JPS6048981A - Production of high-purity tocopherol - Google Patents
Production of high-purity tocopherolInfo
- Publication number
- JPS6048981A JPS6048981A JP58156318A JP15631883A JPS6048981A JP S6048981 A JPS6048981 A JP S6048981A JP 58156318 A JP58156318 A JP 58156318A JP 15631883 A JP15631883 A JP 15631883A JP S6048981 A JPS6048981 A JP S6048981A
- Authority
- JP
- Japan
- Prior art keywords
- tocopherol
- carbon dioxide
- dioxide gas
- supercritical carbon
- purity
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
Description
【発明の詳細な説明】
技術分野
本発明は高純度トコフェロールの製造方法に関し、更に
詳しくは超臨界炭酸ガス？使用して高純度トコフェロー
ルの製造方法に関する。[Detailed Description of the Invention] Technical Field The present invention relates to a method for producing high-purity tocopherol, and more particularly to supercritical carbon dioxide gas? The present invention relates to a method for producing high purity tocopherol using the present invention.
従来技術
トコフェａ−ルは多くの植物油中に存在するビタミンＥ
生理活性や酸化防止能を有する物質でα。Prior Art Tocopherol is a vitamin E present in many vegetable oils.
α is a substance with physiological activity and antioxidant ability.
β、γ、δ及びξなどの各同族体よりなり、従来、大豆
スカム油、小麦はい芽油などの天然物から溶剤抽出、分
子蒸留、イオン交換樹脂処理、晶析などの操作により分
離精製していた。しかしながら。It consists of homologues such as β, γ, δ, and ξ, and has traditionally been separated and purified from natural products such as soybean scum oil and wheat germ oil by operations such as solvent extraction, molecular distillation, ion exchange resin treatment, and crystallization. was. however.
このような従来法では原料中の脂肪酸やグリセライドの
分離は比較的容易であるが、原料中のトコフェロール類
／ステロール類の分離係数が小さく、目的物質である分
離トコフェロールの純度を高めるのが困難であ−た。精
製トコフェロールの純度？高めようとして繰り返し分子
蒸留した場合には高熱部での滞留時間が増大し製品の熱
劣化が起るという問題かあ。た。このため従来法では精
製トコフェロール製品の純度は最大約６０〜７０係程度
に過ぎなかった。Although it is relatively easy to separate fatty acids and glycerides in raw materials using such conventional methods, the separation coefficient of tocopherols/sterols in raw materials is small, making it difficult to increase the purity of the target substance, separated tocopherols. Oh. Purity of purified tocopherol? If molecular distillation is repeated to increase the temperature, the residence time in the high-temperature zone will increase, leading to thermal deterioration of the product. Ta. Therefore, in the conventional method, the purity of purified tocopherol products was only about 60-70% at maximum.
発明の目的
従って、本発明の目的は、前記した従来技術の欠点を排
除し、高純度（例えば純度８０チ以上）のトコフェロー
ルχ製造すゐ方法を提供することＣ二ある。OBJECTS OF THE INVENTION Accordingly, an object of the present invention is to eliminate the drawbacks of the prior art described above and to provide a method for producing tocopherol χ with high purity (for example, purity of 80% or more).
発明の構成
本発明に従った高純度トコフェロールの製造方法は、ト
コフェロール含有原料又はその粗精製品Ｖ超臨界炭酸ガ
スと接触せしめてトコフェロール？抽出することから成
る。Structure of the Invention The method for producing high-purity tocopherol according to the present invention comprises contacting a tocopherol-containing raw material or a crude product thereof with supercritical carbon dioxide gas to produce tocopherol. Consists of extracting.
発明の構成及び効果の具体的説明
以下に本発明に従った高純度トコフェロールの製造方法
（：つき、更に詳しく説明する。Detailed Description of the Structure and Effects of the Invention The method for producing high-purity tocopherol according to the present invention will be described in more detail below.
