WO2022035159A1 - Method for separating tocopherols from vegetable oil deodorizer distillate - Google Patents

Method for separating tocopherols from vegetable oil deodorizer distillate Download PDF

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WO2022035159A1
WO2022035159A1 PCT/KR2021/010502 KR2021010502W WO2022035159A1 WO 2022035159 A1 WO2022035159 A1 WO 2022035159A1 KR 2021010502 W KR2021010502 W KR 2021010502W WO 2022035159 A1 WO2022035159 A1 WO 2022035159A1
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oil
tocopherols
tocopherol
isolating
vegetable oils
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PCT/KR2021/010502
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French (fr)
Korean (ko)
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김진성
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김진성
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Priority claimed from KR1020210000824A external-priority patent/KR20220019605A/en
Priority claimed from KR1020210099641A external-priority patent/KR102389517B1/en
Application filed by 김진성 filed Critical 김진성
Publication of WO2022035159A1 publication Critical patent/WO2022035159A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
    • A61K31/35—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom
    • A61K31/352—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom condensed with carbocyclic rings, e.g. methantheline 
    • A61K31/353—3,4-Dihydrobenzopyrans, e.g. chroman, catechin
    • A61K31/355—Tocopherols, e.g. vitamin E
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
    • A61K36/18—Magnoliophyta (angiosperms)
    • A61K36/185—Magnoliopsida (dicotyledons)
    • A61K36/48—Fabaceae or Leguminosae (Pea or Legume family); Caesalpiniaceae; Mimosaceae; Papilionaceae

Definitions

  • the present invention relates to a method for isolating tocopherols from deodorized distillates of vegetable oils.
  • a supercritical fluid is a state of matter placed at a temperature and pressure above a critical point.
  • it is a fluid that exists at a temperature and pressure condition above the critical point, which exhibits intermediate characteristics between liquid and gas, and has the advantage of being able to easily control the states of solubility, viscosity, diffusion coefficient, etc. there is.
  • Water and carbon dioxide can be used as supercritical fluids.
  • Carbon dioxide used as a supercritical fluid has a low critical point compared to other fluids, and is widely used due to advantages such as colorlessness, nonflammability, nontoxicity, and nonreactivity with solute.
  • carbon dioxide in a supercritical state dissolves various substances well.
  • the supercritical carbon dioxide in which the target is dissolved is below the critical point, the carbon dioxide is vaporized and only the solute remains. At this time, the vaporized carbon dioxide can be recovered and recycled.
  • This supercritical fluid extraction technology is a method of extracting useful substances using the specific properties of a fluid under a temperature and pressure near or above the critical point of the fluid. It is suitable for the pharmaceutical, food, and fragrance industries because it enables rapid extraction and phase separation, and separation of temperature-sensitive substances without denaturation and decomposition.
  • Such vegetable oils include soybean oil, corn oil, rapeseed oil (rapeseed oil or canola oil), rice bran oil, sesame oil, perilla oil, safflower oil, sunflower oil, cottonseed oil, peanut oil, olive oil, palm oil, palm oil, and red pepper seed oil.
  • soybean oil is a vegetable oil composed of fatty acids beneficial to health.
  • soybean oil accounts for 67% of the total edible oil production and is a typical household edible oil.
  • the main extraction methods for extracting edible oil from oil resources such as soybean, sesame, and perilla are mechanical compression method and solvent extraction method.
  • the extraction of edible oil from soybeans generally uses solvent extraction. It is a method of extracting flakes obtained by pre-treatment of soybeans by dissolving them in an organic solvent, then recovering the solvent and obtaining the remaining fats and oils.
  • raw milk directly milked from soybeans contains various kinds of impurities and unpleasant odor components, so it is not suitable for consumption as raw milk.
  • Impurities contained in crude oil include gum substances (phospholipids), free fatty acids, oxidized lipids (peroxides and secondary oxides), pigment components (carotenoids and chlorophylls), and volatile odor components such as ketones and aldehydes.
  • soybean oil refining process consists of degumming, alkali refining, bleaching, and deodorization.
  • the degumming process is a generic term for mucus impurities contained in crude oil and is called gum (mainly phospholipid components).
  • Degumming is a process for removing gums contained in crude oil.
  • the gum substance contained in crude oil can cause problems of separation and sedimentation during storage of crude oil, and it is essential to remove it because it causes coloration of edible oils and fats during heating.
  • the purpose of deoxidation is to remove free fatty acids present in degummed oil. In the deoxidation process, some residual gum (phospholipids), metal components, and pigment components are also removed along with the removal of free fatty acids.
  • the bleaching process is a process of adsorbing and removing color components by adding an adsorbent.
  • Deodorization is the last step of the refining process, and is a process for producing edible oils and fats having a clear color without an unpleasant odor by removing volatile substances that emit an unpleasant odor.
