KR940002715B1 - Method for separation and purification of natural tocopherol for deodorized sluge of soybean oil - Google Patents
Method for separation and purification of natural tocopherol for deodorized sluge of soybean oil Download PDFInfo
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- 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
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Abstract
Description
본 발명은 대두유 탈취 부산물로부터 천연토코페롤을 분리, 정제하는 방법에 관한 것으로서, 더욱 상세하게 설명하면 대두유 탈취 부산물을 특정 혼합용매로 처리하여 스테롤 혼합물을 제거하고, 메틸에스테르화시킨후, 음이온 교환수지컬럼(column)에 통과시켜 얻은 토코페롤을 다시 분자증류법으로 농축함으로써 고순도 토코페롤을 고수율로 다량 정제할 수 있는 새롭고 생산성이 매우 높은 분리, 정제방법에 관한 것이다.The present invention relates to a method for separating and purifying natural tocopherol from soybean oil deodorization by-products, and in more detail, treating a soybean oil deodorization by-product with a specific mixed solvent to remove the sterol mixture, methyl esterification, and anion exchange resin column. The present invention relates to a new and highly productive separation and purification method capable of purifying high-purity tocopherol in high yield by concentrating the tocopherol obtained by passing through a column again in molecular distillation.
일반적으로 식물성 식용유를 제조하는 공정의 마지막 단계에서는 2-6㎜Hg로 감압된 상태에서 식용유에 고온(200~260℃)의 수증기를 흡입시킴으로써 불쾌한 유취성분을 제거하는 탈취공정을 수행하게되며, 그 결과로써 다량의 부산물이 얻어지게 된다.In general, in the last step of the process of manufacturing vegetable cooking oil, deodorizing process is performed to remove unpleasant odorous components by inhaling steam of high temperature (200 ~ 260 ℃) in cooking oil under reduced pressure to 2-6mmHg, As a result, a large amount of by-products are obtained.
이와같은 탈취 부산물은 탈취용 증류탑의 윗부분과 아래부분에서 각각 배출되는데, 전자는 휘발도가 높은 물질들로 이루어진 혼합 응축물로서 일반적으로 셀 드레인 콘센트레이드(shell drain concentrate) 또는 조지방산이라고 하며, 후자는 스팀 에젝터(steam ejector)와 연결된 기압응축기(barometric condenser) 출구에서 배출되는 혼합물로서 hot-well skimmings, hot well scum, clabber, deodorizer trap oil 또는 scum이라 칭하고, 이 두 물질을 모아 가열하려 수분을 제거하면, 점도가 매우 높고 반고체 상태인 갈색물질이 회수되는데 이것을 통상 탈취 부산물이라고 일컫는다.These deodorization by-products are discharged from the upper and lower portions of the deodorizing distillation column, respectively. The former is a mixed condensate composed of highly volatile substances, commonly referred to as shell drain concentrate or crude fatty acid. Is a mixture discharged from a barometric condenser outlet connected to a steam ejector, called hot-well skimmings, hot well scum, clabber, deodorizer trap oil, or scum. When removed, a very high viscosity, semisolid solid is recovered which is commonly referred to as deodorization by-product.
일반적으로 식물유 탈취 부산물의 조성은 그 사용원료에 따라서 현격한 차이가 있을뿐만아니라 같은 원료일지라도 그 수확시기나 산지 등이 다를 경우에도 적지 않은 차이가 있기는 하지만, 대두유 탈취 부산물의 경우에는 대체로 토코페롤이 8~15% 정도로서 비교적 높게 함유되어 있으며, 또한 스테롤류, 글리세라이드류, 유리지방산류, 탄화수소류 등의 고부가 가치성 원료물질들도 함께 포함되어 있는 것으로 알려져 있다.In general, the composition of vegetable oil deodorization by-products is not only significantly different depending on the raw materials used, but even when the same raw materials are used, even when the harvest season or the production region are different. It is relatively high as 8-15%, and it is also known to contain high value-added raw materials such as sterols, glycerides, free fatty acids and hydrocarbons.
