JP3858512B2 - Purification method of β-phenylethyl alcohol - Google Patents
Purification method of β-phenylethyl alcohol Download PDFInfo
- Publication number
- JP3858512B2 JP3858512B2 JP10001399A JP10001399A JP3858512B2 JP 3858512 B2 JP3858512 B2 JP 3858512B2 JP 10001399 A JP10001399 A JP 10001399A JP 10001399 A JP10001399 A JP 10001399A JP 3858512 B2 JP3858512 B2 JP 3858512B2
- Authority
- JP
- Japan
- Prior art keywords
- phenylethyl alcohol
- crude
- extractive distillation
- supply pipe
- weight
- 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 - Fee Related
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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することができ、香料用の優れた香気を有する高純度のβ−フェニルエチルアルコ−ルを得ることができる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することができ、香料用の優れた香気を有する高純度のβ−フェニルエチルアルコ−ルを得ることができる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、下記の工程を含む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。
アルカリ洗浄工程：粗製β−フェニルエチルアルコールをアルカリ水溶液で洗浄する工程であって、アルカリ水溶液は濃度１〜５０重量％の苛性ソーダ水溶液であり、アルカリ水溶液の量は粗製β−フェニルエチルアルコール１００重量部に対し５〜５０重量部であり、温度２０〜１００℃で洗浄し、回転翼を内装したアルカリ洗浄槽を用いる工程
抽出蒸留工程：アルカリ洗浄後の粗製β−フェニルエチルアルコールを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、抽出蒸留塔の中段に設けられた供給管を通してアルカリ洗浄後の粗製β−フェニルエチルアルコールを供給し、抽出溶媒は粗製β−フェニルエチルアルコールの供給管より下部に設けられている供給管より供給し、粗製β−フェニルエチルアルコール及び抽出溶媒はいずれも連続的に供給し、抽出蒸留塔において、減圧下、温度５０〜２００℃、還流比０．１〜５０の条件で抽出蒸留を行い、塔頂の留出管より揮発性の高い抽出蒸留溶媒と異臭を有する不純物を留出させ、抽出蒸留塔の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
【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】
本発明のアルカリ洗浄工程は、粗製β−フェニルエチルアルコールをアルカリ水溶液で洗浄する工程である。アルカリ水溶液としては、濃度１〜５０重量％の苛性ソーダ水が用いられ、洗浄時の温度は２０〜１００℃であり、用いるアルカリ水溶液の量は、粗製β−フェニルエチルアルコール１００重量部に対し５〜５０重量部である。
【０００７】
本発明においては、このアルカリ洗浄工程を次の抽出蒸留工程と組み合わせることによって、より効果的に粗製βーフェニルエチルアルコールから異臭成分を選択的に分離除去することができ、香料用の優れた香気を有する高純度のβーフェニルエチルアルコールを得ることができる。抽出蒸留工程で用いる抽出溶媒としては、臭気成分の除去効率の観点から、水と１，２−プロパンジオールとの混合比が１：９〜７：３である混合液が用いられる。
【０００８】
抽出蒸留を図１に基づいて説明する。供給管（１）から原料である粗製β−フェニルエチルアルコールを、供給管（２）からアルカリ水溶液を、各々アルカリ洗浄槽（３）へ供給し、両者を接触させた後、抽出蒸留塔（７）の中段に設けられた供給管（５）を通して供給する。一方、溶媒である水と１，２−プロパンジオールの混合液は、供給管（５）より下部に設けられている供給管（６）より供給する。粗製β−フェニルエチルアルコール及び溶媒は、いずれも連続的に供給される。抽出蒸留塔（７）において抽出蒸留が行われ、塔頂の留出管（８）より揮発性の高い抽出蒸留溶媒と異臭を有する不純物が留出する。抽出蒸留塔（７）の塔底より精製されたβ−フェニルエチルアルコールを抜出管（９）を通して取り出す。抽出蒸留の条件としては、減圧下、温度５０〜２００℃、還流比０．１〜５０が用いられる。