  • steam is blown into the edible oil heated to a high temperature (180 ⁇ 260°C) in a high vacuum to remove volatile odor components.
  • Deodorization is performed sequentially through 4 to 6 trays in a continuous vacuum deodorization tower, (1) pre-heating, (2) heating, (3) steam stripping, (4)
  • the final deodorized milk is produced through four processes of cooling. In this process, free fatty acids and volatile odor components are removed by volatilization.
  • deodorization distillates By condensing the components removed by volatilization in the deodorization process in this way, a by-product called deodorization distillates can be obtained.
  • deodorized distillates contain substances that have industrial added value and can be used as raw materials for the food industry.
  • Another object of the present invention is to provide a tocopherol separated by the method for isolating the tocopherol.
  • the present invention relates to a method for separating tocopherol from deodorized distillates of vegetable oils and fats, and useful components such as phytosterols, fatty acid methyl esters and tocopherols from discarded deodorized distillates of vegetable oils and fats can be recovered with high efficiency.
  • FIG. 2 shows a supercritical pilot facility 100 for performing a supercritical process of separating tocopherol from a pretreatment sample (feed materials) obtained by pretreating a deodorized distillate of vegetable oil using a supercritical fluid.
  • FIG. 3 is another embodiment, a supercritical pilot facility 200 for performing a supercritical process of separating tocopherol using a supercritical fluid from a pretreatment sample obtained by pretreating a deodorizing distillate of vegetable oil. it has been shown
  • the present invention comprises the steps of pre-treating the deodorizing distillate of vegetable oil; and mixing the supercritical fluid with the pre-treatment sample obtained in the pre-treatment process and separating tocopherol.
  • the method for separating tocopherol from the deodorized distillate of vegetable oil includes the step of pre-treating the deodorized distillate of vegetable oil.
  • the vegetable oil may be selected from the group consisting of soybean oil, corn oil, rapeseed oil, rice bran oil, sesame oil, perilla oil, safflower oil, sunflower oil, cottonseed oil, peanut oil, olive oil, palm oil, palm oil and red pepper seed oil, but in this not limited
  • the term "deodorization distillates” refers to a process of degumming, deoxidation, decolorization, and deodorization in order to remove various kinds of impurities and unpleasant odor components contained in milked crude oil using a mechanical compression method and a solvent extraction method. It means obtained by condensing the components that are removed by volatilization in the deodorization process after passing through in turn.
  • tocopherol is a vitamin that is contained in a lot of vegetable oils such as soybean oil, rapeseed oil, sesame oil, perilla oil, cottonseed oil, palm oil, etc., does not dissolve in water and is non-toxic.
  • Tocopherol is a representative antioxidant naturally present, and ⁇ , ⁇ , ⁇ , ⁇ homologues exist in vegetable oils (see Table 2).
  • the pretreatment step as shown in Figure 1, the step of performing a methyl esterification reaction; performing a methanolysis reaction; performing crystallization, pressure dehydration and recrystallization; Alternatively, it may include performing a thin film distillation process.
  • fatty acid methyl ester is a material produced by a catalytic reaction between fatty acids and methanol, and is generally obtained by esterification by reacting fatty acids with methanol under an alkali catalyst.
  • Fatty acid ester is the most basic molecular structure of biodiesel, and is obtained from vegetable oil by transesterification, and the fatty acid methyl ester is usefully used as biodiesel by undergoing a distillation process using a thin film distillation device in the thin film distillation process to be described later. can be
  • a fatty acid methyl ester can be produced by a transesterification reaction by mixing methanol and a catalyst in the vegetable oil and deodorizing distillate.
  • An acid catalyst may be used as the catalyst, and specifically, it may be selected from the group consisting of acetic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, hydrofluoric acid, hydrobromic acid, lactic acid, formic acid, propionic acid, and mixtures thereof, and more specifically Sulfuric acid may be used.
  • glycerides and sterol esters contained in the vegetable oil deodorization distillate may be converted into fatty acid methyl esters and sterols, respectively, by the methanolysis reaction.
  • the methanolysis reaction may be performed by mixing methanol and a basic catalyst after obtaining only an oil phase after the methyl esterification reaction is completed.
  • the basic catalyst in the reaction is sodium hydroxide (NaOH), sodium carbonate (Na 2 CO 3 ), sodium alkoxide (Sodium alkoxide), potassium hydroxide (KOH), potassium carbonate (K 2 CO 3 ), and potassium alkoxide (Potassium alkoxide) It may be selected from the group consisting of, specifically, sodium methoxide may be used.
  • phytosterol can be separated by crystallization, pressure dehydration process and recrystallization process.