本発明者等は前記したトコフェロールの精製方法の問題
点を解決すべく、液体クロマトグラフ法による分離精製
、各種媒体による抽出精製、吸着剤による分離精製ｌど
について鋭意検討？進めた結果、驚くべきことに超臨界
状態の炭酸ガス？使用することによってトコフェロール
含有物質から高純度のトコフェロールＹ抽出すゐことが
できることを見出した。In order to solve the problems of the above-mentioned tocopherol purification method, the present inventors have earnestly studied methods such as separation and purification using liquid chromatography, extraction and purification using various media, and separation and purification using adsorbents. As a result, surprisingly, carbon dioxide gas was found in a supercritical state? It has been found that by using this method, highly purified tocopherol Y can be extracted from tocopherol-containing substances.
即ち、本発明に従えば、臨界圧力（Ｐｃ＝ ７２．８ａ
ｔａ ）及び臨界温度（Ｔｃ＝３１ ℃）を超える超臨
界炭酸ガス、好捷しくは圧力フ２．８ａｔａ超〜５００
ａｔａ及び温度３１℃超〜９０℃、更に好ましくは圧
力１００〜３００ａｔａ及び温度３５〜７５℃の超臨界
炭酸ガスをトコフェロール含有原料又はその粗精製品と
接触せしめることによって ４トコフエロールに富む成
分ン効率良く超臨界炭酸ガス中に抽出することができ、
ステロール類やグ（３）
リセライド類は原液側Ｃ：残存せしめてトコフェロール
を効果的に濃縮することができる。なお、超臨界状態に
達しない通常の液化炭酸ガスによる抽出の場合は、炭酸
ガス単位重量当りのトコフェロール抽出量が超臨界状態
の場合に比べて１桁以上小さく、工業的に成立させるの
は難しい。That is, according to the present invention, the critical pressure (Pc=72.8a
ta ) and supercritical carbon dioxide gas exceeding the critical temperature (Tc = 31 °C), preferably at a pressure of more than 2.8 ata to 500 °C.
4 tocopherol-rich components by contacting supercritical carbon dioxide at a pressure of 100 to 300 ata and a temperature of 35 to 75 °C with a tocopherol-containing raw material or a crude product thereof. Can be extracted into supercritical carbon dioxide,
Sterols and (3) lycerides can be left on the undiluted solution side C: to effectively concentrate tocopherols. In addition, in the case of extraction using normal liquefied carbon dioxide gas that does not reach a supercritical state, the amount of tocopherol extracted per unit weight of carbon dioxide is more than an order of magnitude smaller than in the case of a supercritical state, and it is difficult to achieve this industrially. .
トコフェロール含有原料又はその粗精製品中のトコフェ
ロールの超臨界炭酸ガスによる抽出は、従来慣用されて
いる任意の抽出装置、例えばミキサーセトラーや棚段塔
、充填塔などの各種同流又は並流接触装置などを使用し
て実施することができ、超臨界状態の炭酸ガス′５ｒ：
使用することを除けば従来の抽出操作と何等変るところ
がない。また連続処理、バッチ処理のいずれも採用する
ことができる。Extraction of tocopherols from tocopherol-containing raw materials or crude products thereof using supercritical carbon dioxide can be carried out using any conventionally used extraction equipment, such as various co-current or co-current contact equipment such as mixer-settlers, tray columns, and packed columns. It can be carried out using carbon dioxide '5r in supercritical state:
There is no difference from conventional extraction operations except for the use. Further, either continuous processing or batch processing can be employed.
