述の活性白土の使用量は、原料の一つであるフェノー
ルに対して０．０１〜１０ ｗｔ％、好ましくは０．５
〜Ｓ Ｖｔ優である。The amount of activated clay used is 0.01 to 10 wt%, preferably 0.5 wt%, based on phenol, which is one of the raw materials.
~S Vt excellent.
（アルキル化反応）
原料混合ガスは、活性白土とフェノールを仕込んだ反応
器に一括して仕込んでもよいが、反応に関与しないＣ４
炭化水素を除去するため連続的に通気・排気を行うのが
好ましい。反応温度は１０〜１２０℃、好ましくは３０
〜８０℃であり、反応時間は１〜１０時間程度である。(Alkylation reaction) The raw material mixed gas may be charged all at once into a reactor containing activated clay and phenol, but C4, which does not participate in the reaction,
Continuous ventilation and evacuation is preferred to remove hydrocarbons. The reaction temperature is 10-120°C, preferably 30°C.
The temperature is ~80°C, and the reaction time is about 1 to 10 hours.
また本反応は常圧または１０ ａｔｍ以下の加圧条件で
行うことができる。Further, this reaction can be carried out under normal pressure or under pressurized conditions of 10 atm or less.
（不活性ガス）
本発明の方法に用いる不活性ガスは、上記活性白土の存
在下フェノールと反応しないガスであれば特に限定され
るものではないが、通常窒素、アルゴン、０１〜４の飽
和炭化水素類などが用いられ、特には窒素が好ましいも
のである。(Inert gas) The inert gas used in the method of the present invention is not particularly limited as long as it does not react with phenol in the presence of the activated clay, but is usually nitrogen, argon, or 01-4 saturated carbonization gas. Hydrogen and the like are used, with nitrogen being particularly preferred.
（転位反応）
アルキル化反応の後に行う転位反応は、（１）アルキル
化反応液に溶存する原料混合ガスを排気又は不活性ガス
吹込み等により除去し、この反応液から使用した触媒を
分離し新しい活性白土の存在下に転位反Ｅｈすせる、又
は、（２）アルキル化反応液に不活性ガスを吹込み溶存
する原料ガスを除去し更に連続して不活性ガスを吹込み
ながら転位反応させる、
以上の方法が採れるが操作性の点で上記（２）の方法が
好ましい。(Rearrangement reaction) In the rearrangement reaction performed after the alkylation reaction, (1) the raw material mixed gas dissolved in the alkylation reaction liquid is removed by exhaust or inert gas injection, and the used catalyst is separated from this reaction liquid. Rearrangement reaction is carried out in the presence of new activated clay, or (2) an inert gas is blown into the alkylation reaction solution to remove the dissolved raw material gas, and then the rearrangement reaction is carried out while continuously blowing inert gas. Although the above methods can be used, method (2) above is preferable in terms of operability.
転位反応の温度は５０〜２００℃、好ましくは８０〜１
３０℃であり、この時間は１〜５時間程度である。The temperature of the rearrangement reaction is 50 to 200°C, preferably 80 to 1
The temperature is 30°C, and the time is about 1 to 5 hours.
尚、転位反応をさせる場合に新たに原料の−っであるフ
ェノール及びアルキル化反応時及び／又は転位反応時に
副生する。 −ｔｅｒｔ−ブチルフェノール、ジーｔｅ
ｒｔ−ブチルフェノールを反応系に追加してもよい。In addition, when the rearrangement reaction is carried out, phenol, which is a raw material, is newly produced as a by-product during the alkylation reaction and/or during the rearrangement reaction. -tert-butylphenol, dite
rt-Butylphenol may be added to the reaction system.
（精製）
転位反応後、触媒の活性白土を口側し、反応液を通常の
方法で分留すること等により目的とする高純度のＰＴＢ
Ｐｔ−［造することができる。(Purification) After the rearrangement reaction, the target high-purity PTB is obtained by placing the activated clay of the catalyst on the side and fractionating the reaction solution using a conventional method.
Pt-[can be formed.
ｕＬ
以下に実施例、比較例を挙げて本発明を更に具体的に説
明する。尚、以下の実験的中％は重量基準である。uL The present invention will be explained in more detail by giving Examples and Comparative Examples below. Note that the following experimental weight percentages are based on weight.
実施列１〜２、比較例１〜２
（アルキル化反応）
攪拌器、温度計、還流管、吹き込み管をつけた４つロフ
ラスコにフェノール： ７０．９ ｆ （７５３ｍｍｏ
ｔ）、１７％含水活性白土（−８，２（Ｈｏ （−５，
６） ： ２．３ ｆを仕込み、４０℃に昇温した。Examples 1-2, Comparative Examples 1-2 (Alkylation reaction) Phenol: 70.9 f (753 mmo
t), 17% hydrated activated clay (-8,2(Ho (-5,
6): 2.3 f was charged and the temperature was raised to 40°C.