그중에서도 식물성 토코페롤은 현재 식용성 유지제품 및 라면 등의 인스턴트식품 제조과정에서 항산화제로서 폭넓게 사용되고 있으며, 특히 비타민-E로 잘 알려져 있는 알파-토코페롤은 의약품 원료와 화장품 첨가제등으로 그 수요가 급격히 늘어나고 있는 매우 유망한 개발품목중 하나로 주목받고 있다.Among them, vegetable tocopherol is widely used as an antioxidant in the manufacture of instant foods such as edible oils and ramens, and alpha-tocopherol, which is well known as vitamin-E, is rapidly increasing as a raw material for pharmaceuticals and cosmetic additives. It is attracting attention as one of the very promising development items.
본발명에서 총칭되어지는 토코페롤이란 천연의 α-,β-,γ-,δ-,ε-,ζ-,η-토코페롤로 불려지는 것들뿐만아니라 합성 토코페롤류 등의 모든 동족체를 모두 포함한다.Tocopherol generically used in the present invention includes all homologues such as synthetic tocopherols as well as those called natural α-, β-, γ-, δ-, ε-, ζ-, η-tocopherols.
이와같은 토코페롤의 분리 및 정제방법으로는 대두유 탈취 부산물 5.1g(토코페롤농도 8.2%)을 알코올에 용해시킨뒤 50㎖의 염기성 음이온 교환수지(OH형)에서 정제하여 0.75g의 순도 66.6%인 토코페롤 농축물을 얻는 방법(일본 특허공개 소 38-23638) ; 면실유 탈취 부산물에서 스테롤 혼합물을 제거한후, 니코티네이트(nicotinate)등으로 토코페롤류가 가지고 있는 페놀성 수산기를 에스테르화시킨다음, 이렇게 얻은 시료 135g을 700㎖의 산성 양이온 교환수지 컬럼에서 분리 및 정제하여 24.3g의 토코페롤 니코티네이트(tocopherol nicotinate)를 얻는 방법(일본 특허공개소 38-23639) ; 그리고 특정 용매추출법으로 스테롤 혼합물을 제거한 대두유 탈취 부산물(토코페롤 농도 15.6% ; 3.86㎏)을 호박산등과 에스테르화 반응시킴으로써, 여기에 함유되어 있는 토코페롤을 산성 유도체 형태로 변형시킨다음, 5500㎖의 염기성 음이온 교환수지 컬럼에서 분리 및 정제하여 고순도의 토코페롤 813g을 얻는 방법(일본특허공개소 41-1618)등이 현재까지 가장 보편적으로 이용되고 있다.The separation and purification of tocopherols was performed by dissolving 5.1 g of soybean oil deodorization by-product (8.2% tocopherol concentration) in alcohol and purifying it in 50 ml of basic anion exchange resin (OH type) to concentrate 0.75g of 66.6% pure tocopherol. Method of obtaining water (Japanese Patent Laid-Open No. 38-23638); After removing the sterol mixture from cottonseed oil deodorization by-product, esterification of phenolic hydroxyl group of tocopherols with nicotinate was carried out, and 135 g of the obtained sample was separated and purified in a 700 ml acidic cation exchange resin column. A method of obtaining 24.3 g of tocopherol nicotinate (Japanese Patent Laid-Open No. 38-23639); And the soybean oil deodorization by-product (tocopherol concentration 15.6%; 3.86 kg) from which the sterol mixture was removed by a specific solvent extraction method was esterified with succinic acid and the like to transform the tocopherol contained therein into an acid derivative form, and then 5500 mL of basic anion. A method of obtaining 813 g of high purity tocopherol by separating and purifying in an exchange resin column (Japanese Patent Laid-Open No. 41-1618) and the like are the most commonly used.
