JP3846101B2 - Purification method of β-phenylethyl alcohol - Google Patents
Purification method of β-phenylethyl alcohol Download PDFInfo
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- JP3846101B2 JP3846101B2 JP10123199A JP10123199A JP3846101B2 JP 3846101 B2 JP3846101 B2 JP 3846101B2 JP 10123199 A JP10123199 A JP 10123199A JP 10123199 A JP10123199 A JP 10123199A JP 3846101 B2 JP3846101 B2 JP 3846101B2
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- phenylethyl alcohol
- extractive distillation
- extraction solvent
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Description
【０００１】
【発明の属する技術分野】
本発明は、β−フェニルエチルアルコールの精製方法に関するものである。更に詳しくは、本発明は、複雑な装置や操作を要することなく、単純な操作のみで、かつ効率的に、粗製β−フェニルエチルアルコ−ルから異臭成分を選択的に分離除去し、香料用の優れた香気を有する高純度β−フェニルエチルアルコ−ルを得ることができ、かつ工程中で使用した溶媒を経済的に使用できるという特徴を有するβ−フェニルエチルアルコールの精製方法に関するものである。
【０００２】
【従来の技術】
β−フェニルエチルアルコ−ルはバラ系香料として、洗浄剤、化粧品等に広く使用されている価値ある物質であり、その使用に際しては高純度でかつ香気のすぐれた製品が要求される。一般に、香料成分は本来の香気に影響を及ぼす不純物が微量でも存在すると製品価値が著しく減少するので、その精製法には特に注意が払われている。これまでに報告されているβ−フェニルエチルアルコ−ルの精製法としては、β−フェニルエチルアルコ−ルをホウ酸又は有機酸エステルに誘導して精製する方法、不純物をシリカゲルに吸着させて精製する方法、高段数の精留塔を用いて精製する方法などがある。しかしながら、これらの方法にはそれぞれ欠点があり、工業的手法としては問題点を有している。すなわちエステル化法ではβ−フェニルエチルアルコ−ルのエステル化工程及びエステルからβ−フェニルエチルアルコ−ルを遊離させる加水分解工程が必要であり、更に酸を循環使用しなければならないなど、経済的に不利である。不純物を吸着させる方法では精製効果が小さく、更にシリカゲルを再生して使用する点には問題がある。蒸留法では高段数の精留塔を用いても、沸点を近似する成分や共沸成分が存在すると満足できる品質のβ−フェニルエチルアルコ−ルを得ることは困難である。
【０００３】
【発明が解決しようとする課題】
かかる現状において、本発明が解決しようとする課題は、複雑な装置や操作を要することなく、単純な操作のみで、かつ効率的に、粗製β−フェニルエチルアルコ−ルから異臭成分を選択的に分離除去し、香料用の優れた香気を有する高純度β−フェニルエチルアルコ−ルを得ることができ、かつ工程中で使用した高価な抽出溶媒（Ａ）をリサイクルすることで経済的に使用できるという特徴を有するβ−フェニルエチルアルコールの精製方法を提供する点に存するものである。
【０００４】
【課題を解決するための手段】
すなわち、本発明は、粗製β−フェニルエチルアルコールの精製方法であって、下記の工程を含み、抽出工程で精製した抽出溶媒（Ａ）を、抽出蒸留工程へリサイクルして再使用するβ−フェニルエチルアルコールの精製方法に係るものである。
抽出蒸留工程：粗製β−フェニルエチルアルコールを、抽出溶媒（Ａ）を用いて抽出蒸留する工程であって、抽出溶媒は水と１，２−プロパンジオールとの混合比が１：９〜７：３である混合液であり、減圧下、温度５０〜２００℃、還流比０．１〜５０の条件で抽出蒸留を行い、塔頂より揮発性の高い抽出蒸留溶媒（Ａ）と異臭を有する不純物が留出し、塔底より精製されたβ−フェニルエチルアルコールを取り出す工程
抽出工程：抽出蒸留工程で使用した後の抽出溶媒（Ａ）を、別の抽出溶媒（Ｂ）を用いて抽出することにより精製する工程であって、別の抽出溶媒（Ｂ）がベンゼン、トルエン及び／又はキシレンを含む芳香族油である工程
【０００５】
【発明の実施の形態】
本発明における原料である粗製β−フェニルエチルアルコールとしては、たとえば酸化スチレンの水素還元による方法、ベンゼンと酸化エチレンとの反応による方法、フェニル酢酸の水素還元による方法及び芳香族炭化水素化合物の酸化反応による方法などから得られるものを用いることができる。
【０００６】