【０００９】
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（１０）を用いた蒸留法などの簡単な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。
【００１０】
【実施例】
以下、本発明を実施例により説明する。
実施例１
アルカリ洗浄槽（３）には洗浄効率を上げるため回転翼を内装したものを用い、温度８０℃で大気圧下で運転を行なった。また、抽出蒸留塔（７）は５０段、精留塔（１０）は１５段の塔を用い、ともに１００ｍｍＨｇの減圧で運転を行った。不純物８．５重量％を含み、異臭を有するβ−フェニルエチルアルコールを供給管（１）より１時間あたり３００部の速度で連続的に供給した。同時に苛性ソーダ濃度２５重量％のアルカリ水をアルカリ洗浄槽（３）に供給管（２）より１時間あたり７０重量部の速度で連続的に供給した。このアルカリ洗浄を行った粗製β−フェニルエチルアルコールは塔頂より数えて２０段目に設けられた供給管（５）より抽出蒸留塔（７）に供給し、一方、抽出蒸留溶媒である水と１，２−プロパンジオールとの混合液（重量比１：１）は塔頂から数えて４０段目に設けられた供給管（６）より１時間あたり５８８重量部の速度で連続的に供給した。このとき異臭成分は塔頂の留出管（８）を通して、１，２−プロパンジオール及び水と共に１時間当たり６１５重量部の速度で留出した。
一方、塔底の抜出管（９）を通して取り出された液を精留塔（１０）の塔頂から８段目に供給したところ、塔頂の留出管（１１）を通して精製β−フェニルエチルアルコールが１時間あたり２５９重量部の速度で留出した。このようにして得られた精製β−フェニルエチルアルコールは、不快な異臭も無く、香料用途に適した品質（純度９９．９重量％）のものであった。
【００１１】
比較例１
原料である粗製β−フェニルエチルアルコールをアルカリ洗浄を通さずに直接、抽出蒸留塔（７）に供給管（５）から供給した以外は、実施例と同じ装置、同条件で運転を行なったところ、得られた精製β−フェニルエチルアルコールは純度が９９．０重量％以下であり、香料用に適する品質のものではなかった。
【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することができ、香料用の優れた香気を有する高純度のβ−フェニルエチルアルコ−ルを得ることができる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。
【図面の簡単な説明】
【図１】本発明のフローの例を示す図である。
【符号の説明】
１ （原料である粗製β−フェニルエチルアルコ−ルの）供給管
２ （アルカリ水溶液の）供給管
３ アルカリ洗浄槽
４ アルカリ洗浄排水
５ 供給管
６ 供給管
７ 抽出蒸留塔
８ 留出管
９ 抜出管
10 精留塔
11 留出管
12 抜出管[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for purifying β-phenylethyl alcohol. More specifically, the present invention can selectively remove off-flavor components from crude β-phenylethyl alcohol with simple operation and efficiently without the need for complicated equipment and operation. The present invention relates to a method for purifying β-phenylethyl alcohol capable of obtaining high-purity β-phenylethyl alcohol having an excellent aroma for fragrances.
[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. The object of the present invention is to provide a method for purifying β-phenylethyl alcohol that can be separated and removed, and that can provide high-purity β-phenylethyl alcohol having an excellent aroma for fragrances.
[0004]
[Means for Solving the Problems]
That is, the present invention relates to a method for purifying crude β-phenylethyl alcohol, which includes the following steps.