그러나, 이러한 기존의 방법들은 대부분이 탈취 부산물 자체 또는 용매추출법 및 분자증류법등을 사용하여 전처리된 것에 피리딘을 촉매로하여 에스테르화시킴으로써 산성 또는 염기성 유도체 형태로 토코페롤을 변형시킨후, 이것을 다시 산성 또는 염기성 이온 교환수지컬럼에 주입하여 분리 및 정제하는 방법들로서 항산화제로 사용되는 토코페롤 농축액을 얻기 위해서는 토코페롤 유도체를 다시 환원시켜야 하는등 전체 공정도 다소 복잡하기 때문에 공정 스케일 엎(scale-up)에 많은 제한이 따르며 결과적으로 산업적 토코페롤 농축법으로 사용하기에는 개선의 여지가 많았다.However, most of these existing methods detoxify tocopherol in the form of acidic or basic derivatives by esterifying pyridine to catalyzed esterification by deodorization by-product itself or solvent extraction and molecular distillation. In order to separate and purify by injecting ion exchange resin column, to obtain the tocopherol concentrate used as an antioxidant, the entire process is somewhat complicated. As a result, there was much room for improvement for industrial tocopherol enrichment.
따라서, 본발명은 종래방법들의 이러한 문제점을 개선하기위해 지방산을 메틸에스테르화시키므로써 대두유 탈취 부산물로부터 고순도의 천연토코페롤을 고수율로 분리, 정제해낼 수 있는 효과적인 방법을 제공하는데 그 목적이 있다.Accordingly, the present invention aims to provide an effective method for separating and purifying high-purity natural tocopherol in high yield from soybean oil deodorization by-products by methyl esterifying fatty acids to improve this problem of conventional methods.
이하, 본발명은 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 대두유 탈취 부산물로부터 천연토코페롤을 분리정제함에 있어서, (가) 대두유 탈취 부산물을 저용성 유기용매로 용해시키고 물 또는 알코올을 첨가하여 결정화된 스테롤 혼합물을 여과, 제거하고, (나) 얻어진 잔류 지방산류을 메틸에스테르화시킨다음, (다) 이를 저급알콜의 유극성 유기용매에 용해하고 염기성 음이온 교환수지에 유입시켜서 산성용매로 용출하는 것을 특징으로 하는 방법인 것이다.In the present invention, in the separation and purification of natural tocopherol from soybean oil deodorization by-product, (A) the soybean oil deodorization by-product is dissolved in a low-soluble organic solvent, and the crystallized sterol mixture is filtered and removed by adding water or alcohol, and (B) the residue obtained. The fatty acid is methyl esterified, and (c) is dissolved in a polar organic solvent of lower alcohol and introduced into a basic anion exchange resin to elute with an acidic solvent.
이하, 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
대두유 탈취부산물에 1~3부피배의 노말-헥산, 노말-헵탄, 아세톤, 또는 메틸에틸케톤 등의 지용성 유기용매를 가함으로써 완전히 용해시킨다음, 물이나 탄소수 1-4개의 알코올류 또는 물이 함유된 알코올류를 지용성 유기용매에 대해 0.1~0.3부피배 첨가하여 스테롤 결정을 생성시키고 동시에 여과한다.Soybean oil deodorized by-products are dissolved by adding 1 to 3 volumes of fat-soluble organic solvents such as normal-hexane, normal-heptane, acetone, or methyl ethyl ketone, and then dissolved in water or alcohols containing 1-4 carbon atoms or water. The alcohols were added 0.1 to 0.3 by volume to the fat-soluble organic solvent to form sterol crystals and simultaneously filtered.
여기서 남은 여액을 5℃ 이하로 냉각하고 재여과함으로써 잔류 스테롤 혼합물을 완전히 제거한 일차시료를 얻는다.The remaining filtrate is cooled to below 5 ° C. and refiltered to obtain a primary sample from which the residual sterol mixture is completely removed.
