KR930005415B1 - Method of tocopherol purification from a soybean oil - Google Patents

Method of tocopherol purification from a soybean oil Download PDF

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KR930005415B1
KR930005415B1 KR1019910001231A KR910001231A KR930005415B1 KR 930005415 B1 KR930005415 B1 KR 930005415B1 KR 1019910001231 A KR1019910001231 A KR 1019910001231A KR 910001231 A KR910001231 A KR 910001231A KR 930005415 B1 KR930005415 B1 KR 930005415B1
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tocopherol
soybean oil
exchange resin
purity
purifying
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KR920014792A (en
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박영훈
정봉현
정수민
손정덕
신현호
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한국과학기술연구원
박원희
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
    • C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
    • C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols

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  • Organic Chemistry (AREA)
  • Pyrane Compounds (AREA)

Abstract

The tocopherol is purifyed by (a) adding mixed solvent of n- hexane and 50 % (v/v) methanol into the soybean oil distillate, (b) removing the sterol of the mixt. by filtering, cooling the filtered soln., and re-filtering, (c) methyl esterifying the mixt. from which sterol is removed, (d) recirculating esterified product at 100-130 deg.C and 10-3-10-4 torr in the molecular distillator to remove fatty acid methyl ester, (e) concentrating the obtd. soln. contg. 50-55 % tocopherol and dissolving in the lower alcohol (I), (f) adsorbing it into alkaline anion exchange resin, and purifying with the (I) contg. 5-10 % acetic acid, and (g) dissolving the purifyed tocopherol in the (I) and passing through cation exchange resin to obtain the final product.

Description

대두유 탈취 증류분으로부터 토코페롤을 정제하는 방법Method for Purifying Tocopherols from Soybean Oil Deodorized Distillates

본 발명은 대두유 탈취 증류분으로부터 토코페롤을 정제하는 방법에 관한 것으로서, 더욱 상세하게는 대두유 탈취 증류분에 함유되어 있는 토코페롤을 분자 증류법에 의해 1차로 분리 농축한다음 음이온 교환수지와 양이온 교환수지를 통과시켜 토코페롤을 고순도로 정제하는 방법에 관한 것이다.The present invention relates to a method for purifying tocopherol from soybean oil deodorized distillate, and more specifically, tocopherol contained in soybean oil deodorized distillate is first concentrated by molecular distillation and then passed through an anion exchange resin and a cation exchange resin. The present invention relates to a method for purifying tocopherol in high purity.

식물성 식용유 제조의 최종 단계에서는 유취성분을 제거하기 위해 탈취공정을 수행하게되며, 이러한 탈취공정의 결과 탈취 유출물이 얻어지게 된다.In the final stage of vegetable oil cooking, a deodorization process is performed to remove odorous components, and the deodorization effluent is obtained as a result of this deodorization process.

이중 대두유 탈취 유출물에는 토코페롤 성분이 8~15%정도 함유되어 있고, 이외에도 스테롤, 유리지방산, 탄화수소와 글리세라이드등과 같은 유용한 물질들이 다량 함유되어 있는 것으로 알려져 있는바, 이러한 성분들의 함량 및 조성은 탈취방법에 따라서 달라질 수 있을 뿐 아니라 동일한 대두의 경우라도 수확시기나 산지등에 따라서도 약간의 차이가 있는 것으로 알려지고 있다.Soybean oil deodorant effluent contains about 8 ~ 15% of tocopherol, and it is known to contain a large amount of useful substances such as sterol, free fatty acid, hydrocarbons and glycerides. Not only can it vary depending on the deodorization method, but even the same soybeans are known to be slightly different depending on the harvest season and the production area.

이중에서도 식물성 토코페롤은 천연 항산화제로 유지 및 라면등의 식품제조에 다량 사용되며, 특히 비타민E인 알파-토코페롤은 의약품, 화장품 등에 주로 사용되고 있다.Among them, vegetable tocopherol is used as a natural antioxidant in a large amount in the manufacture of foods such as fats and oils and ramen. Especially, alpha-tocopherol, which is vitamin E, is mainly used in medicines and cosmetics.