Alkaline washing step: washing the crude β-phenylethyl alcohol with an alkaline aqueous solution, wherein the alkaline aqueous solution is a caustic soda solution having a concentration of 1 to 50% by weight, and the amount of the alkaline aqueous solution is 100 parts by weight of the crude β-phenylethyl alcohol 5 to 50 parts by weight, a process using an alkali cleaning tank washed at a temperature of 20 to 100 ° C. and equipped with a rotor blade. Extractive distillation process: a process of extracting and distilling crude β-phenylethyl alcohol after alkali cleaning The extraction solvent is a mixed solution in which the mixing ratio of water and 1,2-propanediol is 1: 9 to 7: 3, and the crude product after alkali washing is passed through a supply pipe provided in the middle stage of the extractive distillation column. β-Phenylethyl alcohol is supplied, and the extraction solvent is a supply pipe provided below the crude β-phenylethyl alcohol supply pipe. The crude β-phenylethyl alcohol and the extraction solvent are both continuously supplied, and in the extractive distillation column, extractive distillation is performed under reduced pressure at a temperature of 50 to 200 ° C. under a reflux ratio of 0.1 to 50. A step of distilling a highly volatile extractive distillation solvent and impurities having a bad odor from a distillation tube at the top of the column and taking out purified β-phenylethyl alcohol from the bottom of the extractive distillation column
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 alkali washing step of the present invention is a step of washing crude β-phenylethyl alcohol with an alkaline aqueous solution. As the alkaline aqueous solution , caustic soda water having a concentration of 1 to 50% by weight is used, the temperature at the time of washing is 20 to 100 ° C., and the amount of the alkaline aqueous solution used is 5 to 100 parts by weight of crude β-phenylethyl alcohol. 50 parts by weight.
[0007]
In the present invention, by combining this alkaline washing step with the following extractive distillation step, it is possible to selectively separate and remove off-flavor components from crude β-phenylethyl alcohol more effectively, and an excellent fragrance for fragrances. Β-phenylethyl alcohol having high purity can be obtained. As the extraction solvent used in the extractive distillation step, a mixed solution having a mixing ratio of water and 1,2-propanediol of 1: 9 to 7: 3 is used from the viewpoint of removal efficiency of odor components .
[0008]
Extractive distillation will be described with reference to FIG . Crude β-phenylethyl alcohol, which is a raw material, is supplied from the supply pipe (1), and an alkaline aqueous solution is supplied from the supply pipe (2) to the alkali washing tank (3). ) Through a supply pipe (5) provided in the middle stage. On the other hand, a mixed liquid of water and 1,2-propanediol as a solvent is supplied from a supply pipe (6) provided below the supply pipe (5). Both the crude β-phenylethyl alcohol and the solvent are continuously supplied. Extractive distillation is performed in the extractive distillation column (7), and an extractive distillation solvent having a high volatility and impurities having a bad odor are distilled from the distillation tube (8) at the top of the column. Purified β-phenylethyl alcohol is removed from the bottom of the extractive distillation column (7) through the extraction tube (9). As conditions for extractive distillation, a temperature of 50 to 200 ° C. and a reflux ratio of 0.1 to 50 are used under reduced pressure .
[0009]
The β-phenylethyl alcohol after the extractive distillation step can be converted to β-phenylethyl alcohol, which is the final product, by performing a simple post-treatment such as a distillation method using a rectifying column (10).
[0010]
【Example】
Hereinafter, the present invention will be described with reference to examples.
Example 1
In order to increase the cleaning efficiency, the alkaline cleaning tank (3) was equipped with a rotor blade and was operated at a temperature of 80 ° C. under atmospheric pressure. The extractive distillation column (7) was a 50-stage column and the rectification column (10) was a 15-stage column, both of which were operated at a reduced pressure of 100 mmHg. Β-Phenylethyl alcohol containing 8.5% by weight of impurities and having a bad odor was continuously supplied from the supply pipe (1) at a rate of 300 parts per hour. At the same time, alkaline water having a caustic soda concentration of 25% by weight was continuously supplied to the alkali cleaning tank (3) from the supply pipe (2) at a rate of 70 parts by weight per hour. The crude β-phenylethyl alcohol subjected to the alkali washing is supplied to the extractive distillation tower (7) from the supply pipe (5) provided at the 20th stage from the top of the tower, while the extractive distillation solvent water and A mixed solution with 1,2-propanediol (weight ratio 1: 1) was continuously supplied at a rate of 588 parts by weight per hour from a supply pipe (6) provided at the 40th stage from the top of the column. . At this time, the off-flavor component was distilled off at a rate of 615 parts by weight per hour together with 1,2-propanediol and water through a distillation tube (8) at the top of the column.