상기의 스테롤 혼합물 석출과정에서 사용한 유기 용매량은 가능한 적게 설정하는것이 좋으나 여과 및 세척공정에 한계가 있기때문에, 본발명에서는 첨가 유기용매량을 탈취부산물의 1-3부피배로 하였다.It is preferable to set the amount of the organic solvent used in the sterol mixture precipitation process as small as possible, but there is a limit in the filtration and washing process.
또한, 이렇게 용해된 탈취부산물에 물 또는 메탄올, 에탄올 등의 저가알코올류를 첨가하는 모든 방법으로도 스테롤을 결정화시킬 수 있지만, 특히, 노말헥산과 50% 메탄올과의 혼합용액을 대두유 탈취 부산물 1㎏에 대하여 1~3ℓ첨가한후 냉각시키면 회수율 및 순도면에서 가장 좋은 결과를 얻은 수 있으며, 그이외 혼합비율의 메탄올 용액을 사용할 경우에는 스테롤 혼합물의 회수율은 현저히 저하되었다.In addition, sterol may be crystallized by all methods of adding water or low-cost alcohols such as methanol and ethanol to the deodorized by-product so dissolved. In particular, a mixed solution of normal hexane and 50% methanol may be 1 kg of soybean oil deodorization by-product. After adding 1 to 3 liters of water, the best results were obtained in terms of recovery and purity. When using a mixed solution of methanol, the recovery rate of the sterol mixture was remarkably decreased.
또한, 상기 노말-헥산, 노말-헵탄, 아세톤 또는 메틸에틸케톤 등의 지용성 유기용매류와 물 또는 메탄올, 에탄올 등의 저가알코올류를 10 : 1 비율로 혼합하여 사용하여도 스테롤 혼합물을 결정화시킬 수 있다.In addition, the sterol mixture can be crystallized by using a mixture of fat-soluble organic solvents such as normal-hexane, normal-heptane, acetone or methyl ethyl ketone and water or low-cost alcohols such as methanol and ethanol in a 10: 1 ratio. have.
상기의 방법으로 얻어진 일차시료에 메탄올, 에탄올 또는 이소프로판올 등의 알코올류를 1 : 1-5의 부피비율로 섞은다음, 전체무게에 대하여 5% 이하의 35%(v/v) 염산을 촉매로 사용하여 60℃-80℃에서 환류시킴으로써 시료에 함유되어 있는 여러가지 지방산류를 에스테르화 시킨다.The primary sample obtained by the above method is mixed with alcohols such as methanol, ethanol or isopropanol in a volume ratio of 1 to 1-5, and then 35% (v / v) hydrochloric acid of 5% or less based on the total weight is used as a catalyst. By refluxing at 60 ℃-80 ℃ to esterify the various fatty acids contained in the sample.
이렇게 얻은 2차 처리시료 200g을 다시 유극성 유기용매에 완전히 녹인다음, 폴리스틸렌 겔(polystylene gel)에 Φ-CH2N+(CH3)3Cl-의 작용기(OH형)가 부착되어 있는 강염기성 음이온수지, 예컨대 앰버라이트 IRA-401이 채워진 음이온 교환수지 컬럼에 유입시키면 토코페롤류만 선택적으로 수지에 흡착되며, 나머지 에스테르지방산류, 탄화수소류, 고급알코올류, 색소의 일부, 그리고 그밖의 여러가지 불순물들은 유출 및 분리된다. 이때 음이온교환수지로서는 상기 앰버라이트 IRA-401 외에 앰버라이트 400,402,411, 도웩스-1,2,3, 다이아이온 SA-100,101,200,201, 또는 두오라이트 40LC, A-42LC를 사용할 수 있다.200 g of the secondary sample thus obtained is completely dissolved in a polar organic solvent, and then a strong base having a functional group (OH type) of Φ-CH 2 N + (CH 3 ) 3 Cl - attached to a polystylene gel. When introduced into an anion resin column filled with an anionic resin, such as Amberlite IRA-401, only tocopherols are selectively adsorbed to the resin. Spills and separates. In this case, as the anion exchange resin, in addition to the Amberlite IRA-401, Amberlite 400,402,411, Dow's-1,2,3, Diaion SA-100,101,200,201, or Duolite 40LC and A-42LC may be used.