  • a sample containing fatty acid methyl ester and tocopherol may be separated by a thin film distillation process.
  • the filtrate containing fatty acid methyl ester and tocopherol separated through crystallization and filter press after the methyl esterification reaction and methane decomposition reaction during the pretreatment process was subjected to a thin film distillation process at 220 ° C.
  • the methyl ester is separated to obtain a sample pretreated with a high concentration of tocopherol.
  • the fatty acid methyl ester can be separated by a thin film distillation process using a thin film evaporator, which can be used as biodiesel.
  • pretreatment samples feed materials obtained in the pretreatment process injected into the supercritical process.
  • the pre-treatment sample obtained in the pre-treatment process, through the pre-treatment process as described above, free fatty acids, glycerides, sterols, and sterol esters are removed from the vegetable oil deodorization distillate, and contains a high concentration of tocopherol.
  • the method of separating tocopherol from the deodorized distillate of vegetable oil includes mixing a supercritical fluid with the pretreatment sample obtained in the pretreatment process and separating the tocopherol.
  • FIG. 2 shows a supercritical pilot facility 100 for performing a supercritical process of separating tocopherol using a supercritical fluid from a pretreated sample obtained by pretreating a deodorizing distillate of vegetable oil.
  • the supercritical pilot facility 100 (pressure up to 600 atm, temperature up to 100° C.) is a main solvent (carbon dioxide) storage tank (1), an auxiliary solvent (ethanol) storage tank (2), a main solvent (carbon dioxide) supply pump ( 3), auxiliary solvent feed pump (4), pretreatment sample storage tank (5), pretreatment sample feed pump (6), countercurrent column (7), raffinate (8), pressure control valve 1 ( 9), separator 1 (10), needle valve 1 (11), impurity outlet (12), pressure control valve 2 (13), separator 2 (14), needle valve 2 (15), tocopherol storage tank (16), It includes a gas outlet (17) and a process automatic control computer (18).
  • carbon dioxide is stored in a main solvent (carbon dioxide) storage tank 1
  • ethanol is stored in an auxiliary solvent (ethanol) storage tank 2
  • Ethanol is used as an auxiliary solvent because it dissolves tocopherol well.
  • the pretreatment sample obtained through the pretreatment process is stored in the pretreatment sample storage tank 5 .
  • the main solvent (carbon dioxide) supply pump 3 and the auxiliary solvent supply pump 4 are operated to supply the main solvent (carbon dioxide) and the auxiliary solvent (ethanol) to the lower part 73 of the countercurrent column 7,
  • the countercurrent column 7 may be filled with a Raschig ring to increase the contact area between the gas and the liquid. After a certain contact time has elapsed, a stream in which tocopherol is concentrated is generated at the top of the countercurrent column 7, and a raffinate 8 is accumulated at the bottom of the countercurrent column 7 .
  • the pressure regulating valve 1 (9) is depressurized, and impurities are discharged to the bottom of the separator 1 (10) through the needle valve 1 (11) to the impurity outlet (12).
  • the pressure control valve 2 (13) is reduced, the tocopherol is stored in the tocopherol storage tank 16 through the needle valve 2 (15) under the separator 2 (separator) 14, and the separator 2 (separator) ( 14), carbon dioxide and ethanol gas are discharged through the gas outlet 17 on the right side.
  • FIG. 3 is another embodiment, a supercritical pilot facility 200 for performing a supercritical process of separating tocopherol using a supercritical fluid from a pretreatment sample obtained by pretreating a deodorizing distillate of vegetable oil. it has been shown
  • a heating jacket 19 is installed outside the countercurrent column 7 of the supercritical pilot facility to the inside of the column. temperature can be adjusted.
  • the high-pressure carburetor 20 may be installed at the upper end of the pressure control valve 1 (9), and the low-pressure carburetor 21 may be installed at the upper end of the separator 2 (14).
  • the pressure control valve 1 (9) and the pressure control valve 2 (13) When the pressure is lowered with the pressure control valve 1 (9) and the pressure control valve 2 (13), the temperature of the fluid drops sharply due to the Joule-Thomson effect.
  • a reflux pump 22 is operated to return the separated tocopherol to the upper 74 or middle 75 of the countercurrent column 7 ) can be injected into the
  • ethanol and carbon dioxide are discharged through the gas outlet 17 from the upper part of the separator 2 (separator) 14, and the ethanol is condensed by the auxiliary solvent (ethanol) condenser 1 (25), and the auxiliary solvent (ethanol) receiver 1 (23) ), and the carbon dioxide is condensed with the main solvent (carbon dioxide) condenser 2 (26), recovered by the main solvent (carbon dioxide) receiver 2 (24), and then further cooled in the cooler 27, and then the main solvent (carbon dioxide) storage tank (1) to be reused.
