JPS5936892B2 - Method for recovering useful substances from cumene process phenol distillation residue - Google Patents
Method for recovering useful substances from cumene process phenol distillation residueInfo
- Publication number
- JPS5936892B2 JPS5936892B2 JP52000356A JP35677A JPS5936892B2 JP S5936892 B2 JPS5936892 B2 JP S5936892B2 JP 52000356 A JP52000356 A JP 52000356A JP 35677 A JP35677 A JP 35677A JP S5936892 B2 JPS5936892 B2 JP S5936892B2
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- cumene
- distillation residue
- methylstyrene
- useful substances
- 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.)
- Expired
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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は、クメン法フェノール製造において、アセトン
、フェノールを蒸留分離した残渣から、クメン、α−メ
チルスチレン、フェノールなどの有用物質を回収する方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for recovering useful substances such as cumene, α-methylstyrene, and phenol from the residue obtained by distilling and separating acetone and phenol in the production of phenol using the cumene process.
クメン法フェノールの製造法は、ベンゼンとプロピレン
とからクメンをつくり、これを酸化してクメンハイドロ
バーオキサイドを得て、ついでこれを酸分裂してアセト
ンとともにフェノールを得るものである。この製造工程
において、ジメチルフェニルカルビノール、アセトフェ
ノン、α−メチルスチレン、クミルフエノール、α−メ
チルスチレン２量体などの副生を伴いクメン法フェノー
ル製造の原単位を低下させる原因となつている。したが
つて、クメンハイドロパーオキサイドの酸分裂後の生成
物を蒸留してアセトンとフェノールを分離した後の残渣
（以下、フェノール蒸留残渣と呼称する）中の副生物か
ら有用物質を効率的に回収することが極めて重要である
。従来、このフェノール蒸留残渣を熱分解して、クメン
、α−メチルスチレン、フェノールなどの有用物質の回
収が行なわれてきたが、従来法による熱分解は、分解に
長時間を要し、回収量も少ないなどの欠点があつた。The cumene method for producing phenol involves producing cumene from benzene and propylene, oxidizing it to obtain cumene hydroperoxide, and then splitting it with an acid to obtain phenol along with acetone. In this production process, dimethylphenyl carbinol, acetophenone, α-methylstyrene, cumylphenol, α-methylstyrene dimer, and other by-products are produced, which causes a reduction in the basic unit of production of phenol using the cumene process. Therefore, useful substances can be efficiently recovered from by-products in the residue (hereinafter referred to as phenol distillation residue) after distilling the product after acid splitting of cumene hydroperoxide to separate acetone and phenol. It is extremely important to do so. Conventionally, this phenol distillation residue has been thermally decomposed to recover useful substances such as cumene, α-methylstyrene, and phenol, but thermal decomposition using conventional methods requires a long time for decomposition, and the amount recovered is There were some drawbacks, such as the lack of
本発明者らは、フェノール蒸留残渣の効果的な熱分解方
法について種々検討を行なつた結果、フェノール蒸留残
渣の熱分解にあたり触媒として、少量のアルミナ系触媒
またはシリカ−アルミナ系触媒を添加することにより、
さらにこれらの触媒に酸を共存させることにより、分解
に要する時間を著しく短縮し、かつクメン、α−メチル
スチレン、フェノールなどの有用物質を効率的に回収で
きることを見い出し、本発明を完成した。The present inventors have conducted various studies on effective thermal decomposition methods for phenol distillation residue, and have found that a small amount of alumina-based catalyst or silica-alumina-based catalyst is added as a catalyst during thermal decomposition of phenol distillation residue. According to
Furthermore, they discovered that by coexisting an acid with these catalysts, the time required for decomposition can be significantly shortened, and useful substances such as cumene, α-methylstyrene, and phenol can be efficiently recovered, and the present invention has been completed.
すなわち、本発明は、フエノール蒸留残渣に、少量のア
ルミナ系触媒またはシリカ−アルミナ系触媒を添加し２
００〜３５０℃に加熱して熱分解することを特徴とする
、クメン法フエノール蒸留残渣から、有用物質を回収す
る方法であり、少量のアルミナ触媒またはシリカ−アル
ミナ系触媒に酸を共存させるとさらに効率的な回収方法
である。That is, the present invention adds a small amount of alumina catalyst or silica-alumina catalyst to the phenol distillation residue.
This is a method for recovering useful substances from the phenol distillation residue of the cumene process, which is characterized by thermal decomposition by heating to 00 to 350°C. This is an efficient collection method.