이어서, 저급알콜과 산성용매가 9~9.8 : 0.2~1의 부피비율로 혼합된 산성 유기용매를 충분히 유입시키면 수지에 흡착되어 있던 토코페롤은 쉽게 용출되며, 순도 56% 이상의 토코페롤을 90% 이상의 회수율로 얻을 수 있다.Subsequently, when sufficient acidic organic solvent mixed with a lower alcohol and an acidic solvent in a volume ratio of 9 to 9.8: 0.2 to 1 is sufficiently introduced, the tocopherols adsorbed on the resin are easily eluted, and tocopherols having a purity of 56% or more with a recovery rate of 90% or more are obtained. You can get it.
또한, 이렇게 분리된 순도 56% 이상의 토코페롤 농축액을 다시 분자증류장치로 처리하면 85%까지 고순도 토코페롤 제품을 얻을 수 있다.In addition, by treating the separated tocopherol concentrate of 56% or more purity with a molecular distillation apparatus again, high purity tocopherol products can be obtained up to 85%.
본발명에서 2차시료를 초리할때는 에탄올 이외에도 유극성 유기용매로서 메탄올, 이소프로판올, n-프로판올, 이소부탄올, n-부탄올과 같은 탄소수 1~4개의 저급알콜 등도 이용 가능하며, 음이온 교환수지로부터 토코페롤을 용출할때 가능한 산성용매로서는 초산이외에 개미산(formic acid)과 옥살산(oxalic acid), 호박산 등도 가능하다.In order to isolate the secondary sample in the present invention, in addition to ethanol, as a polar organic solvent, lower alcohols having 1 to 4 carbon atoms such as methanol, isopropanol, n-propanol, isobutanol, and n-butanol can be used. In addition to acetic acid, formic acid solvents available during elution may be formic acid, oxalic acid, succinic acid, and the like.
상술한 바와같이 본발명은 기존의 토코페롤 분리 및 정제방법과는 달리 지방산류를 메틸에스테르화시키기 때문에 토코페롤 회수율을 90% 이상 유지시키면서도 단위 수지량당 처리원료량을 매우 높게 할 수 있는 생산성이 매우 높은 방법일 뿐만아니라 또한 여기에 사용된 이온교환 수지의 활성화 조작 및 조건이 극히 단순하여 재현성이 높고, 수지의 재사용이 가능하기때문에 경제성 및 실용성이 매우 높은 토코페롤의 농축방법이라 할 수 있다.As described above, unlike the conventional method of separating and purifying tocopherol, the present invention uses methyl esterification of fatty acids, and thus a highly productive method capable of increasing the amount of raw materials per unit resin amount while maintaining tocopherol recovery of 90% or more. In addition, the activation operation and conditions of the ion exchange resin used herein are extremely simple and highly reproducible, and since the resin can be reused, it can be said to be a method of concentrating tocopherol having high economical efficiency and practicality.
이하, 본발명을 실시예에 의거 상세히 설명하겠는바, 본발명이 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.
본 실시예에서는, 스테롤 혼합물만 제거한 1차 처리시료와 본발명에서 새로이 개발한 방법으로 처리된 2차 처리시료 각각에서의 단위 수지양당 원료처리양에 대한 회수율 및 농축도의 변화를 살펴봄으로써, 본발명 공정에서의 최적 조업조건을 알아보았다.In the present embodiment, the present invention is examined by examining the change in the recovery rate and the concentration of the raw material amount per unit resin amount in each of the primary treatment sample in which only the sterol mixture is removed and the secondary treatment sample treated by the method newly developed in the present invention. The optimum operating conditions in the process were investigated.