  • the height of the countercurrent column 7 may be increased or a distillation process may be additionally added using a molecular distiller.
  • the main solvent and the auxiliary solvent may be injected into the lower portion of the countercurrent column, and the pretreatment sample obtained in the pretreatment process may be injected into the upper portion or the middle portion of the countercurrent column.
  • the tocopherol separation step the temperature in the countercurrent (countercurrent) column is 30 ⁇ 60 °C, the pressure is 300 ⁇ 600 bar, the retention time of the pretreatment sample obtained in the pretreatment process in the column may be 30 ⁇ 120 minutes.
  • the temperature of the countercurrent column can be adjusted to 30 to 60° C. and the pressure to 300 to 600 bar, and the retention time of the pretreatment sample obtained during the pretreatment in the column is 30 It can be ⁇ 120 minutes.
  • the temperature in the column is 40° C.
  • the pressure is 400 bar
  • the residence time of the pre-treatment sample obtained in the pre-treatment process in the column may be 90 minutes.
  • the pretreatment sample and the main solvent obtained in the pretreatment process may be injected in a weight ratio of 1: 5 to 30, and the main solvent and the auxiliary solvent in a weight ratio of 1: 0.05 to 0.3. More specifically, the pretreatment sample and the main solvent obtained in the pretreatment process may be injected in a weight ratio of 1:10, and the main solvent and the auxiliary solvent in a weight ratio of 1:0.1.
  • carbon dioxide may be used as the main solvent as a supercritical fluid.
  • ethanol may be used as the auxiliary solvent, and the auxiliary solvent may increase the solubility of tocopherol to increase the extraction or separation yield of tocopherol from the pretreatment sample and increase the purity.
  • the present invention provides tocopherol separated by the method for separating tocopherol from the deodorized distillate of vegetable oil as described above.
  • deodorized distillate of vegetable oil and "method of separating tocopherol from deodorized distillate of vegetable oil” are the same as described above.
  • Acid value is the number of mg of KOH required to neutralize free fatty acids contained in 1 g of fat and oil, and measures the amount of free fatty acids in which fatty acids are not in a bound form as glycerides. If the acid value is high, it means that the fats and oils have deteriorated.
  • the saponification (saponification) number is the number of mg of KOH required to completely saponify 1 g of fat. Since the saponification value is inversely proportional to the molecular weight of the constituent fatty acids of the fats and oils, fats with a high content of lower fatty acids have a large saponification value, and oils and fats with a high content of higher fatty acids have a low saponification value.
  • composition analysis result of the soybean oil deodorization distillate is shown in Table 2.
  • free fatty acids (FFA) 52.2%, glycerides (Gly) 21.4%, squalene 3.11%, tocopherol 9.23%, sterols 5.47%, and impurities 8.59 % was included.
  • impurities included long chain paraffins, sterol esters, pigments and waxes.
  • a stationary and neutralization process was performed to separate the oil phase into the upper part and the water phase into the lower part.
  • methanol 570 kg and sodium methoxide (NaOCH 3 ) 25 kg were injected and refluxed at 70° C. for 120 minutes, followed by methanolysis (methanolysis).
  • methanolysis reaction glycerides and sterol esters contained in soybean oil deodorizing distillate (DOD) are converted into fatty acid methyl esters (FAMEs) and sterols, respectively.
  • DOD soybean oil deodorizing distillate
  • 1,400 kg of ethanol was added to 200 kg of crude sterol obtained in step 2-3, dissolved at 70° C. for 2 hours, cooled and crystallized at 25° C. for 6 hours, followed by centrifugation. In addition, 20 kg per hour was dried to obtain purified phytosterols with a purity of 93 to 97%.
  • a supercritical pilot facility pressure up to 600 atm, temperature up to 100° C.
  • a countercurrent column (diameter 60 mm, height 4 m) was used, and a raschig ring was filled inside the column.
  • the pilot test was conducted at a pressure of 200 to 500 atm, and a temperature in the range of 30°C to 80°C, with a weight ratio of 1:10 for the pretreatment sample and solvent, 1:0.1 for the solvent and co-solvent, and a retention time in the column of 30 to 120 minutes. was changed to .
  • Table 3 compares tocopherol purity and extraction yield using the supercritical extraction method according to pressure and temperature. As a result, as shown in Table 3, the tocopherol extraction yield and purity were the highest at a pressure of 400 atmospheres and a temperature of 40°C, and when the residence time in the column was 90 minutes, the tocopherol extraction yield and purity were the highest.
  • the separated tocopherol was analyzed using high performance liquid chromatography (HPLC), and the results are shown in FIG. 4 .
  • HPLC high performance liquid chromatography
  • Shimadzu SPD-10A detector 295 nm (UV length) and silica-gel column were used.