本発明の方法によれば、フエノール蒸留残渣の熱分解に
要する時間は、従来法にくらべ著しく短縮され、フエノ
ール蒸留残渣中の、ジメチルフエニルカルビノール、α
−メチルスチレン２量体およびクミルフエノールなどは
、効率的にα−メチルスチレンに転化し、すなわち、ジ
メチルフエニルカルビノールは脱水されてα−メチルス
チレンに、α−メチルスチレン２量体は解重合してα−
メチルスチレンに、またクミルフエノールはフエノール
とα−メチルスチレンに分解され、主としてα−メチル
スチレン、フエノールおよびクメンを高い収量で回収す
ることができる。本発明に用いられる触媒は、アルミナ
系またはシリカ−アルミナ系であり、アルミナ系触媒と
しては、γ−アルミナが良く、シリカ−アルミナ系触媒
としては、石油クラツキング用に市販されているシリカ
−アルミナ触媒、酸性白土または合成ゼオライトなどが
使用され、具体的には、ＳｉＯ２と：Ａｌ２Ｏ３が５０
：５０〜９０：１０のものである。According to the method of the present invention, the time required for thermal decomposition of phenol distillation residue is significantly shortened compared to the conventional method, and dimethylphenyl carbinol, α
- Methylstyrene dimer, cumylphenol, etc. are efficiently converted to α-methylstyrene, that is, dimethylphenyl carbinol is dehydrated to α-methylstyrene, and α-methylstyrene dimer is decomposed. Polymerizes to α-
Cumylphenol is decomposed into phenol and α-methylstyrene, and mainly α-methylstyrene, phenol, and cumene can be recovered in high yields. The catalyst used in the present invention is an alumina-based or a silica-alumina-based catalyst. As an alumina-based catalyst, γ-alumina is preferable, and as a silica-alumina-based catalyst, a silica-alumina catalyst commercially available for petroleum cracking is used. , acid clay or synthetic zeolite, etc. are used, specifically, SiO2 and: Al2O3 are 50
:50 to 90:10.
これらの触媒の使用量は、フエノール蒸留残渣に対して
、通常、０．５〜１０ｗｔ％の範囲であり、好ましくは
、２〜５ｗｔ％の範囲である。これらの触媒の添加によ
りフエノール蒸留残渣の熱分解は、効率的に行なわれる
が、酸を共存させると、熱分解の効率はさらに向上する
。The amount of these catalysts used is usually in the range of 0.5 to 10 wt%, preferably in the range of 2 to 5 wt%, based on the phenol distillation residue. By adding these catalysts, the phenol distillation residue is efficiently thermally decomposed, but when an acid is present, the thermal decomposition efficiency is further improved.
酸としては、硫酸、燐酸などの無機酸、またはパラトル
エンスルホン酸などの有機酸を使用する。酸の使用量は
、フエノール蒸留残渣に対して、通常、０．１〜３ｗｔ
％の範囲であり、好ましくは、０．３〜０．８ｗｔ７０
である。本発明の方法において、反応温度は、２００〜
３５０℃の範囲、好ましくは、２４０〜３１０℃の範囲
であり、反応圧力は、常圧もしくは加圧のいずれでも良
いが、常圧下の操作が工業的に有利である。As the acid, an inorganic acid such as sulfuric acid or phosphoric acid, or an organic acid such as para-toluenesulfonic acid is used. The amount of acid used is usually 0.1 to 3 wt based on the phenol distillation residue.
% range, preferably 0.3 to 0.8wt70
It is. In the method of the present invention, the reaction temperature is from 200 to
The reaction temperature is in the range of 350°C, preferably in the range of 240 to 310°C, and the reaction pressure may be either normal pressure or increased pressure, but operation under normal pressure is industrially advantageous.
本発明の方法は、回分操作、連続操作のいずれでも実用
できるものであり、本方法によりフエノール蒸留残渣か
ら、α−メチルスチレン、フエノール、クメンなどの有
用物質が効率的に回収できるためフエノール製造の原単
位が著しく向上するとともに、分解時間の短縮により装
置の小型化が可能となり、本発明の方法の工業的価値は
大きい。The method of the present invention can be put to practical use in either batch or continuous operation, and useful substances such as α-methylstyrene, phenol, and cumene can be efficiently recovered from the phenol distillation residue, making it suitable for phenol production. The method of the present invention has great industrial value because the basic unit is significantly improved and the decomposition time is shortened, making it possible to downsize the apparatus.