[실시예 1]Example 1
대두유 탈취부산물 1㎏에 10 : 1 부피비율의 노말헥산과 50%(v/v) 메탄올의 혼합 유기용매 1.2ℓ를 가하고 서서히 교반하면서 5℃ 이하로 냉각한다음, 재결정법으로 스테롤 혼합물을 여과 및 제거하여 일차시료를 얻는다. 여기서 얻어진 일차시료에 다시 메탄올을 3배의 부피비율로 섞고 전체무게에 5% 이하 정도로 35%(v/v) 염산촉매를 넣은 다음, 60-80℃에서 환류시킴으로써 지방산류를 메틸에스테르화여 이차시료를 충분히 확보한후, 40,80,120,150g의 1차 처리시료(토코페롤 함량 16%)와 40,80,120,150,200,250g의 2차 처리시료(토코페롤 함량 17%)를 정확히 정량한후, 각각을 유극성 유기매인 에탄올로 용해하여 실험 시료로 준비한다.To 1 kg of soybean oil deodorized by-product, 1.2 l of a mixed organic solvent of 10: 1 volume ratio of normal hexane and 50% (v / v) methanol was added thereto, cooled to 5 ° C. or lower with gentle stirring, and the sterol mixture was filtered by recrystallization. Remove to obtain a primary sample. The primary sample obtained here was mixed with methanol at a volume ratio of 3 times, 35% (v / v) hydrochloric acid catalyst was added to the total weight of about 5% or less, and the mixture was refluxed at 60-80 ° C. to methyl esterify the fatty acid. After adequately secured, 40,80,120,150g of primary treatment sample (tocopherol content 16%) and 40,80,120,150,200,250g of secondary treatment sample (tocopherol content 17%) were accurately quantified, respectively, Dissolve in and prepare as an experimental sample.
그리고 염기성 음이온 교환수지 앰버라이트 IRA-401을 직경 4㎝, 길이 22㎝의 원통 유리관에 충진시킨후, 여기에 앞에서 준비한 실험시료들을 유속 3~5㎖/min로 유입시켜 토코페롤을 수지에 흡착시키고 다시 에탄올 100~300㎖로 수지를 세척하여 고급알코올, 에스테르지방산류 등을 제거한다음, 10% 초산이 함유된 에탄올용액 500~1200㎖로 이온교환수지에 흡착된 토코페롤을 용출시킨다. 이 용출액을 진공 증류시켜 용매를 제거함으로써 토코페롤 농축액을 얻는 동시에 고성능 액체크로마토그래피를 사용하여 토코페롤 함량을 정량했다.After filling the basic anion exchange resin Amberlite IRA-401 into a cylindrical glass tube 4cm in diameter and 22cm in length, the test samples prepared above were introduced at a flow rate of 3 to 5ml / min to adsorb tocopherol to the resin and again. The resin is washed with 100-300 ml of ethanol to remove higher alcohols, ester fatty acids, and the like, and the tocopherol adsorbed on the ion exchange resin is eluted with 500-1200 ml of ethanol solution containing 10% acetic acid. The eluate was vacuum distilled to remove the solvent to obtain a tocopherol concentrate, and the tocopherol content was quantified using high performance liquid chromatography.
다음 표 1은 앞에서 기술한 모든 시료를 가지고 동일한 작업을 반복 수행함으로써 각 경우에서의 토코페롤의 농축도와 회수율을 살펴본 것을 종합적으로 정리하여 나타낸 것이다.Table 1 summarizes the results of the concentration and recovery of tocopherol in each case by repeating the same operation with all the samples described above.
[표 1]TABLE 1
스테롤 혼합물만 제거된 1차 처리시료의 경우에서는 농축도가 1.5배 이상 증가하지 않을뿐만아니라 회수율도 대체로 저조하였으나 지방산류를 메틸에스테르화시킨 2차 처리시료의 경우에서는 단위 수지량당 처리 원료량이 0.7(g/㎖) 이상일 경우에도 3.3~3.9배의 높은 농축도를 나타내었으며, 결과적으로 순도 55% 이상 최고 66.4%의 토코페롤 농축물을 회수율 90% 이상으로 얻을 수 있다.In the case of the first treatment sample in which only the sterol mixture was removed, the concentration was not increased more than 1.5 times, and the recovery was generally low. In the case of the second treatment sample in which the fatty acid was methyl esterified, the amount of raw material per unit resin amount was 0.7 (g / Ml), the concentration was 3.3 ~ 3.9 times higher. As a result, a tocopherol concentrate with a purity of 55% or more and up to 66.4% can be obtained with a recovery rate of 90% or more.