한편, 대두유 탈취 증류분으로부터 상기와 같이 이용되는 토코페롤을 분리하는 방법으로는 탈취증류분에 노말-헥산(n-hexane), 아세톤(acetone)등과 같은 유기용매를 첨가하여 결정으로 석출된 스테롤을 제거한후, 잔여 시료중 지방산을 에스테르화시켜 분자증류(molecular distillation)법에 의해 토코페롤을 농축하는 방법[미국특허 제2,317,353호 및 제2,349,375호, 일본특허공개소 50-106,710호]이 가장 보편적으로 이용되고 있다.On the other hand, as a method of separating the tocopherols used as described above from the soybean oil deodorized distillate, an organic solvent such as n-hexane, acetone, etc. is added to the deodorized distillate to remove sterols precipitated as crystals. After the esterification of the fatty acid in the residual sample to concentrate the tocopherol by molecular distillation method (US Patent Nos. 2,317,353 and 2,349,375, Japanese Patent Publication No. 50-106,710) is the most commonly used have.

그러나, 이러한 종래의 방법들은 최종 토코페롤의 농도가 40~50% 정도에 불과하므로 좀더 고순도의 토코페롤을 최종산물로 얻기 위해서는 새로운 분리방법의 개발이 요구되었다. 따라서, 일본특허공개소 38-23638호에서는 고순도의 토코페롤을 정제하기 위해 대두유 탈취증류분을 염기성 음이온교환 수지로 처리하여 토코페롤을 정제 농축하는 방법이 제안되어 순도가 65~68%까지 향상된 토코페롤을 최종산물로 얻은바 있다. 그러나, 이러한 방법은 토코페롤을 보다 고순도로 정제하는데는 개선의 여지가 있었다.However, these conventional methods require only 40 to 50% of the final tocopherol concentration. Therefore, in order to obtain higher purity tocopherol as a final product, development of a new separation method is required. Therefore, Japanese Patent Application Laid-Open No. 38-23638 proposes a method of purifying and concentrating tocopherol by treating soybean oil deodorization distillate with basic anion exchange resin in order to purify tocopherol of high purity. Obtained as a product. However, this method has room for improvement in purifying tocopherol to higher purity.

이에 본 발명자들은 상기와 같은 기존 방법들에 나타난 제 문제점을 개선하기 위해 오랜시간과 노력을 투자하여 연구 개발한 끝에 대두유 탈취증류분으로부터 토코페롤을 정제함에 있어서, 분자증류법에 의해 토코페롤을 1차로 농축한후 음이온 교환수지와 양이온 교환수지를 사용하여 비교적 간단하게 토코페롤을 고순도로 정제할 수 있는 새로운 방법을 개발하게되어 본 발명을 완성하게 되었다.Accordingly, the present inventors invested a long time and effort to improve the problems shown in the existing methods, and in the purification of tocopherol from soybean oil deodorized distillate, the first concentration of tocopherol by molecular distillation method After using the anion exchange resin and the cation exchange resin to develop a new method that can be purified tocopherol in a relatively simple high purity to complete the present invention.

따라서, 본 발명은 대두유 탈취 증류분으로부터 토코페롤을 정제함에 있어서, 종래와는 달리 분자 증류장치에 의해 1차로 분리 농축된 시료를 이용하여 음이온교환수지와 양이온교환수지를 사용하여 고순도 고수율로 토코페롤을 정제해내는 개선된 방법을 제공하는데 그 목적이 있다.Therefore, in the present invention, in purifying tocopherol from soybean oil deodorized distillate, tocopherol is obtained in high purity and high yield using an anion exchange resin and a cation exchange resin using a sample separated and concentrated primarily by a molecular distillation apparatus. The aim is to provide an improved method of purification.

이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명은 대두유탈취 증류분으로부터 토코페롤을 정제함에 있어서, 분자증류기로 1차 분리하고 50~55%로 농축시킨 토코페롤 시료를 저급1가알코올인 에탄올, 메탄올, 이소프로판올, 노말프로판올, 이소부탄올, 노말부탄올 등에 용해시켜서 염기성음이온 교환수지에 흡착시킨다음, 이를 다시 5~10%초산을 함유하는 상기의 저급1가 알코올 용액에 용출시켜 토코페롤을 1차 정제한다음 이를 다시 저급1가 알코올에 용해한후 양이온교환수지를 통과시켜서 됨을 특징으로 하는 토코페롤의 정제방법이다.In the present invention, in the purification of tocopherol from soybean oil deodorized distillate, the tocopherol sample firstly separated by molecular distillation and concentrated to 50-55% is ethanol, methanol, isopropanol, normal propanol, isobutanol, and normal butanol which are lower monohydric alcohols. After dissolving the same in a basic anion exchange resin, and then eluting it in the lower monohydric alcohol solution containing 5-10% acetic acid to first purify the tocopherol, and then dissolve it in the lower monohydric alcohol and then cation exchange. It is a purification method of tocopherol characterized by passing the resin.