本発明の抽出蒸留工程は、粗製β−フェニルエチルアルコールを、抽出溶媒（Ａ）を用いて抽出蒸留する工程であって、抽出溶媒は水と１，２−プロパンジオールとの混合比が１：９〜７：３である混合液であり、減圧下、温度５０〜２００℃、還流比０．１〜５０の条件で抽出蒸留を行い、塔頂より揮発性の高い抽出蒸留溶媒（Ａ）と異臭を有する不純物が留出し、塔底より精製されたβ−フェニルエチルアルコールを取り出す工程である。
【０００７】
抽出蒸留する方法は、粗製β−フェニルエチルアルコールを、抽出溶媒（Ａ）を用いて抽出蒸留する工程であって、抽出溶媒は水と１，２−プロパンジオールとの混合比が１：９〜７：３である混合液であり、減圧下、温度５０〜２００℃、還流比０．１〜５０の条件で抽出蒸留を行い、塔頂より揮発性の高い抽出蒸留溶媒（Ａ）と異臭を有する不純物が留出し、塔底より精製されたβ−フェニルエチルアルコールを取り出すものである。
【０００８】
本発明の抽出工程は、抽出蒸留工程で使用した後の抽出溶媒（Ａ）を、別の抽出溶媒（Ｂ）を用いて抽出することにより精製する工程であって、別の抽出溶媒（Ｂ）がベンゼン、トルエン及び／又はキシレンを含む芳香族油である工程である。
【０００９】
溶媒の経済的使用及び使用済溶媒の後処理コストの削減の観点から、抽出工程で精製後の抽出溶媒（Ａ）は、抽出蒸留工程へリサイクルして再使用する。一方、異臭を有する不純物を含む抽出溶媒（Ｂ）は、たとえば芳香族プラントでの通常の蒸留等の既知の操作により容易に精製可能である。
【００１０】
抽出蒸留工程後のβ−フェニルエチルアルコールは、たとえば精留塔を用いた蒸留法などの後処理を施すことにより最終製品であるβ−フェニルエチルアルコールとすることができる。
【００１１】
【実施例】
以下、本発明を実施例により説明する。
実施例１
抽出蒸留塔は６２段、溶媒抽出搭は１０２段、精留塔は充填高さ３２メートルの充填搭を用い、抽出蒸留塔は１４０ｍｍＨｇの減圧、溶媒抽出搭は２４０ｋＰａ−Ｇの加圧、精留塔は２００ｍｍＨｇの減圧運転とした。抽出蒸留塔の搭頂より数えて２３段目より不純物６．５％を含み、異臭を有する粗製β−フェニルエチルアルコールを、１時間あたり２１０重量部の速度で抽出蒸留搭に供給した。一方、後段の抽出工程からリサイクルされる抽出溶媒（Ａ）である水と１，２プロパンジオールとの混合液（重量比 １：３）は、搭頂より数えて５０段目から１時間あたり３９０重量部の速度で供給した。このとき、異臭成分は塔頂より水と１，２プロパンジオールとの混合液とともに１時間あたり４２０重量部の速度で留出し、精製のため抽出工程に連続的に供給した。抽出工程において、抽出溶媒（Ｂ）のトルエンは、溶媒抽出搭の下段に１時間あたり１５０重量部の速度で供給した。この結果、溶媒抽出搭の搭頂からはトルエンと異臭を有する不純物を１時間あたり１８０重量部の速度で留出し、塔底からは精製された抽出溶媒（Ａ）である水と１，２プロパンジオールとの混合液（重量比 １：３）を抜出し抽出蒸留塔にリサイクルした。一方、抽出蒸留搭の搭底から取り出されるβ−フェニルエチルアルコールを精留塔の充填高さを上から数えて１４ｍより供給したところ、精留塔塔頂より精製β−フェニルエチルアルコールが１時間あたり１６５重量部速度で留出した。ここで得られたβ−フェニルエチルアルコールは、純度９９．９％を有し不快な異臭も無く香料用途に適した品質のものであった。
【００１２】
【発明の効果】
以上説明したとおり、本発明により、複雑な装置や操作を要することなく、単純な操作のみで、かつ効率的に、粗製β−フェニルエチルアルコ−ルから異臭成分を選択的に分離除去し、香料用の優れた香気を有する高純度β−フェニルエチルアルコ−ルを得ることができ、かつ工程中で使用した溶媒を経済的に使用できるという特徴を有するβ−フェニルエチルアルコールの精製方法を提供することができた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for purifying β-phenylethyl alcohol. More specifically, the present invention selectively removes off-flavor components from crude β-phenylethyl alcohol by simple operation and efficiently without requiring complicated devices and operations, and is used for perfume. The present invention relates to a method for purifying β-phenylethyl alcohol, which is characterized in that high-purity β-phenylethyl alcohol having an excellent odor can be obtained and the solvent used in the process can be economically used. .
