JPS6157309B2 - - Google Patents
Info
- Publication number
- JPS6157309B2 JPS6157309B2 JP8790979A JP8790979A JPS6157309B2 JP S6157309 B2 JPS6157309 B2 JP S6157309B2 JP 8790979 A JP8790979 A JP 8790979A JP 8790979 A JP8790979 A JP 8790979A JP S6157309 B2 JPS6157309 B2 JP S6157309B2
- Authority
- JP
- Japan
- Prior art keywords
- tocopherols
- toluene
- esterification reaction
- methyl esterification
- resin
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 52
- 229930003799 tocopherol Natural products 0.000 claims description 31
- 239000011732 tocopherol Substances 0.000 claims description 31
- 235000019149 tocopherols Nutrition 0.000 claims description 20
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000005886 esterification reaction Methods 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 claims description 13
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 235000010384 tocopherol Nutrition 0.000 claims description 11
- 229960001295 tocopherol Drugs 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000003925 fat Substances 0.000 claims description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 5
- 239000008158 vegetable oil Substances 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 4
- 235000019871 vegetable fat Nutrition 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- XMGZWGBXVLJOKE-UHFFFAOYSA-N acetic acid;toluene Chemical compound CC(O)=O.CC1=CC=CC=C1 XMGZWGBXVLJOKE-UHFFFAOYSA-N 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GZIFEOYASATJEH-VHFRWLAGSA-N δ-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-VHFRWLAGSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- GZIFEOYASATJEH-UHFFFAOYSA-N D-delta tocopherol Natural products OC1=CC(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 235000019774 Rice Bran oil Nutrition 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 229940087168 alpha tocopherol Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000002285 corn oil Substances 0.000 description 1
- 235000005687 corn oil Nutrition 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 235000010389 delta-tocopherol Nutrition 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- -1 for example Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000010382 gamma-tocopherol Nutrition 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 239000002478 γ-tocopherol Substances 0.000 description 1
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
- 239000002446 δ-tocopherol Substances 0.000 description 1
Landscapes
- Pyrane Compounds (AREA)
Description
【発明の詳細な説明】
本発明は、植物油脂の精製工程で副生する低濃
度トコフエロール含有物質からトコフエロールを
新規に分離する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for separating tocopherols from low-concentration tocopherol-containing substances produced as by-products in the refining process of vegetable oils and fats.
大豆油、綿実油、米ぬか油、トウモロコシ油等
植物油脂中にはトコフエロールが存在し、α−ト
コフエロールは例えばビタミンＥ強化剤に、β−
及びγ−トコフエロールは例えばα−トコフエロ
ール製造原料に、δ−トコフエロールは油脂食品
の酸化防止剤の原料に使用される。 Tocopherols exist in vegetable oils such as soybean oil, cottonseed oil, rice bran oil, and corn oil.
For example, γ-tocopherol is used as a raw material for producing α-tocopherol, and δ-tocopherol is used as a raw material for antioxidants for oil and fat foods.
植物油脂の脱臭等の精製工程で副生する脱臭留
出物、脱臭スラツジ、ホツトウエル油滓等低濃度
トコフエロール含有物質から、トコフエロールを
分離する方法として、従来各種の方法が提案され
ているが、いずれも工業的には収率上、簡便さの
点で問題があつた。 Various methods have been proposed to separate tocopherols from substances containing low concentrations of tocopherols, such as deodorized distillate, deodorized sludge, hotwell oil soapstock, etc., which are produced as by-products in refining processes such as deodorizing vegetable oils and fats. However, industrially, there were problems in terms of yield and simplicity.