前記のようにして、超臨界炭酸ガス相に抽出されたトコ
フェロールに富む成分は、先ず抽出装置から抜き出した
超臨界炭酸ガスを減圧又は温度変化せしめることＣ二よ
って炭酸ガス中への溶解度？減少させ、適当な気液分離
器によって抽出された（４）
トコフェロールＣ二富む液相と炭酸ガスとを分離せしめ
、高純度（一般には７０〜９０ ％ ）のトコフェロー
ルを回収すると共に炭酸ガスは例えばコンプレッサーに
より再加圧し、再度トコフエａ−ル抽出媒体として循環
使用することができる。The tocopherol-rich components extracted into the supercritical carbon dioxide phase as described above are determined by first reducing the pressure or changing the temperature of the supercritical carbon dioxide extracted from the extraction device. (4) The liquid phase rich in tocopherol C and the carbon dioxide gas are separated, and the tocopherols of high purity (generally 70-90%) are recovered, and the carbon dioxide gas is extracted by a suitable gas-liquid separator, e.g. It can be re-pressurized by a compressor and recycled as a tocopher air extraction medium.
このようにして本発明方法Ｃ二従えば、製品の熱劣化を
伴なうことなく高純度のトコフェロールを高収率で製造
することができ、また使用する抽出媒体が炭酸ガスであ
るため、従来法におけるように人体に有害で環境を汚染
する有機溶媒？使用する必要がなく、得られた製品中の
残留溶媒の毒性を問題とならない。In this way, if method C2 of the present invention is followed, high-purity tocopherol can be produced in high yield without thermal deterioration of the product, and since the extraction medium used is carbon dioxide, Are organic solvents harmful to the human body and polluting the environment as stipulated in the law? There is no need to use it, and the toxicity of residual solvents in the resulting product is not an issue.
本発明方法（：おいては、従来トコフエ０−ルの製造ｇ
ニ一般的に使用されている大豆スカム油、小麦はい１油
などの天然物をそのまま使用してトコフェロールを高純
度で抽出することもでき、或いは従来法Ｃ二よ−て純度
６０〜７０チ程度まで濃縮シタトコフェロール粗精製品
を本発明方法で超臨界炭酸ガスで抽出して更（＝精製し
て高純度のトコフェロール？得ることがで六る。ｔた、
本発明方法で製造した高純度トコフェロールは更に分子
蒸留法などによ−て精製して純度を高めることもできる
。本発明方法に従−てトコフェロール？抽出した抽出残
液は原料トコフェロール中ζ二混合して再度使用したり
、前処理又はトコフェロール粗精製工程に混合して再度
抽出原液として循環使用することができる。The method of the present invention (in which conventional tocopherol production g
D. Tocopherol can be extracted with high purity by using commonly used natural products such as soybean scum oil and wheat husk oil, or with conventional method C2, the purity is about 60-70%. It is possible to obtain high-purity tocopherol by extracting the crude product of sitatocopherol concentrated to 100% using supercritical carbon dioxide gas using the method of the present invention.
The high purity tocopherol produced by the method of the present invention can be further purified by a molecular distillation method or the like to increase its purity. Tocopherol according to the method of the invention? The extracted residual liquid can be mixed with the raw material tocopherol and used again, or mixed in the pretreatment or tocopherol rough purification step and recycled as an extraction stock solution again.
実施例
以下、本発明ン実施例に従うて更に詳細に説明するが、
本発明の技術的範囲をこれらの実施例に駆足するもので
ないことはいうまでもない。以下の例Ｃ二おいて１％」
は特ζ二ことわらない限り「重を係」乞意味する。EXAMPLES Below, the present invention will be explained in more detail according to examples.
It goes without saying that the technical scope of the present invention is not limited to these Examples. 1% in the following example C2
unless otherwise specified.
実施例１
大豆脱臭スカムより公知の済媒抽出及び分子蒸留Ｃ二よ
って得た純度５５．３ ％の粗トコソエロール（組成：
トコフェロール５５．３１１ステロール４０．２％、ス
クヮレン２．５％、グリセライド１，４チ、脂肪酸及び
そのエステル０．６％）を塔径１００譚及び充填高さ１
０（１０ｍの充填塔（充横物：６ｍＤＩＸＯＮバッキン
グ）の塔頂部より供給速度１０ｋｇ／ｈｒで供給し、塔
底部から圧力２５０ ａｔｍ及び温度６０℃の超臨界炭
酸ガス８０ ｋｇ ／ ｈｒ の供給速度で供給して粗
トコフェロールと超臨界炭酸ガスとを充填塔内にて向流
接触せしめた。この間、充填塔は塔本体周囲に設けたジ
ャケットに温水ｒ循環せしめて塔内温度？６０℃に保持
し１こ。Example 1 Crude tocosoerol with a purity of 55.3% (composition:
Tocopherol 55.311 sterol 40.2%, squalene 2.5%, glyceride 1.4%, fatty acid and its ester 0.6%) were added to the column with a column diameter of 100 mm and a filling height of 1 mm.