[0002]
[Prior art]
β-Phenylethyl alcohol is a valuable substance widely used in detergents, cosmetics, etc. as a rose-based fragrance, and high purity and excellent fragrance products are required for its use. In general, special attention is paid to the refining method of a perfume ingredient, because the product value is significantly reduced if there is even a trace amount of impurities affecting the original aroma. The methods for purifying β-phenylethyl alcohol reported so far include a method of purifying β-phenylethyl alcohol by inducing it into boric acid or an organic acid ester, and purifying by adsorbing impurities on silica gel. And a purification method using a rectification tower having a high number of stages. However, each of these methods has drawbacks and has problems as an industrial method. In other words, the esterification method requires an esterification step of β-phenylethyl alcohol and a hydrolysis step of liberating β-phenylethyl alcohol from the ester, and further, an acid must be recycled. Disadvantageous. In the method of adsorbing impurities, the purification effect is small, and there is a problem in that silica gel is regenerated and used. In the distillation method, it is difficult to obtain β-phenylethyl alcohol having a satisfactory quality if a component having an approximate boiling point or an azeotropic component is present even if a rectifying column having a high number of stages is used.
[0003]
[Problems to be solved by the invention]
Under such circumstances, the problem to be solved by the present invention is to selectively select off-flavor components from crude β-phenylethyl alcohol by simple operation and efficiently without requiring complicated devices and operations. It can be separated and removed to obtain high-purity β-phenylethyl alcohol having an excellent aroma for fragrances, and can be used economically by recycling the expensive extraction solvent (A) used in the process. Therefore, the present invention provides a method for purifying β-phenylethyl alcohol having the following characteristics.
[0004]
[Means for Solving the Problems]
That is, the present invention is a method for purifying crude β-phenylethyl alcohol, which includes the following steps, and the extraction solvent (A) purified in the extraction step is recycled to the extractive distillation step for reuse. The present invention relates to a method for purifying ethyl alcohol.
Extractive distillation step: a step of subjecting crude β-phenylethyl alcohol to extractive distillation using an extraction solvent (A), wherein the extraction solvent has a mixing ratio of water and 1,2-propanediol of 1: 9 to 7: 3 is a mixed liquid, and is subjected to extractive distillation under reduced pressure at a temperature of 50 to 200 ° C. and a reflux ratio of 0.1 to 50, and has an extractive distillation solvent (A) having a high volatility from the top of the column and an odor Distills and removes purified β-phenylethyl alcohol from the bottom of the column
Extraction step: a step of purifying the extraction solvent (A) after use in the extractive distillation step by extracting with another extraction solvent (B), wherein the other extraction solvent (B) is benzene, toluene And / or an aromatic oil containing xylene
DETAILED DESCRIPTION OF THE INVENTION
Examples of the crude β-phenylethyl alcohol as a raw material in the present invention include a method by hydrogen reduction of styrene oxide, a method by reaction of benzene and ethylene oxide, a method by hydrogen reduction of phenylacetic acid, and an oxidation reaction of an aromatic hydrocarbon compound. What is obtained from the method by, etc. can be used.