本発明者は、従来法に比べ工業上有利にトコフ
エロールを分離する方法を開発すべく検討した結
果、植物油脂の精製工程で副生する低濃度トコフ
エロール含有物質から、これをメチルエステル化
反応、該反応物を強塩基性樹脂処理、及び該樹脂
に吸着したトコフエロールを溶出操作に付して、
トコフエロールを分離する方法において、
(1) メチルエステル化反応をトルエン中で行い、
(2) 該メチルエステル化反応生成物のトルエン層
をそのまま強塩基性樹脂にて処理し、
(3) 酸を含むトルエンを展開溶媒として該樹脂に
吸着したトコフエロールを溶出する
ことによつて、エステル化反応溶媒及び溶出操作
の展開溶媒の両方に同一有機溶媒、トルエンを主
として使用できることになり、上記目的を達成す
ることを見出し本発明を完成するに至つた。 As a result of research to develop a method for separating tocopherols that is industrially more advantageous than conventional methods, the present inventors conducted a methyl esterification reaction to separate tocopherols from low-concentration tocopherol-containing substances produced by-product in the refining process of vegetable oils and fats. The reaction product is treated with a strong basic resin, and the tocopherols adsorbed on the resin are subjected to an elution operation,
In the method for separating tocopherols, (1) a methyl esterification reaction is carried out in toluene, (2) the toluene layer of the methyl esterification reaction product is directly treated with a strong basic resin, and (3) a methyl esterification reaction is carried out in toluene. By eluting the tocopherols adsorbed on the resin using toluene as a developing solvent, the same organic solvent, toluene, can be used primarily as both the esterification reaction solvent and the developing solvent for the elution operation, thereby achieving the above objective. This discovery led to the completion of the present invention.
本発明におけるメチルエステル化反応において
は溶媒としてトルエンを使用する以外は、常法の
メチルエステル化反応を採用することができる。 In the methyl esterification reaction in the present invention, a conventional methyl esterification reaction method can be employed, except that toluene is used as a solvent.
得られたメチルエステル化反応生成物よりトル
エン層を分離し、そのまま強塩基性樹脂で処理す
ればよいが、カラムを使用して処理してもよく、
またバツチ的に処理してもよい。樹脂との処理方
法自体は常法を採用すればよい。 The toluene layer may be separated from the obtained methyl esterification reaction product and treated directly with a strong basic resin, but it may also be treated using a column.
Alternatively, it may be processed in batches. Any conventional method may be used for the treatment with the resin.
本発明における溶出工程は展開溶媒として酸を
含むトルエンを用いる。酸としては例えば、酢
酸、ホウ酸、ギ酸を使用すればよい。溶出方法そ
れ自体は常法を採用すればよい。 The elution step in the present invention uses toluene containing acid as a developing solvent. As the acid, for example, acetic acid, boric acid, or formic acid may be used. The elution method itself may be a conventional method.
なお、本発明方法で使用することができる強塩
基性樹脂としては例えばダウケミカル社製「ダウ
エツクス」、ロームアンドハース社製「アンバー
ライト」、三菱化成工業(株)製「ダイヤイオン」、三
菱化成工業(株)製「デユオライト」等強塩基性イオ
ン交換樹脂があげられる。この場合、常法により
OH型として使用する。 Examples of strong basic resins that can be used in the method of the present invention include "Dowex" manufactured by Dow Chemical Company, "Amberlite" manufactured by Rohm and Haas, "Diaion" manufactured by Mitsubishi Chemical Corporation, and Mitsubishi Chemical Corporation. Examples include strong basic ion exchange resins such as "Duolite" manufactured by Kogyo Co., Ltd. In this case, according to the usual method
Use as OH type.
もちろん、トコフエロールの溶出操作におい
て、順次カラムより流出する溶出液を、例えば外
観観察、薄層クロマトグラフイー、ガスクロマト
グラフイー、液体クロマトグラフイーによつて各
種トコフエロール、α−、β−、γ−、又はδ−
体、あるいはそれらを主として含む分画を分離し
て各々を濃縮精製すれば各種トコフエロールを選
択的に分離することができる。 Of course, in the elution operation of tocopherols, the eluate flowing out from the column is sequentially analyzed by visual observation, thin layer chromatography, gas chromatography, liquid chromatography to determine the various tocopherols, α-, β-, γ-, or δ−
Various tocopherols can be selectively separated by separating the tocopherols or fractions mainly containing them and concentrating and purifying each.
本発明方法によれば、高純度のトコフエロール
を効率的にかつ簡便に分離できる。 According to the method of the present invention, highly pure tocopherols can be efficiently and easily separated.
以下実施例により本発明を詳細に説明する。 The present invention will be explained in detail below with reference to Examples.