이와같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.

본 발명은 대두유탈취 증류분으로부터 토코페롤을 정제함에 있어서, 대두유탈취 증류분에 노말-헥산과 50%(v/v) 메탄올의 혼합용매를 가한다음 이를 -10℃~5℃로 냉각시켜서 스테롤을 제거하고, 이렇게 스테롤이 제거된 시료를 메틸에스테르화 시킨후 100~130℃, 10-3~10-4토르에서 분자증류에 의해 지방산 메틸에스테르를 제거한 다음, 다시 170~200℃, 10-3~10-4토르에서 분자증류하여 순도 50~55%의 토코페롤을 1차로 분리 농축하였으며, 1차로 분리농축된 시료를 더욱 고순도로 정제하기 위해 이온교환수지를 통과시켰다. 여기에 사용된 이온교환수지는 간단히 재생시켜 반복사용이 가능하므로 본 방법은 공업적 토코페롤 정제법으로 매우 유리하다.In the present invention, in purifying tocopherol from soybean oil deodorized distillate, a mixed solvent of normal-hexane and 50% (v / v) methanol is added to the soybean oil deodorized distillate and then cooled to -10 ° C to 5 ° C to remove sterols. After methyl esterification of the sterol-removed sample, fatty acid methyl ester was removed by molecular distillation at 100-130 ° C, 10 -3-10 -4 Torr, and then again 170-200 ° C, 10 -3 -10 Molecular distillation at -4 torr was first concentrated to 50% to 55% purity of tocopherol, and the first separated and concentrated sample was passed through an ion exchange resin to further refine the purity. Since the ion exchange resin used herein can be simply regenerated and repeatedly used, this method is very advantageous as an industrial tocopherol purification method.

본 발명에서는 기존의 방법들을 개선하여 대두유탈취 증류분에 함유되어 있는 토코페롤을 분리하기 위하여 혼합용매를 이용하여 스테롤을 제거하고, 분자증류기로 농축한 토코페롤을 원료로 하여 음이온 및 양이온 교환수지를 이용하여 고순도로 정제하는 새롭고 효과적인 방법이다.In the present invention, to remove the tocopherol contained in the soybean oil deodorized distillate by improving the existing methods, sterols are removed by using a mixed solvent, using an anion and a cation exchange resin as a raw material tocopherol concentrated by molecular distillation It is a new and effective way to purify to high purity.

본 발명에 따르면 토코페롤을 효율적으로 정제하기 위해서 분자증류기를 이용하여 1차로 분리농축한 50~55% 순도의 토코페롤을 유극성 유기용매인 저급1가 알코올, 예컨대 에탄올에 용해한후, 이것을 음이온교환수지 중 -CH2N+(CH3)3Cl-와 같은 강염기성 작용기를 가지는(예 : Amberlite IRA -401등) 수지탑에 통과시켜 탄화수소, 고급알코올, 색소의 일부 및 이외의 불순물을 제거하고 토코페롤 물질만 선택적으로 수지에 흡착시키고 나서 산성 유기용매인 5~10% 초산을 함유하는 에탄올용액으로 토코페롤을 용출시켜 고순도의 토코페롤을 얻었다.According to the present invention, in order to efficiently purify tocopherol, 50-55% purity tocopherol, which is primarily separated and concentrated by molecular distillation, is dissolved in a lower monohydric alcohol, such as ethanol, which is a polar organic solvent, and then, in anion exchange resin. -CH 2 N + (CH 3) 3 Cl - with a strongly basic functional group, such as (for example: Amberlite IRA -401, etc.) was passed through the resin column hydrocarbon, higher alcohol, removing the impurities and part of the coloring material other than the tocopherol Only after selectively adsorbing to the resin, tocopherol was eluted with an ethanol solution containing 5-10% acetic acid as an acidic organic solvent to obtain high purity tocopherol.

이때, 55 이하의 초산농도를 사용하게 되면 보다 많은 양의 용축액이 소요되므로 비경제적이며, 10% 이상의 초산농도의 경우에는 오히려 토코페롤 이외의 불순물이 용출될 가능성이 있으므로 적합하지 않다.At this time, the use of acetic acid concentration of 55 or less is more economical because it takes a larger amount of the stock solution, and in the case of acetic acid concentration of 10% or more, it is not suitable because impurities other than tocopherol may be eluted.