[0006]
The extractive distillation step of the present invention is a step of subjecting crude β-phenylethyl alcohol to extractive distillation using an extraction solvent (A), and the extraction solvent has a mixing ratio of water and 1,2-propanediol of 1: 9-7: 3, which is an extractive distillation under reduced pressure at a temperature of 50 to 200 ° C. under a reflux ratio of 0.1 to 50, and an extractive distillation solvent (A) having a higher volatility from the top of the column. This is a step in which impurities having a bad odor are distilled off and purified β-phenylethyl alcohol is taken out from the bottom of the column.
[0007]
The method of extractive distillation is a step of extractive distillation of crude β-phenylethyl alcohol using the extraction solvent (A), wherein the extraction solvent has a mixing ratio of water and 1,2-propanediol of 1: 9 to It is a mixed solution of 7: 3, and it is subjected to extractive distillation under reduced pressure at a temperature of 50 to 200 ° C. and a reflux ratio of 0.1 to 50, so that a highly volatile extractive distillation solvent (A) and off-flavor are produced from the top of the column. The impurities which have are distilled off, and the purified β-phenylethyl alcohol is taken out from the bottom of the column.
[0008]
The extraction step of the present invention is a step of purifying the extraction solvent (A) after use in the extractive distillation step by extracting with another extraction solvent (B), which is another extraction solvent (B). Is an aromatic oil containing benzene, toluene and / or xylene.
[0009]
From the viewpoint of economical use of the solvent and reduction in post-treatment costs of the used solvent, the extraction solvent (A) after purification in the extraction step is recycled to the extractive distillation step and reused . On the other hand, the extraction solvent (B) containing impurities having a bad odor can be easily purified by known operations such as ordinary distillation in an aromatic plant.
[0010]
The β-phenylethyl alcohol after the extractive distillation step can be converted into β-phenylethyl alcohol as a final product by performing post-treatment such as a distillation method using a rectifying column.
[0011]
【Example】
Hereinafter, the present invention will be described with reference to examples.
Example 1
The extraction distillation column uses 62 stages, the solvent extraction tower uses 102 stages, the rectification tower uses a packed tower with a packing height of 32 meters, the extraction distillation tower uses a vacuum of 140 mmHg, the solvent extraction tower uses a pressure of 240 kPa-G, and rectification. The tower was operated at a reduced pressure of 200 mmHg. From the 23rd stage counted from the top of the extractive distillation column, crude β-phenylethyl alcohol containing 6.5% impurities and having a bad odor was fed to the extractive distillation tower at a rate of 210 parts by weight per hour. On the other hand, a mixed liquid (weight ratio 1: 3) of water and 1,2 propanediol, which is the extraction solvent (A) recycled from the subsequent extraction step, is 390 per hour from the 50th stage counted from the top. It was fed at a rate of parts by weight. At this time, the off-flavor component was distilled off at a rate of 420 parts by weight per hour together with a mixed solution of water and 1,2 propanediol from the top of the tower and continuously supplied to the extraction step for purification. In the extraction step, toluene as the extraction solvent (B) was supplied to the lower stage of the solvent extraction column at a rate of 150 parts by weight per hour. As a result, from the top of the solvent extraction tower, toluene and an odorous impurity were distilled off at a rate of 180 parts by weight per hour, and the purified extraction solvent (A), water, and 1,2 propane were distilled from the bottom of the tower. The mixed solution with diol (weight ratio 1: 3) was extracted and recycled to the extractive distillation column. On the other hand, when β-phenylethyl alcohol taken out from the bottom of the extractive distillation column was supplied from 14 m, counting the filling height of the rectifying column from the top, purified β-phenylethyl alcohol was supplied from the top of the rectifying column for 1 hour. Distilled at a rate of 165 parts by weight per round. The β-phenylethyl alcohol obtained here had a purity of 99.9%, had no unpleasant odor, and had a quality suitable for perfume use.
[0012]
【The invention's effect】
As described above, according to the present invention, the odorous component is selectively separated and removed from the crude β-phenylethyl alcohol by simple operation and efficiently without requiring a complicated apparatus or operation, and a fragrance. The present invention provides a method for purifying β-phenylethyl alcohol, which is characterized in that a high-purity β-phenylethyl alcohol having an excellent odor can be obtained and the solvent used in the process can be economically used. I was able to.