実施例 １
混合スラツジ（大豆油とナタネ油から得られる
脱臭スラツジの混合物）714ｇを硫酸の存在下メ
タノール（400ml）及びトルエン（400ml）の混合
溶媒でメチルエステル化反応を行つた後、油状物
質を分離して、メチルエステル化油1.0Kg（総ト
コフエロール含量10.5％、トコフエロール量105
ｇ、酸価３mg以下、トルエン含量30％）を得た。
次に三菱化成工業(株)製、強塩基性樹脂「ダイヤイ
オン PA−306S」900mlをガラスカラム（６×56
cm）に充填し、常法によりOH-型とした後、ト
ルエンで置換し、これに先に得たエステル化油
1.0Kgを15ml／分の速度で通液し、非吸着分を流
出除去後10％酢酸−トルエン溶液3.600mlを15
ml／分の速度でカラムに流出し、トコフエロール
類を溶出した。溶出液中の酢酸を、80℃の温水で
処理し、完全に除去した。次に溶媒を留去し、ト
コフエロール濃縮油105ｇ（純度92％（液体クロ
マトグラフイーによる）、トコフエロール量96.6
ｇ、収率92％）を得た。Example 1 714 g of mixed sludge (a mixture of deodorized sludge obtained from soybean oil and rapeseed oil) was subjected to a methyl esterification reaction with a mixed solvent of methanol (400 ml) and toluene (400 ml) in the presence of sulfuric acid, and then the oily substance was Separated and methyl esterified oil 1.0Kg (tocopherol content 10.5%, tocopherol amount 105
g, acid value 3 mg or less, toluene content 30%).
Next, apply 900 ml of the strong basic resin “Diaion PA-306S” manufactured by Mitsubishi Chemical Industries, Ltd. to a glass column (6 x 56
cm), converted to OH - form by a conventional method, and then replaced with toluene, and added to the previously obtained esterified oil.
1.0Kg was passed through the liquid at a rate of 15ml/min, and after removing the unadsorbed content, 3.600ml of 10% acetic acid-toluene solution was added for 15 minutes.
It flowed into the column at a rate of ml/min to elute the tocopherols. Acetic acid in the eluate was completely removed by treatment with 80°C warm water. Next, the solvent was distilled off, and 105 g of tocopherol concentrated oil (purity 92% (by liquid chromatography), tocopherol amount 96.6
g, yield 92%).
実施例 ２
大豆油の脱臭処理により副産物として得られる
脱臭留出物157ｇを硫酸の存在下、メタノール
（90ml）及びトルエン（90ml）の混合溶媒でメチ
ルエステル化反応を行い、次いで油状物質を分離
してメチルエステル化油219ｇ（純トコフエロー
ル含量8.0％、トコフエロール量17.5ｇ、酸価３
mg以下、トルエン含量30％）を得た。次に、三菱
化成工業(株)製、強塩基性樹脂「ダイヤイオン
PA−306S」140mlをガラスカラム（3.8×40cm）
に充填し、常法によりOH-型とした後、トルエ
ンで置換し、上記に調製したメチルエステル化油
219ｇを2.0ml／分の速度で通液し非吸着分（ステ
ロール類、脂肪酸メチルエステル類等）を完全に
流出除去してから10％酢酸トルエン溶液560mlを
2.5ml／分の速度で流しトコフエロール類を溶出
した。この溶出液中の酢酸を、80℃の温水で処理
し除去後溶媒を留去し、トコフエロール濃縮油
16.9ｇ（純度90％、トコフエロール量15.2ｇ、収
率86.9％）を得た。Example 2 157 g of deodorized distillate obtained as a by-product from the deodorizing treatment of soybean oil was subjected to a methyl esterification reaction in a mixed solvent of methanol (90 ml) and toluene (90 ml) in the presence of sulfuric acid, and then the oily substance was separated. Methyl esterified oil 219g (pure tocopherol content 8.0%, tocopherol amount 17.5g, acid value 3)
mg, toluene content 30%). Next, we introduced the strong basic resin “Diaion” manufactured by Mitsubishi Chemical Industries, Ltd.
PA−306S” 140ml into a glass column (3.8×40cm)
The methyl esterified oil prepared above was filled into the OH - form by a conventional method, and then replaced with toluene.
219 g of the solution was passed through the solution at a rate of 2.0 ml/min to completely remove non-adsorbed components (sterols, fatty acid methyl esters, etc.), and then 560 ml of 10% acetic acid toluene solution was added.