以下、実施例および比較例により本発明の方法をを具体
的に説明する。なお、実施例中の触媒および酸のＷｔ７
Ｏはフエノール蒸留残渣に対するものである。実施例
１
ガラス製の３００ｍｔのリービヒ冷却管付蒸留フラスコ
にフエノール蒸留残渣１５０．０９（フエノール蒸留残
渣は、フエノール３７．８７９、アセトフエノン４０．
０４９、ジメチルフエニルカルビノール１４．１３９、
α−メチルスチレン２量体１５．０８９、オルトクミル
フエノール４．７９９、パラクミルフエノール２４．３
２９、未知物質４，１０９および重質物９．６７９であ
る）を入れ、さらに粉状シリカ−アルミナ触媒（ＳｉＯ
２８４〜８６％、Ａｌ２Ｏ３ｌ４〜１６％）７．５９（
５．０ｗｔ％）を添加し、撹拌しながら徐々に加熱して
、最終的には３４０℃まで加熱した。The method of the present invention will be specifically explained below using Examples and Comparative Examples. In addition, Wt7 of the catalyst and acid in the examples
O is for phenol distillation residue. Example
1 Phenol distillation residue 150.09% in a glass distillation flask with a 300mt Liebig condenser (the phenol distillation residue contains phenol 37.879% and acetophenone 40.09%).
049, dimethylphenyl carbinol 14.139,
α-methylstyrene dimer 15.089, orthocumylphenol 4.799, paracumylphenol 24.3
29, unknown substance 4,109 and heavy substance 9,679), and then powdered silica-alumina catalyst (SiO
284-86%, Al2O3l4-16%) 7.59 (
5.0 wt%) was added thereto, and the mixture was gradually heated while stirring, and finally heated to 340°C.
約４時間を要して加熱し、留出・物を得た。留出量は、
原料に対し７７．８ｗｔ７０の１１６．７９であり、留
出物をガスクロマトグラフイで分析した結果、留出物は
、クメン１１．８４ｆ！、α−メチルスチレン３０．２
５９、フエノール３８．３６９、アセトフエノン２５．
４５９、その他１０．７７であつた。比較例 １
実施例１で使用したものと同一のフエノール蒸留残渣１
５０．０ｇを触媒を添加しないで徐々に加熱して最．終
的に３４０℃まで加熱した。It took about 4 hours to heat and a distillate was obtained. The distillate amount is
It was 116.79 which is 77.8wt70 with respect to the raw material, and as a result of analyzing the distillate by gas chromatography, the distillate was cumene 11.84f! , α-methylstyrene 30.2
59, phenol 38.369, acetophenone 25.
459, others 10.77. Comparative Example 1 Phenol distillation residue 1 same as that used in Example 1
50.0g was gradually heated without adding a catalyst until it reached the maximum temperature. Finally, it was heated to 340°C.
この間１４．５時間を要し、留出量は原料に対して６６
．９ｗｔ％の１００．４ｆ１であり、留出物はガスクロ
マトグラフイによる分析の結果、クメン１５．７０９、
α−メチルスチレン１７．６７９、フエノール３１．６
５９、アセトフエノン２０．９２９、その他１４．４６
９であつた。実施例 ２
実施例１と同じ方法で同一のフエノール蒸留残渣１５０
．０ｇに粉伏γ−アルミナ触媒７．５９（５．０ｗｔ％
）を加え、撹拌しながら徐々に加熱して最終的に３２７
℃まで加熱した。During this time, 14.5 hours were required, and the distillation amount was 66% compared to the raw material.
．． The distillate was analyzed by gas chromatography and found to be cumene 15.709,
α-methylstyrene 17.679, phenol 31.6
59, acetophenone 20.929, others 14.46
It was 9. Example 2 The same phenol distillation residue 150 was prepared in the same manner as in Example 1.
．． 0g powdered γ-alumina catalyst 7.59 (5.0wt%
) and gradually heat while stirring until the final temperature is 327.
Heated to ℃.
加熱に要した時間は３，５時間であつた。留出量は、原
料に対して８０．７ｗｔ％の１２１．１ｇであり、留出
物は、ガスクロマトグラフイによる分析の結果、クメン
７．９７９、α−メチルスチレン２７．５４ｇ、フエノ
ール３７．１２ｆ１１アセトフエノン２５．２４９、未
知物質９．２５９および重質物１３．８９９であつた。
実施例 ３実施例１と同じ方法で同一のフエノール蒸留
残渣１５０．０ｆ１に粉状シリカ−アルミナ触媒（Ｓｉ
Ｏ２８４〜８６７０．ｓＡ１２０３１４〜１６７０）７
．５９（５．０ｗｔ７０）を加え、さらにｐ−トルエン
スルホン酸１．２ｇ（０．８ｗｔ％）を添加し、撹拌し
ながら徐々に加熱して 終的に３４５℃まで加熱した。The time required for heating was 3.5 hours. The amount of distillate was 121.1 g, which is 80.7 wt% based on the raw material, and as a result of analysis by gas chromatography, the distillate was 7.979 cumene, 27.54 g α-methylstyrene, and 37.12 g phenol. The amounts were 25.249 for acetophenone, 9.259 for unknown substances, and 13.899 for heavy substances.