[실시예 2]Example 2
실시예 1에서 얻은 토코페롤 농축물 100g(순도 60%)을 다시 170~190℃의 온도와 10-3~10-4㎜Hg의 진공조건에서 분자증류법으로 농축하여 순도 70% 이상의 토코페롤 제품을 얻었다.100 g (60% purity) of the tocopherol concentrate obtained in Example 1 was further concentrated by molecular distillation at a temperature of 170 to 190 ° C and a vacuum condition of 10 -3 to 10 -4 mmHg to obtain a tocopherol product having a purity of 70% or more.
일반적으로 항산화제로서 상품화되고 있는 천연토코페롤 농축액은 그 순도가 50~70% 정도이기때문에 본 발명에서 새로이 도입된 방법으로만 생산되는 천연토코페롤 농축액도 충분히 항산화제로서 상품가치가 있으며, 분자증류기를 사용하면 이보다 더 높은 순도의 토코페롤도 얻을 수 있다.In general, the natural tocopherol concentrate commercialized as an antioxidant has a purity of about 50-70%, and thus, the natural tocopherol concentrate produced only by the method newly introduced in the present invention is sufficiently valuable as an antioxidant and has a molecular distillation. Higher purity tocopherols can be obtained.
이상에서 알 수 있는 바와같이 천연토코페롤을 대두유 탈취 증류분에서 농축하는 일본 특허공개소 38-23639와 본발명을 비교할 경우에 본발명은 단위 수지양당 원료 처리량이 6배이상 증가하였기때문에 매우 생산성이 높을 뿐만아니라 본발명과 유사한 처리능력이 있는 일본 특허공개소 41-1618의 경우와 같이 토코페롤에 호박산 등과 같은 산성기를 도입하는 화학반응을 거치지 않고, 지방산류에 메틸에스테르화 반응을 시킴에 따라 순수 천연토코페롤을 손쉽게 얻게 됨으로써 공정 자체를 대폭 줄일 수 있다는 장점도 있다.As can be seen from the above, when the present invention is compared with Japanese Patent Publication No. 38-23639, which concentrates natural tocopherol in soybean oil deodorized distillate, the present invention is very productive because the processing amount of raw materials per unit resin amount is increased by 6 times or more. In addition, as in the case of Japanese Patent Publication No. 41-1618, which has a similar treatment capacity to the present invention, the natural natural tocopherol is subjected to a methyl esterification reaction to fatty acids without undergoing a chemical reaction of introducing acidic groups such as succinic acid into tocopherol. The benefit of this is that the process itself can be significantly reduced.
Claims (9)
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| EP1487554A2 (en) * | 2002-03-18 | 2004-12-22 | I.P. Holdings, L.L.C. | Methods for treating deodorizer distillate |
| CN107954969A (en) * | 2017-11-29 | 2018-04-24 | 徐小毛 | The extraction process of high quality vitamin E |
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| KR100619115B1 (en) * | 2004-04-19 | 2006-08-31 | (주)타렉스 | Method To Separate Sterol That There Is No Smell Of Great Soya From Greate Soya Milk Deodorization Distillation Quantity |
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| EP1487554A2 (en) * | 2002-03-18 | 2004-12-22 | I.P. Holdings, L.L.C. | Methods for treating deodorizer distillate |
| EP1487554A4 (en) * | 2002-03-18 | 2006-11-15 | I P Holdings L L C | Methods for treating deodorizer distillate |
| CN107954969A (en) * | 2017-11-29 | 2018-04-24 | 徐小毛 | The extraction process of high quality vitamin E |
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