The tocopherols were eluted by flowing at a rate of 2.5 ml/min. After removing the acetic acid in this eluate with 80℃ hot water, the solvent was distilled off and the tocopherol concentrated oil was extracted.
16.9g (purity 90%, tocopherol amount 15.2g, yield 86.9%) was obtained.
Claims (1)
エロール含有物質から、これをメチルエステル化
反応、該反応物を強塩基性樹脂処理、及び該樹脂
に吸着したトコフエロールを溶出操作に付して、
トコフエロールを分離する方法において、 (1) メチルエステル化反応をトルエン中で行い、 (2) 該メチルエステル化反応生成物のトルエン層
をそのまま強塩基性樹脂にて処理し、 (3) 酸を含むトルエンを展開溶媒として該樹脂に
吸着したトコフエロールを溶出する。 ことを特徴とするトコフエロールを分離する方
法。[Scope of Claims] 1 A methyl esterification reaction of a low-concentration tocopherol-containing substance produced as a by-product in the refining process of vegetable oils and fats, treatment of the reaction product with a strong basic resin, and an operation to elute the tocopherols adsorbed on the resin. In addition to
In the method for separating tocopherols, (1) a methyl esterification reaction is carried out in toluene, (2) the toluene layer of the methyl esterification reaction product is directly treated with a strong basic resin, and (3) a methyl esterification reaction is carried out in toluene. The tocopherols adsorbed on the resin are eluted using toluene as a developing solvent. A method for separating tocopherols, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8790979A JPS5612383A (en) | 1979-07-11 | 1979-07-11 | Separation of tocopherol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8790979A JPS5612383A (en) | 1979-07-11 | 1979-07-11 | Separation of tocopherol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5612383A JPS5612383A (en) | 1981-02-06 |
| JPS6157309B2 true JPS6157309B2 (en) | 1986-12-06 |
Family
ID=13928036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8790979A Granted JPS5612383A (en) | 1979-07-11 | 1979-07-11 | Separation of tocopherol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5612383A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6193178A (en) * | 1984-10-12 | 1986-05-12 | Agency Of Ind Science & Technol | Separation of tocotrienols |
| JP6548087B2 (en) * | 2015-05-18 | 2019-07-24 | 国立大学法人東北大学 | Selective separation of vitamin E |
-
1979
- 1979-07-11 JP JP8790979A patent/JPS5612383A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5612383A (en) | 1981-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2143441C (en) | Recovery of tocopherol and sterol | |
| US5985344A (en) | Process for obtaining micronutrient enriched rice bran oil | |
| JPH072827A (en) | Recovery of tocopherol and sterol | |
| EP0790990B1 (en) | Process for the production of tocopherol and tocopherol/tocotrienol concentrates | |
| JP5752341B2 (en) | Special palm oil products and other special vegetable oil products | |
| JP5803671B2 (en) | Method for reducing chloropropanols and their forming substances and glycidol fatty acid esters in glyceride oils and fats | |
| EP1689353B1 (en) | Recovery of phytonutrients from oils | |
| MXPA04002116A (en) | Methods for treating deodorizer distillate. | |
| JP2006225661A (en) | Improvement of qualities of crude oil and fat and recovery of minor ingredient | |
| GB2090836A (en) | Method for the preparation of tocotrienol concentrates from oleaginous materials | |
| Gunawan et al. | Isolation and purification of fatty acid steryl esters from soybean oil deodorizer distillate | |
| JPS6157309B2 (en) | ||
| JPS6193178A (en) | Separation of tocotrienols | |
| JPH08100131A (en) | Method of recovering carotene | |
| Quek et al. | Commercial extraction of vitamin E from food sources | |
| US5670668A (en) | Crystalline tocotrienol esters | |
| KR940002715B1 (en) | Method for separation and purification of natural tocopherol for deodorized sluge of soybean oil | |
| KR830000794B1 (en) | Process for preparing oil-containing high purity phosphatidylcholine | |
| JPH11263786A (en) | Production of isoflavone compound | |
| JPS595178A (en) | Separation of tocopherol and tocotrienol | |
| KR930005415B1 (en) | Method of tocopherol purification from a soybean oil | |
| NO118403B (en) | ||
| US2486540A (en) | Vitamin e preparation | |
| JPS61151186A (en) | Method of concentrating tocotrienol and tocopherol | |
| JPS6155917B2 (en) |