On the other hand, when the liquid taken out through the bottom extraction pipe (9) was supplied to the eighth stage from the top of the rectification tower (10), purified β-phenylethyl was passed through the top distillation pipe (11). Alcohol distills at a rate of 259 parts by weight per hour. The purified β-phenylethyl alcohol thus obtained had no unpleasant odor and was of a quality (purity 99.9% by weight) suitable for fragrance use.
[0011]
Comparative Example 1
When the raw β-phenylethyl alcohol, which is the raw material, was directly operated without passing through the alkali washing, and was supplied to the extractive distillation column (7) from the supply pipe (5), the operation was performed under the same conditions and conditions as in the examples. The purified β-phenylethyl alcohol thus obtained had a purity of 99.0% by weight or less and was not of a quality suitable for fragrance use.
[0012]
【The invention's effect】
As described above, according to the present invention, it is possible to selectively separate and remove off-flavor components from crude β-phenylethyl alcohol by simple operation and efficiently without requiring complicated devices and operations. It was possible to provide a method for purifying β-phenylethyl alcohol capable of obtaining high-purity β-phenylethyl alcohol having an excellent aroma for fragrances.
[Brief description of the drawings]
FIG. 1 is a diagram showing an example of a flow of the present invention.
[Explanation of symbols]
1 Supply pipe (of raw β-phenylethyl alcohol as raw material) 2 Supply pipe (of alkaline aqueous solution) 3 Alkali washing tank 4 Alkaline washing drain 5 Supply pipe 6 Supply pipe 7 Extractive distillation tower 8 Distillation pipe 9 Extraction tube
10 rectifying tower
11 Distillate pipe
12 Extraction pipe
Claims (1)
アルカリ洗浄工程：粗製β−フェニルエチルアルコールをアルカリ水溶液で洗浄する工程であって、アルカリ水溶液は濃度１〜５０重量％の苛性ソーダ水溶液であり、アルカリ水溶液の量は粗製β−フェニルエチルアルコール１００重量部に対し５〜５０重量部であり、温度２０〜１００℃で洗浄し、回転翼を内装したアルカリ洗浄槽を用いる工程
抽出蒸留工程：アルカリ洗浄後の粗製β−フェニルエチルアルコールを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、抽出蒸留塔の中段に設けられた供給管を通してアルカリ洗浄後の粗製β−フェニルエチルアルコールを供給し、抽出溶媒は粗製β−フェニルエチルアルコールの供給管より下部に設けられている供給管より供給し、粗製β−フェニルエチルアルコール及び抽出溶媒はいずれも連続的に供給し、抽出蒸留塔において、減圧下、温度５０〜２００℃、還流比０．１〜５０の条件で抽出蒸留を行い、塔頂の留出管より揮発性の高い抽出蒸留溶媒と異臭を有する不純物を留出させ、抽出蒸留塔の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A method for purifying crude β-phenylethyl alcohol, comprising the following steps.