吹き込み管より原料混合ガス（イソブタン２．３％、ｎ
−ブタン６．２％、ｎ−ブテン３４．３％、イソブチレ
ン５６．７％、ブタジェン０．１％）を８．８ｔ／ｈｒ
の流速で吹き込み６時間反応させた。各時間毎の反応液
組成を下表に示す。０８ＢＰ及びＰＳＢＰの副生は極め
て少量であった。The raw material mixed gas (isobutane 2.3%, n
-butane 6.2%, n-butene 34.3%, isobutylene 56.7%, butadiene 0.1%) at 8.8t/hr
The mixture was blown into the solution at a flow rate of 100 ml and reacted for 6 hours. The reaction solution composition for each time period is shown in the table below. By-products of 08BP and PSBP were extremely small.
（注）ＰｈＯＨ：フェノール
０ＴＢＰ ： ｏ −ｔｅｒｔ−ブチルフェノールＤＴ
ＢＰ ニジーｔｅｒｔ−ブチルフェノール（転位反応）
アルキル化反応を６時間行った反応液を用い、表ＩＫ示
す混合ガス除去方法で１２０℃、１時間転位反応を行っ
た。結果を表１に示す。(Note) PhOH: Phenol 0TBP: o-tert-butylphenol DT
BP Nizi tert-butylphenol (rearrangement reaction) Using a reaction solution that had been subjected to an alkylation reaction for 6 hours, a rearrangement reaction was carried out at 120° C. for 1 hour using the mixed gas removal method shown in Table IK. The results are shown in Table 1.
表１
比較例３
含水率２．６％の低含水量の活性白土（Ｈｏ（−８，２
）を使用し、反応時間を３時間とした以外は実施例１と
同様にアルキル化反応を行った。その結果、アルキル化
反応生成物中には０８ＢＰ：０゜３１％、ＰＳＢＰ：
０１５％の副生があった。Table 1 Comparative Example 3 Activated clay with a low water content of 2.6% (Ho(-8,2
) was used, and the alkylation reaction was carried out in the same manner as in Example 1, except that the reaction time was 3 hours. As a result, the alkylation reaction product contained 08BP: 0°31%, PSBP:
There was a by-product of 0.015%.
Claims (1)
混合ガスとフェノールを活性白土の存在下１０〜１２０
℃の温度範囲でアルキル化反応させ、次いで５０〜２０
０℃の温度範囲で転位反応させてｐ−ｔｅｒｔ−ブチル
フェノールを製造する方法において、アルキル化反応後
に反応系から該混合ガスを除去しかつ使用した触媒を新
しい活性白土に変えて転位反応させるか又は不活性ガス
を通じながらアルキル化反応後に反応系から該混合ガス
を除去し続いて不活性ガスを通じながら転位反応させる
ことを特徴とする高純度ｐ−ｔｅｒｔ−ブチルフェノー
ルの製造法。(1) Mixed gas containing isobutylene and n-butenes as main components and phenol in the presence of activated clay at 10-120%
The alkylation reaction is carried out in the temperature range of 50-20 °C.
In a method for producing p-tert-butylphenol by carrying out a rearrangement reaction in a temperature range of 0°C, the mixed gas is removed from the reaction system after the alkylation reaction, and the used catalyst is replaced with fresh activated clay and the rearrangement reaction is carried out, or A method for producing high-purity p-tert-butylphenol, which comprises performing an alkylation reaction while passing an inert gas, removing the mixed gas from the reaction system, and then carrying out a rearrangement reaction while passing an inert gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60070445A JPS61251633A (en) | 1985-04-03 | 1985-04-03 | Production of highly pure p-tert-butylphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60070445A JPS61251633A (en) | 1985-04-03 | 1985-04-03 | Production of highly pure p-tert-butylphenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61251633A true JPS61251633A (en) | 1986-11-08 |
Family
ID=13431700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60070445A Pending JPS61251633A (en) | 1985-04-03 | 1985-04-03 | Production of highly pure p-tert-butylphenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61251633A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357241C (en) * | 2002-09-12 | 2007-12-26 | 株式会社可乐丽 | Method for manufacturing 4-alkylphenols |
| US7692047B2 (en) | 2006-09-26 | 2010-04-06 | Secretary, Department Of Science & Technology | Process for the alkylation of phenols |
-
1985
- 1985-04-03 JP JP60070445A patent/JPS61251633A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357241C (en) * | 2002-09-12 | 2007-12-26 | 株式会社可乐丽 | Method for manufacturing 4-alkylphenols |
| US7692047B2 (en) | 2006-09-26 | 2010-04-06 | Secretary, Department Of Science & Technology | Process for the alkylation of phenols |
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