Claims (1)
抽出蒸留工程：粗製β−フェニルエチルアルコールを、抽出溶媒（Ａ）を用いて抽出蒸留する工程であって、抽出溶媒は水と１，２−プロパンジオールとの混合比が１：９〜７：３である混合液であり、減圧下、温度５０〜２００℃、還流比０．１〜５０の条件で抽出蒸留を行い、塔頂より揮発性の高い抽出蒸留溶媒（Ａ）と異臭を有する不純物が留出し、塔底より精製されたβ−フェニルエチルアルコールを取り出す工程
抽出工程：抽出蒸留工程で使用した後の抽出溶媒（Ａ）を、別の抽出溶媒（Ｂ）を用いて抽出することにより精製する工程であって、別の抽出溶媒（Ｂ）がベンゼン、トルエン及び／又はキシレンを含む芳香族油である工程 A method for purifying crude β-phenylethyl alcohol, comprising the following steps, wherein the extraction solvent (A) purified in the extraction step is recycled to the extractive distillation step and reused.
Extractive distillation step: a step of subjecting crude β-phenylethyl alcohol to extractive distillation using an extraction solvent (A), wherein the extraction solvent has a mixing ratio of water and 1,2-propanediol of 1: 9 to 7: 3 is a mixed liquid, and is subjected to extractive distillation under reduced pressure at a temperature of 50 to 200 ° C. and a reflux ratio of 0.1 to 50, and has an extractive distillation solvent (A) having a high volatility from the top of the column and an odor Distills and removes purified β-phenylethyl alcohol from the bottom of the column
Extraction step: a step of purifying the extraction solvent (A) after use in the extractive distillation step by extracting with another extraction solvent (B), wherein the other extraction solvent (B) is benzene, toluene And / or an aromatic oil containing xylene
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10123199A JP3846101B2 (en) | 1999-04-08 | 1999-04-08 | Purification method of β-phenylethyl alcohol |
| NL1014776A NL1014776C2 (en) | 1999-04-07 | 2000-03-28 | Purification of beta-phenyl ethyl alcohol for fragrance in detergents and cosmetics, by extractive distillation of crude beta-phenyl ethyl alcohol using an extracting solvent followed by extracting the solvent using another solvent |
| SG200001858A SG82692A1 (en) | 1999-04-07 | 2000-03-31 | Method for purifying beta-phenylethyl alcohol |
| KR1020000017331A KR100734801B1 (en) | 1999-04-07 | 2000-04-03 | Method for Purifying β-phenylethyl Alcohol |
| ES200000864A ES2168057B1 (en) | 1999-04-07 | 2000-04-05 | METHOD FOR PURIFYING BETA-PHENYLETHYL ALCOHOL |
| CNB001049674A CN1170797C (en) | 1999-04-07 | 2000-04-05 | Purification method of β-phenylethanol |
| US09/543,588 US6207867B1 (en) | 1999-04-07 | 2000-04-05 | Method for purifying β-phenylethyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10123199A JP3846101B2 (en) | 1999-04-08 | 1999-04-08 | Purification method of β-phenylethyl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000290206A JP2000290206A (en) | 2000-10-17 |
| JP3846101B2 true JP3846101B2 (en) | 2006-11-15 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10123199A Expired - Fee Related JP3846101B2 (en) | 1999-04-07 | 1999-04-08 | Purification method of β-phenylethyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3846101B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402493C (en) * | 2003-03-31 | 2008-07-16 | 科学与工业研究委员会 | Method for recovering pure acrylonitrile |
| JP5003172B2 (en) * | 2007-01-18 | 2012-08-15 | 住友化学株式会社 | Purification method of β-phenylethyl alcohol |
| CN117088756A (en) * | 2023-08-21 | 2023-11-21 | 万华化学集团股份有限公司 | A method for recovering 2-phenylethanol from heavy oil in styrene production process |
-
1999
- 1999-04-08 JP JP10123199A patent/JP3846101B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JP2000290206A (en) | 2000-10-17 |
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