  • the mobile phase was calculated using n-hexane: propanol (99:1, v/v) and DL-alpha-tocopherol as a standard material.
  • tocopherol is contained in soybean oil deodorized distillate (DOD), and it was possible to extract at a yield of 80% or more using the pretreatment process and supercritical process of the present invention.
  • DOD soybean oil deodorized distillate

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Abstract

The present invention relates to a method for separating tocopherols from vegetable oil deodorizer distillate. Phytosterols and fatty acid methyl esters can be separated by pre-treating discarded vegetable oil deodorizer distillate. In addition, the deodorizer distillate can be pre-treated to obtain a pre-treated sample removed of free fatty acids, glycerides, sterols, and sterol esters, and tocopherols can be efficiently collected by using the pre-treated sample, and thus can be used as a raw material of food antioxidants, cosmetics, health functional foods, etc.

Description

식물성 유지의 탈취 증류물로부터 토코페롤을 분리하는 방법Method for Isolation of Tocopherols from Deodorized Distillates of Vegetable Oils
본 발명은 식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법에 관한 것이다. The present invention relates to a method for isolating tocopherols from deodorized distillates of vegetable oils.
초임계 유체(Supercritical fluid)는 임계점 이상의 온도와 압력에 놓인 물질 상태로, 물질의 온도와 압력이 임계점(supercritical point)을 넘어 액체와 기체를 구분할 수 없는 상태가 된 유체를 말한다. 즉, 임계점(critical point) 이상의 온도와 압력 조건에서 존재하는 유체로 액체와 기체의 중간 특성을 나타내며 밀도를 연속적으로 변화시킬 수 있기 때문에 용해도, 점도, 확산계수 등의 상태를 쉽게 조절할 수 있는 장점이 있다. A supercritical fluid is a state of matter placed at a temperature and pressure above a critical point. In other words, it is a fluid that exists at a temperature and pressure condition above the critical point, which exhibits intermediate characteristics between liquid and gas, and has the advantage of being able to easily control the states of solubility, viscosity, diffusion coefficient, etc. there is.
초임계 유체로 물과 이산화탄소를 사용할 수 있다. 초임계 유체로 사용되는 이산화탄소는 다른 유체에 비해 임계점이 낮고, 무색, 불연성, 무독성 및 용질과의 비반응성과 같은 이점으로 인해 많이 이용되고 있다. 또한, 초임계 상태의 이산화탄소는 여러 가지 물질을 잘 용해한다. 목표물을 용해한 초임계 이산화탄소를 임계점 이하로 하면, 이산화탄소는 기화하여 용질만이 남는다. 이 때, 기화된 이산화탄소는 회수가 가능하여 재활용이 가능하다. Water and carbon dioxide can be used as supercritical fluids. Carbon dioxide used as a supercritical fluid has a low critical point compared to other fluids, and is widely used due to advantages such as colorlessness, nonflammability, nontoxicity, and nonreactivity with solute. In addition, carbon dioxide in a supercritical state dissolves various substances well. When the supercritical carbon dioxide in which the target is dissolved is below the critical point, the carbon dioxide is vaporized and only the solute remains. At this time, the vaporized carbon dioxide can be recovered and recycled.
이러한 초임계 유체 추출기술은 유체의 임계점 근처 또는 그 이상의 온도와 압력 하에 유체의 특이적 성질을 이용하여 유용물질을 추출하는 방법으로 비교적 낮은 온도에서 수행되므로 열에 민감한 천연물질의 분리 및 정제에 많이 이용되고 있으며, 빠른 추출과 상 분리가 가능하고, 온도에 민감한 물질을 변성 및 분해없이 분리할 수 있어 의약, 식품, 향료 산업에 적합하다.This supercritical fluid extraction technology is a method of extracting useful substances using the specific properties of a fluid under a temperature and pressure near or above the critical point of the fluid. It is suitable for the pharmaceutical, food, and fragrance industries because it enables rapid extraction and phase separation, and separation of temperature-sensitive substances without denaturation and decomposition.
한편, 가정에서는 다양한 종류의 식물성 유지류를 섭취하고 있다. 이러한 식물성 유지류에는 콩기름, 옥수수기름, 채종유(유채유 또는 카놀라유), 미강유, 참기름, 들기름, 홍화유, 해바라기유, 목화씨기름, 땅콩기름, 올리브유, 팜유류, 야자유, 고추씨기름 등이 있다.Meanwhile, at home, various types of vegetable oils and fats are consumed. Such vegetable oils include soybean oil, corn oil, rapeseed oil (rapeseed oil or canola oil), rice bran oil, sesame oil, perilla oil, safflower oil, sunflower oil, cottonseed oil, peanut oil, olive oil, palm oil, palm oil, and red pepper seed oil.