Example 3 A powdered silica-alumina catalyst (Si
O284-8670. sA120314-1670)7
．． 59 (5.0 wt 70) was added thereto, and further 1.2 g (0.8 wt %) of p-toluenesulfonic acid was added, and the mixture was gradually heated while stirring to finally reach 345°C.
約２．７５時間を要し留出物を得た。留出量は、原料に
対して８０．９ｗｔ％の１２１．３であり、留出物は、
ガスクロマトグラフイによる分析の結果から、クメン３
．４１ｇ、α−メチルスチレン４７．６７９、フエノー
ル４１．８６９、アセトフエノン２０．２７９、その他
８．０９９であつた。実施例 ４
実施例１と同じ方法で同一のフエノール蒸留残渣１５０
．０ｇに粉状シリカ−アルミナ触媒（ＳｉＯ２８４〜８
６％、Ａｌ２Ｏ３ｌ４〜１６％）７．５ｇ（５．０ｗｔ
７０）をカロえ、さらに硫酸０．４９（０．３ｗｔ％）
を添加し、撹拌しながら徐々に加熱して最終的に３４０
℃まで加熱した。It took about 2.75 hours to obtain a distillate. The distillate amount was 121.3 which is 80.9wt% based on the raw material, and the distillate was
From the results of analysis by gas chromatography, cumene 3
．． 41 g, α-methylstyrene: 47.679, phenol: 41.869, acetophenone: 20.279, and others: 8.099. Example 4 The same phenol distillation residue 150 was prepared in the same manner as in Example 1.
．． Powdered silica-alumina catalyst (SiO284~8
6%, Al2O3l4~16%) 7.5g (5.0wt
70) and further added 0.49 (0.3 wt%) of sulfuric acid.
and gradually heated while stirring until the final temperature reached 340℃.
Heated to ℃.
Claims (1)
アセトンを蒸留分離した残渣を熱分解するにあたり、ア
ルミナ系触媒またはシリカ−アルミナ系触媒の存在下に
熱分解することを特徴とする、クメン法フェノール蒸留
残渣から、クメン、α−メチルスチレン、フェノールな
どの有用物質を回収する方法。 ２ クメン法フェノールの製造において、フェノール、
アセトンを蒸留分離した残渣を熱分解するにあたり、ア
ルミナ系触媒またはシリカ−アルミナ系触媒と酸の共存
下に熱分解することを特徴とする、クメン法フェノール
蒸留残渣から、クメン、α−メチルスチレン、フェノー
ルなどの有用物質を回収する方法。[Claims] 1. In the production of phenol by the cumene process, phenol,
Cumene, α-methylstyrene, phenol, etc. are extracted from the phenol distillation residue by the cumene method, which is characterized by thermally decomposing the residue obtained by distilling and separating acetone in the presence of an alumina-based catalyst or a silica-alumina-based catalyst. method of recovering useful substances. 2 In the production of phenol using the cumene method, phenol,
Cumene, α-methylstyrene, A method to recover useful substances such as phenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52000356A JPS5936892B2 (en) | 1977-01-07 | 1977-01-07 | Method for recovering useful substances from cumene process phenol distillation residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52000356A JPS5936892B2 (en) | 1977-01-07 | 1977-01-07 | Method for recovering useful substances from cumene process phenol distillation residue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5387320A JPS5387320A (en) | 1978-08-01 |
| JPS5936892B2 true JPS5936892B2 (en) | 1984-09-06 |
Family
ID=11471533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP52000356A Expired JPS5936892B2 (en) | 1977-01-07 | 1977-01-07 | Method for recovering useful substances from cumene process phenol distillation residue |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5936892B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01151898U (en) * | 1988-03-24 | 1989-10-19 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60123434A (en) * | 1983-12-06 | 1985-07-02 | Mitsui Toatsu Chem Inc | Treatment of phenol distillation residue in the cumene process |
| JPS61293936A (en) * | 1985-06-21 | 1986-12-24 | Kureha Chem Ind Co Ltd | Liquid-phase dehydration of alcohol having aromatic side-chain at alpha-site |
| JP2543074B2 (en) * | 1987-04-09 | 1996-10-16 | 三井石油化学工業株式会社 | Method for recovering useful substances from phenol distillation residue |
-
1977
- 1977-01-07 JP JP52000356A patent/JPS5936892B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01151898U (en) * | 1988-03-24 | 1989-10-19 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5387320A (en) | 1978-08-01 |
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