0 (10 m packed column (filled side: 6 m DIXON backing) was supplied at a supply rate of 10 kg/hr from the top of the column, and supercritical carbon dioxide gas at a pressure of 250 atm and a temperature of 60°C was supplied from the bottom of the column at a supply rate of 80 kg/hr. The crude tocopherol and supercritical carbon dioxide were brought into countercurrent contact in the packed tower.During this time, the packed tower was kept at an internal temperature of -60°C by circulating hot water through a jacket provided around the main body of the tower. 1 piece.
その結果、塔頂から流出する炭酸ガス中には純度８０．
８−のトコフェロールが１３ｋｆ／ｈｒの割合で抽出さ
れた。As a result, the carbon dioxide gas flowing out from the top of the tower had a purity of 80.
8-tocopherols were extracted at a rate of 13 kf/hr.
比較例１
実施例１において、超臨界炭酸ガスＣ二代えて圧力５９
］ｖ／ｄＧ及び温度２２℃の液化炭酸ガスを用いて粗ト
コフェロールの精製実験を実施したが、純度７６．０％
のトコ７、ｏ−ル８Ｑ’ｆ／ ｈｒ Ｌ／か得ることが
できなかった。Comparative Example 1 In Example 1, supercritical carbon dioxide C2 was replaced with a pressure of 59
]v/dG and liquefied carbon dioxide gas at a temperature of 22°C, a crude tocopherol purification experiment was conducted, and the purity was 76.0%.
Toko 7, o-le 8Q'f/hr L/ could not be obtained.
実施例２
トコフェロール’ｋ１５％含ム大豆スカム油（トコフェ
ロール１５チ脂肪酸及びそのエステル２２チ、ステロー
ル１８９６、スクワレ７６幅、グリセラ（７）
イド３９係）娶実施例１と同一装置にて２２ｏ１ｖ／ｄ
Ｇ、５８℃で処理したところ、トコフェロール含有’！
１６１、ステロール含有率６％でグリセライド？殆ど含
有しない粗トコフェロールが１．ｌ吻／ｈｒの割合で得
られた。但しこのとき原料及びＣＯ２の供給速度は実施
例１と同一であった。得られた粗トコフェロールを分子
蒸留にかけることにより純度６８％の精製トコフェロー
ルを得ることができた。Example 2 Soybean scum oil containing 15% tocopherol'k (tocopherol 15 fatty acids and 22 esters thereof, sterol 1896, squale 76, glycerol (7) id 39) 22o1v/d in the same equipment as Example 1
G. Contains tocopherol when treated at 58℃!
161, Glyceride with 6% sterol content? Almost no crude tocopherol is contained in 1. Obtained at a rate of 1 snout/hr. However, at this time, the feed rates of raw materials and CO2 were the same as in Example 1. By subjecting the obtained crude tocopherol to molecular distillation, purified tocopherol with a purity of 68% could be obtained.