이 중 콩기름은 건강에 이로운 지방산으로 구성된 식물성 기름으로 가격이 저렴하고 다양한 음식에 이용할 수 있어서 전세계적으로 많이 소비되고 있다. 우리나라에서도 콩기름은 전체 식용유 생산량의 67%를 차지하는 기름으로 대표적인 가정용 식용유이며, 호텔, 외식, 급식 시장과 식품가공시장에서도 튀김유와 쇼트닝·마가린의 원료로도 사용되고 있다.Among them, soybean oil is a vegetable oil composed of fatty acids beneficial to health. In Korea, soybean oil accounts for 67% of the total edible oil production and is a typical household edible oil.
이러한 콩, 참깨, 들깨 등의 유지자원으로부터 식용유를 추출하는 주요 추출법은 기계적 압착법과 용제 추출법이 있다. 콩으로부터 식용유의 착유는 일반적으로 용제 추출법을 사용한다. 콩을 전처리하여 얻은 압편(flake)을 유기 용제에 용해시켜 추출한 후 용제는 회수하고 남아 있는 유지를 얻어내는 방식이다. 그러나, 콩에서 바로 착유한 원유에는 여러 종류의 불순물 및 불쾌한 냄새성분들이 함유되어 있어서 원유 상태로는 식용으로는 적합하지 않다. 원유에 함유된 불순물은 검질(인지질), 유리지방산, 산화지방질(과산화물 및 2차 산화물), 색소성분(카로테노이드 및 엽록소류), 케톤 및 알데하이드 등의 휘발성 이취성분 등이 있다. 이들 불순물들은 식용유에 불쾌취를 제공하며, 가열할 경우 색이 진해지는 가열 착색의 원인이 되며, 산화 안정성 및 저장성을 떨어뜨리는 요인이 된다. 이들 불순물들은 원유 추출 공정에서 필연적으로 원유와 함께 추출되어 존재하게 되므로 식용을 목적으로 할 경우에는 이들 불순물을 제거하는 공정이 필수적이다.The main extraction methods for extracting edible oil from oil resources such as soybean, sesame, and perilla are mechanical compression method and solvent extraction method. The extraction of edible oil from soybeans generally uses solvent extraction. It is a method of extracting flakes obtained by pre-treatment of soybeans by dissolving them in an organic solvent, then recovering the solvent and obtaining the remaining fats and oils. However, raw milk directly milked from soybeans contains various kinds of impurities and unpleasant odor components, so it is not suitable for consumption as raw milk. Impurities contained in crude oil include gum substances (phospholipids), free fatty acids, oxidized lipids (peroxides and secondary oxides), pigment components (carotenoids and chlorophylls), and volatile odor components such as ketones and aldehydes. These impurities give edible oil an unpleasant odor, cause heat discoloration that thickens when heated, and deteriorate oxidative stability and storability. Since these impurities are inevitably extracted together with crude oil in the crude oil extraction process, the process of removing these impurities is essential for edible purposes.
따라서, 콩 등의 유지 자원에서 추출하여 얻은 원유를 식용에 적합한 품질을 얻기 위해서는 정제가 필요하다. 콩기름 정제 공정은 탈검(degumming), 탈산(alkali refining), 탈색(bleaching), 탈취(deodorization)로 이루어져 있다.Therefore, it is necessary to refine the crude oil obtained by extracting it from oil and fat resources such as soybeans to obtain a quality suitable for consumption. The soybean oil refining process consists of degumming, alkali refining, bleaching, and deodorization.