이렇게 얻은 농축 토코페롤의 순도를 더욱 높이기 위해 다시 유극성 유기용매인 에탄올에 시료를 녹여 양이온교환수지중 -SO3 -H+와 같은 강산성작용기를 가지는(예 : Amberlite IR-120)수지탑에 통과시키면 비극성 물질들만 수지에 흡착되고, 극성물질인 토코페롤은 유기용매와 함께 흘러나오게 되므로 이 용매를 증류시키면 고순도의 토코페롤을 얻을 수 있다.In order to further increase the purity of the concentrated tocopherol, the sample was dissolved in ethanol, a polar organic solvent, and passed through a resin tower having a strong acidic functional group such as -SO 3 - H + in the cation exchange resin (for example, Amberlite IR-120). Only non-polar substances are adsorbed on the resin, and tocopherol, which is a polar substance, flows out together with the organic solvent, so that distillation of the solvent yields a high purity tocopherol.

상술한 바와같이 본 발명에 따르면 종래와는 달리 대두유탈취 증류분에서 1차로 토코페롤을 50~55% 정도로 농축시킨 다음, 음이온 및 양이온교환수지를 차례로 통과시켜 고순도 토코페롤을 얻는 방법으로서, 종래에 방법에 비해 순도가 약 20% 이상 향상된 새롭고 매우 효과적인 방법인 것이다.As described above, according to the present invention, the tocopherol is first concentrated in a soybean oil deodorized distillate, about 50 to 55%, and then an anion and a cation exchange resin are sequentially passed to obtain a high purity tocopherol. It is a new and very effective way to improve purity by about 20% or more.

이하, 본 발명을 실시예에 의거 상세히 설명하겠는바, 본 발명이 실시예에 의거 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to Examples.

[실시예 1]Example 1

토코페롤을 함유하고 있는 대두유탈취 증류분에 노말-헥산과 50%(v/v) 메탄올을 10 : 1의 부피비율로 넣고 충분히 교반한후 석출된 스테롤 결정을 여과하여 제거하고 여과지를 통과한 여과액을 냉각한 다음 재석출된 스테롤을 제거하였다.Normal-hexane and 50% (v / v) methanol were added to a volume ratio of 10: 1 in soybean oil deodorized distillate containing tocopherol, and after sufficient stirring, the precipitated sterol crystals were filtered off and the filtrate passed through the filter paper. After cooling, the reprecipitated sterol was removed.

스테롤이 제거된 잔여시료를 지방산 메틸에스테르화시킨후, 이 시료를 100~130℃, 10-3-10-4토르에서 재순환 분자 증류하여 메틸에스테르화된 지방산을 제거하고, 그 잔류액을 다시 170~200℃, 10-3-10-4토르에서 재순환 분자증류하여 순도 51.1%인 토코페롤 농축물을 얻었다.After fatty acid methyl esterification of the residual sample with sterols removed, the sample was recycled to molecular distillation at 100-130 ° C and 10 -3 -10 -4 torr to remove the methyl esterified fatty acid, and the residue was again 170. Recycle molecular distillation at ˜200 ° C., 10 −3 −10 −4 Torr to obtain a tocopherol concentrate having a purity of 51.1%.

이 시료 6g을 에탄올 20~30ml에 용해한 후, 염기성 음이온 교환수지인 Amberlite IRA-401로 충진된 직경 4cm, 길이 60cm인 유리원통에 유속 2ml/min로 흘려보내어 토코페롤을 수지에 흡착시킨 다음, 에탄올 300ml로 수지를 세척하여 고급알코올, 지방산 등을 제거하였다. 수지에 흡착된 토코페롤은 10% 초산을 함유하는 에탄올 용액 약 500ml를 유속 5ml/min로 흘려보내 흡착된 토코페롤을 수지에서 용출시켰으며, 이 용출액에서 용제를 제거하여 순도 77.4%의 토코페롤 농축물 3.4g을 얻었다.6 g of this sample was dissolved in 20-30 ml of ethanol, and then flowed into a glass cylinder of 4 cm diameter and 60 cm length filled with basic anion exchange resin Amberlite IRA-401 at a flow rate of 2 ml / min to adsorb tocopherol to the resin, and then 300 ml of ethanol. The resin was washed with to remove higher alcohol, fatty acids and the like. Tocopherol adsorbed on the resin flowed about 500ml of ethanol solution containing 10% acetic acid at a flow rate of 5ml / min, and the adsorbed tocopherol was eluted from the resin, and the solvent was removed from the eluate to obtain 3.4.4% pure tocopherol concentrate 3.4g. Got.