Alkaline washing step: washing the crude β-phenylethyl alcohol with an alkaline aqueous solution, the alkaline aqueous solution being a caustic soda solution having a concentration of 1 to 50% by weight, and the amount of the alkaline aqueous solution is 100 parts by weight of the crude β-phenylethyl alcohol 5 to 50 parts by weight, a process using an alkali cleaning tank washed at a temperature of 20 to 100 ° C. and equipped with a rotor blade. Extractive distillation process: a process of extractive distillation of crude β-phenylethyl alcohol after alkali cleaning The extraction solvent is a mixed solution in which the mixing ratio of water and 1,2-propanediol is 1: 9 to 7: 3, and the crude product after alkali washing is passed through a supply pipe provided in the middle stage of the extractive distillation column. β-Phenylethyl alcohol is supplied, and the extraction solvent is a supply pipe provided below the crude β-phenylethyl alcohol supply pipe. The crude β-phenylethyl alcohol and the extraction solvent are both continuously supplied, and in the extractive distillation tower, extractive distillation is performed under reduced pressure at a temperature of 50 to 200 ° C. and a reflux ratio of 0.1 to 50. A step of distilling a highly volatile extractive distillation solvent and impurities having a bad odor from the distillation tube at the top of the column and taking out purified β-phenylethyl alcohol from the bottom of the extractive distillation column
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10001399A JP3858512B2 (en) | 1999-04-07 | 1999-04-07 | Purification method of β-phenylethyl alcohol |
| 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 |
|---|---|---|---|
| JP10001399A JP3858512B2 (en) | 1999-04-07 | 1999-04-07 | Purification method of β-phenylethyl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000290205A JP2000290205A (en) | 2000-10-17 |
| JP3858512B2 true JP3858512B2 (en) | 2006-12-13 |
Family
ID=14262681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10001399A Expired - Fee Related JP3858512B2 (en) | 1999-04-07 | 1999-04-07 | Purification method of β-phenylethyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3858512B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102005036314A1 (en) * | 2005-07-29 | 2007-02-01 | Isp Biochema Schwaben Gmbh | Microbicidal composition for combatting organisms comprises 2-methyl-3-isothiazolone and active compound(s) from activated methylol groups-containing compounds, quats to polyquats, carbamates, organic acids or aromatic alcohols |
| JP5003172B2 (en) * | 2007-01-18 | 2012-08-15 | 住友化学株式会社 | Purification method of β-phenylethyl alcohol |
| JP5174646B2 (en) * | 2007-12-18 | 2013-04-03 | 花王株式会社 | Method for deodorizing organic solvents |
| JP7669674B2 (en) | 2020-12-01 | 2025-04-30 | 住友ベークライト株式会社 | Method for purifying cyclic compounds |
-
1999
- 1999-04-07 JP JP10001399A patent/JP3858512B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000290205A (en) | 2000-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3232678B2 (en) | Acetic acid recovery method | |
| JPH04503358A (en) | A method for producing a DMT intermediate product of constant purity and a method for reprocessing the product into very pure DMT and/or medium to high purity terephthalic acid. | |
| JP3858512B2 (en) | Purification method of β-phenylethyl alcohol | |
| JP3160983B2 (en) | Purification method of ethyl acetate | |
| US2863882A (en) | Producing and recovering terpenic oxidation products | |
| JP5003172B2 (en) | Purification method of β-phenylethyl alcohol | |
| US4359365A (en) | Method of purification of β-phenylethyl alcohol | |
| JP2004528393A (en) | Method for removing formic acid from aqueous solution | |
| JPS6058211B2 (en) | Purification method of β-phenylethyl alcohol | |
| JPH09151158A (en) | Purification of acetic acid | |
| CN1321959C (en) | Purification of 1,3-propanediol by distillation | |
| JP3846101B2 (en) | Purification method of β-phenylethyl alcohol | |
| JP3552306B2 (en) | Method for producing propylene oxide and styrene monomer | |
| KR100734801B1 (en) | Method for Purifying β-phenylethyl Alcohol | |
| JPS58183641A (en) | Purification of methyl (meth)acrylate | |
| JP2924563B2 (en) | Purification method of ethyl acetate | |
| JP2002308806A (en) | Method for purifying 2-phenyl-1-propanol | |
| JPS6058898B2 (en) | Purification method of β-phenylethyl alcohol | |
| JPH0725814A (en) | Production of highly pure acetic acid | |
| JPH10109948A (en) | Isopropyl alcohol purification method | |
| JPH03181440A (en) | Purification of acrylic acid by distillation | |
| JP4348890B2 (en) | Method for purifying gamma-butyrolactone | |
| JPH0120137B2 (en) | ||
| JP2004182848A (en) | Method for adjusting benzyl alcohol content in phenethyl alcohol for flavoring | |
| JP2002308807A (en) | Method for purifying 2-phenyl-1-propanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20051125 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20051220 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060124 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060725 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060801 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060829 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060911 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090929 Year of fee payment: 3 |
|
| RD05 | Notification of revocation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: R3D05 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100929 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110929 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110929 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120929 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130929 Year of fee payment: 7 |
|
| LAPS | Cancellation because of no payment of annual fees |