탈검 과정은 원유에 함유된 점액상의 불순물을 총칭하여 검질(주로 인지질 성분)이라고 한다. 탈검이란 원유에 함유된 검질을 제거하기 위한 공정이다. 원유에 함유된 검질은 원유의 저장 중에 분리, 침전하는 문제가 발생할 수 있고, 가열 시에 식용유지의 착색 원인이 되기 때문에 필수적으로 제거해야 한다. 탈산의 목적은 탈검유에 존재하는 유리 지방산을 제거하는 것이다. 탈산 공정에서는 유리 지방산의 제거와 함께 잔여 검질(인지질), 금속성분 및 색소성분 등도 일부 함께 제거된다. 탈색(Bleaching)공정은 흡착제를 첨가하여 색소성분을 흡착하여 제거하는 공정이다. 이 과정에서 잔여 비누분, 인지질 등도 동시에 제거된다. 탈취(Deodorization)는 정제공정의 가장 마지막 단계로서, 불쾌한 냄새를 내는 휘발성 물질을 제거하여 불쾌한 냄새가 없는 맑은 색을 갖는 식용 유지를 제조하기 위한 과정이다. 탈취과정에서는 높은 진공 상태에서 높은 온도(180~260℃)로 가열된 식용유지 내부로 수증기(Steam)를 불어넣어 휘발성 냄새 성분을 제거한다. 탈취는 연속식 진공 탈취 타워(Deodorization Tower)내에 4~6단의 트레이(tray)를 순차적으로 통과하면서 (1) 예비 가열, (2) 가열, (3) 수증기 주입(steam stripping), (4) 냉각의 4 가지 공정을 거쳐 최종 탈취유를 생산하게 된다. 이 과정에서 유리 지방산 및 휘발성 냄새성분들은 휘발하여 제거된다. The degumming process is a generic term for mucus impurities contained in crude oil and is called gum (mainly phospholipid components). Degumming is a process for removing gums contained in crude oil. The gum substance contained in crude oil can cause problems of separation and sedimentation during storage of crude oil, and it is essential to remove it because it causes coloration of edible oils and fats during heating. The purpose of deoxidation is to remove free fatty acids present in degummed oil. In the deoxidation process, some residual gum (phospholipids), metal components, and pigment components are also removed along with the removal of free fatty acids. The bleaching process is a process of adsorbing and removing color components by adding an adsorbent. In this process, residual soap powder and phospholipids are also removed at the same time. Deodorization is the last step of the refining process, and is a process for producing edible oils and fats having a clear color without an unpleasant odor by removing volatile substances that emit an unpleasant odor. In the deodorization process, steam is blown into the edible oil heated to a high temperature (180~260℃) in a high vacuum to remove volatile odor components. Deodorization is performed sequentially through 4 to 6 trays in a continuous vacuum deodorization tower, (1) pre-heating, (2) heating, (3) steam stripping, (4) The final deodorized milk is produced through four processes of cooling. In this process, free fatty acids and volatile odor components are removed by volatilization.
이와 같이 탈취공정에서 휘발되어 제거되는 성분들을 응축하면 탈취 증류물(deodorization distillates)이라는 부산물을 얻을 수 있다. 이러한 탈취 증류물에는 산업적으로 부가가치가 있고 식품산업의 원료로 이용할 수 있는 물질이 함유되어 있다. By condensing the components removed by volatilization in the deodorization process in this way, a by-product called deodorization distillates can be obtained. These deodorized distillates contain substances that have industrial added value and can be used as raw materials for the food industry.
이에 본 발명에서는 버려지는 탈취 증류물에서 유용성분을 고효율로 회수하는 방법을 개발하고자 하였다.Therefore, in the present invention, it was attempted to develop a method for efficiently recovering useful components from discarded deodorizing distillates.
본 발명의 목적은 식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법 을 제공하는 것이다.It is an object of the present invention to provide a method for separating tocopherols from deodorized distillates of vegetable oils.
본 발명의 다른 목적은 상기 토코페롤을 분리하는 방법에 의해 분리된 토코페롤을 제공하는 것이다.Another object of the present invention is to provide a tocopherol separated by the method for isolating the tocopherol.
본 발명은 식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법에 관한 것으로서, 버려지는 식물성 유지의 탈취 증류물에서 피토스테롤, 지방산메틸 에스테르 그리고 토코페롤 등의 유용성분을 고효율로 회수가 가능한 장점이 있다. The present invention relates to a method for separating tocopherol from deodorized distillates of vegetable oils and fats, and useful components such as phytosterols, fatty acid methyl esters and tocopherols from discarded deodorized distillates of vegetable oils and fats can be recovered with high efficiency.
도 1은 식물성 유지의 탈취 증류물을 전처리하는 과정을 나타낸 것이다.1 shows the process of pre-treatment of deodorizing distillate of vegetable oil.
도 2는 식물성 유지의 탈취 증류물을 전처리하여 얻은 전처리 시료(feed materials)를 초임계 유체를 이용하여 토코페롤을 분리하는 초임계 공정을 진행하기 위한 초임계 pilot 설비(100)를 나타낸 것이다. 2 shows a supercritical pilot facility 100 for performing a supercritical process of separating tocopherol from a pretreatment sample (feed materials) obtained by pretreating a deodorized distillate of vegetable oil using a supercritical fluid.
도 3은 또 다른 실시 태양으로, 식물성 유지의 탈취 증류물을 전처리하여 얻은 전처리 시료를 초임계 유체를 이용하여 토코페롤을 분리하는 초임계 공정을 진행하기 위한 초임계 파일럿(pilot) 설비(200)를 나타낸 것이다. 3 is another embodiment, a supercritical pilot facility 200 for performing a supercritical process of separating tocopherol using a supercritical fluid from a pretreatment sample obtained by pretreating a deodorizing distillate of vegetable oil. it has been shown
도 4는 압력 400기압, 온도 40℃에서 컬럼 내 체류 시간이 90분이었을 때, 분리된 토코페롤을 HPLC(High Performance Liquid Chromatography)를 이용하여 분석한 결과이다. 4 is a result of analyzing the separated tocopherol using HPLC (High Performance Liquid Chromatography) when the retention time in the column was 90 minutes at a pressure of 400 atmospheres and a temperature of 40°C.