[실시예 2]Example 2

실시예 1에서 얻어진 토코페롤을 더욱 고순도로 농축시키기 위하여 양이온 교환수지인 Amberlite IR-120을 실시예 1과 같은 유리원통에 충전한 후, 실시예 1에서 얻어진 농축 토코페롤 3g을 20ml의 에탄올에 용해하여 유속 2ml/min로 흘려보내고 계속해서 에탄올 300ml 정도를 유속 5ml/min로 흘러보내 수지에 흡착되지 않고 에탄올에 녹아 나온 토코페롤 용액을 회수한 다음, 에탄올을 증류하여 순도 85.5%의 토코페롤 농축물 2.61g을 얻었다.In order to further concentrate the tocopherol obtained in Example 1, Amberlite IR-120, a cation exchange resin, was charged in the same glass cylinder as in Example 1, and then 3 g of the concentrated tocopherol obtained in Example 1 was dissolved in 20 ml of ethanol and flow rate The solution was flowed at 2 ml / min, and 300 ml of ethanol was continuously flowed at a flow rate of 5 ml / min to recover a tocopherol solution dissolved in ethanol without being adsorbed to the resin, and then ethanol was distilled to obtain 2.61 g of a tocopherol concentrate having a purity of 85.5%. .

[비교예 1~3][Comparative Examples 1-3]

대두유탈취 증류분으로부터 염기성 음이온 교환수지를 이용 토코페롤을 농축하는 기존의 방법(일본특허공개소 38-23638호)에 따라 스테롤, 지방산등 유용물질이 제거되지 않은 대두유탈취 증류분(토코페롤 농도 8.25)을 음이온 교환수지에 통과시켜 토코페롤을 농축하여 순도가 66.6%인 토코페롤 농축물을 얻었다(비교예 1).Soybean oil deodorized distillate (tocopherol concentration 8.25), which is free of useful substances such as sterols and fatty acids according to the existing method of concentrating tocopherols using a basic anion exchange resin from soybean oil deodorized distillate (Japanese Patent Publication No. 38-23638). Tocopherol was concentrated by passing through an anion exchange resin to obtain a tocopherol concentrate having a purity of 66.6% (Comparative Example 1).

이외에도 면실유 탈취 부산물을 분자 증류기로 지방산을 대부분을 제거한 토코페롤 농축물(순도 31.7%)을 상기와 같은 방법으로 염기성 음이온 교환수지인 Duolite A-42LC와 Dowex 2를 사용한 결과 순도는 각각 68%와 65%이었다(비교예 2 및 3).In addition, the tocopherol concentrate (purity 31.7%), in which the cotton oil deodorization by-products were removed from the fatty acid using a molecular distiller, was purified using the basic anion exchange resin, Duolite A-42LC and Dowex 2, in which the purity was 68% and 65%, respectively. (Comparative Examples 2 and 3).

본 발명의 실시예 1과 비교예의 결과로부터 본 발명의 방법이 종래의 방법(비교예)에 비해 토코페롤 순도면에서 10%이상 더 향상시킬 수 있고 실시예 2의 경우는 순도가 19% 이상 더 향상되었음을 알 수 있었다.From the results of Example 1 and Comparative Example of the present invention, the method of the present invention can be improved by 10% or more in terms of purity of tocopherol compared to the conventional method (Comparative Example), and in Example 2, the purity is further improved by 19% or more. It was found.

Claims (1)

대두유탈취 증류분으로부터 토코페롤을 정제함에 있어서, 분자증류기로 1차 분리하여 50~55%로 농축시킨 토코페롤 시료를 저급1가 알코올에 용해시켜서 염기성 음이온 교환수지에 흡착시킨다음, 5~10% 초산을 함유하는 저급1가 알코올 용액으로 용출시켜 토코페롤을 1차 정제한다음 이를 다시 저급1가 알코올에 용해한후 양이온 교환수지를 통과시켜서 됨을 특징으로 하는 대두유탈취 증류분으로부터 토코페롤을 정제하는 방법.In purifying tocopherol from soybean oil deodorized distillate, the tocopherol sample, which was first separated by molecular distillation and concentrated to 50-55%, was dissolved in lower monohydric alcohol and adsorbed onto basic anion exchange resin, and then 5-10% acetic acid was added. A method of purifying tocopherol from a soybean oil deodorizing distillate characterized in that it is eluted with a lower monohydric alcohol solution to first purify the tocopherol and then dissolved in the lower monohydric alcohol and then passed through a cation exchange resin.
KR1019910001231A 1991-01-25 1991-01-25 Method of tocopherol purification from a soybean oil KR930005415B1 (en)

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