特許出願人 昭和電工株式会社 特許出願代理人 弁理士 宵 木 朗 弁理士 西 舘 和 之 弁理士 石 １） 敬 弁理士 山 口 昭 之 弁理士 西 山 雅 也 （８）patent applicant Showa Denko Co., Ltd. patent application agent Patent attorney Akira Yoi Patent attorney Kazuyuki Nishidate Patent Attorney Ishi 1) Takashi Patent attorney Akira Yamaguchi Patent Attorney Masaya Nishiyama (8)
Claims (1)
炭酸ガスと接触せしめてトコフェロールを抽出すること
を特徴とする高純度トコフェロールの製造方法。1. A method for producing high-purity tocopherol, which comprises bringing a tocopherol-containing raw material or a crude product thereof into contact with supercritical carbon dioxide gas to extract tocopherol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58156318A JPS6048981A (en) | 1983-08-29 | 1983-08-29 | Production of high-purity tocopherol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58156318A JPS6048981A (en) | 1983-08-29 | 1983-08-29 | Production of high-purity tocopherol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6048981A true JPS6048981A (en) | 1985-03-16 |
| JPS6157310B2 JPS6157310B2 (en) | 1986-12-06 |
Family
ID=15625174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58156318A Granted JPS6048981A (en) | 1983-08-29 | 1983-08-29 | Production of high-purity tocopherol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6048981A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6333337A (en) * | 1986-06-17 | 1988-02-13 | インデナ・エッセ・ピ・ア | Extraction of drug from oily fruit |
| US6159347A (en) * | 1998-01-29 | 2000-12-12 | Eastman Chemical Company | Methods for separating a tocol from a tocol-containing mixture |
| US6706898B2 (en) | 1998-01-29 | 2004-03-16 | Archer-Daniels-Midland Company | Methods for separating a tocopherol from a tocopherol-containing mixture |
| US6867308B2 (en) | 2001-09-19 | 2005-03-15 | Archer-Daniels-Midland Company | Process for separation of tocopherols |
| JP2006097011A (en) * | 2004-09-01 | 2006-04-13 | Malaysian Palm Oil Board | Special palm oil product and other special vegetable oil product |
| JP2009530426A (en) * | 2006-02-10 | 2009-08-27 | キャロテック エスディーエヌ．ビーエイチディー． | Process for producing highly enriched fractions of natural compounds from palm oil or palm oil derivatives |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03176881A (en) * | 1989-12-01 | 1991-07-31 | Konica Corp | Magnetic disk |
| JPH06290447A (en) * | 1992-09-09 | 1994-10-18 | Matsushita Electric Ind Co Ltd | Magnetic recording medium for data storage |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1356749A (en) * | 1971-06-03 | 1974-06-12 | Hag Ag | Method of production vegetable fats and oils |
-
1983
- 1983-08-29 JP JP58156318A patent/JPS6048981A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1356749A (en) * | 1971-06-03 | 1974-06-12 | Hag Ag | Method of production vegetable fats and oils |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6333337A (en) * | 1986-06-17 | 1988-02-13 | インデナ・エッセ・ピ・ア | Extraction of drug from oily fruit |
| US6159347A (en) * | 1998-01-29 | 2000-12-12 | Eastman Chemical Company | Methods for separating a tocol from a tocol-containing mixture |
| US6224717B1 (en) | 1998-01-29 | 2001-05-01 | Eastman Chemical Company | Methods for separating a tocotrienol from a tocol-containing mixture and compositions thereof |
| US6706898B2 (en) | 1998-01-29 | 2004-03-16 | Archer-Daniels-Midland Company | Methods for separating a tocopherol from a tocopherol-containing mixture |
| US6867308B2 (en) | 2001-09-19 | 2005-03-15 | Archer-Daniels-Midland Company | Process for separation of tocopherols |
| JP2006097011A (en) * | 2004-09-01 | 2006-04-13 | Malaysian Palm Oil Board | Special palm oil product and other special vegetable oil product |
| JP2013100506A (en) * | 2004-09-01 | 2013-05-23 | Malaysian Palm Oil Board | Special palm oil product and other special vegetable oil products |
| JP2009530426A (en) * | 2006-02-10 | 2009-08-27 | キャロテック エスディーエヌ．ビーエイチディー． | Process for producing highly enriched fractions of natural compounds from palm oil or palm oil derivatives |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6157310B2 (en) | 1986-12-06 |
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