이하 본 명세서에 대하여 더욱 상세히 설명한다.Hereinafter, the present specification will be described in more detail.
이를 구체적으로 설명하면 다음과 같다. 한편, 본 발명에서 개시된 각각의 설명 및 실시형태는 각각에 대한 다른 설명 및 실시형태에도 적용될 수 있다. 즉, 본 발명에 개시된 다양한 요소들의 모든 조합이 본 발명의 범주에 속한다. 또한, 하기에 기술된 구체적인 서술에 의하여 본 발명의 범주가 제한된다고 볼 수 없다.This will be described in detail as follows. On the other hand, each description and embodiment disclosed in the present invention may be applied to other descriptions and embodiments for each. That is, all combinations of the various elements disclosed herein fall within the scope of the present invention. In addition, it cannot be seen that the scope of the present invention is limited by the specific descriptions described below.
본 명세서에서 사용되는 「포함하는」과 같은 표현은, 해당 표현이 포함되는 문구 또는 문장에서 특별히 다르게 언급되지 않는 한, 다른 실시 예를 포함할 가능성을 내포하는 개방형 용어(open-ended terms)로 이해되어야 한다.An expression such as "comprising" used in this specification is understood as an open-ended term containing the possibility of including other embodiments, unless otherwise specified in the phrase or sentence in which the expression is included. should be
본 발명의 설명 및 청구범위에서 사용된 용어나 단어는, 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선을 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여, 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor must properly understand the concept of the term in order to best describe his invention. Based on the principle that can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.
상기 목적을 달성하기 위한 하나의 양태로서, 본 발명은 식물성 유지의 탈취 증류물을 전처리 하는 단계; 및 상기 전처리 과정에서 얻은 전처리 시료에 초임계 유체를 혼합하고 토코페롤을 분리하는 단계;를 포함하는, 식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법을 제공한다. As one aspect for achieving the above object, the present invention comprises the steps of pre-treating the deodorizing distillate of vegetable oil; and mixing the supercritical fluid with the pre-treatment sample obtained in the pre-treatment process and separating tocopherol.
본 발명에서 상기 식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법은 식물성 유지의 탈취 증류물을 전처리 하는 단계를 포함한다.In the present invention, the method for separating tocopherol from the deodorized distillate of vegetable oil includes the step of pre-treating the deodorized distillate of vegetable oil.
본 발명에서 상기 식물성 유지는 콩기름, 옥수수기름, 채종유, 미강유, 참기름, 들기름, 홍화유, 해바라기유, 목화씨기름, 땅콩기름, 올리브유, 팜유류, 야자유 및 고추씨기름으로 이루어진 군에서 선택될 수 있으나, 이에 제한되지 않는다.In the present invention, the vegetable oil may be selected from the group consisting of soybean oil, corn oil, rapeseed oil, rice bran oil, sesame oil, perilla oil, safflower oil, sunflower oil, cottonseed oil, peanut oil, olive oil, palm oil, palm oil and red pepper seed oil, but in this not limited
본 발명에서 용어 "탈취 증류물(deodorization distillates)"은 기계적 압착법과 용제 추출법 등을 이용하여 착유한 원유에 포함된 여러 종류의 불순물 및 불쾌한 냄새성분들을 제거하기 위해 탈검, 탈산, 탈색, 및 탈취 과정을 차례로 거친 후, 탈취 공정에서 휘발되어 제거되는 성분들을 응축하여 얻은 것을 의미한다. In the present invention, the term "deodorization distillates" refers to a process of degumming, deoxidation, decolorization, and deodorization in order to remove various kinds of impurities and unpleasant odor components contained in milked crude oil using a mechanical compression method and a solvent extraction method. It means obtained by condensing the components that are removed by volatilization in the deodorization process after passing through in turn.
본 발명에서 용어 "토코페롤(Tocopherol)"은 콩기름, 채종유, 참기름, 들기름, 면실유, 야자유 등 식물성 유지에 많이 함유되어 있으며 물에는 용해되지 않고 독성이 없는 비타민이다. 토코페롤은 천연에 존재하는 대표적인 항산화제로, 식물성 유지에는 α,β,γ,δ동족체가 존재한다(표 2 참조).In the present invention, the term "tocopherol (Tocopherol)" is a vitamin that is contained in a lot of vegetable oils such as soybean oil, rapeseed oil, sesame oil, perilla oil, cottonseed oil, palm oil, etc., does not dissolve in water and is non-toxic. Tocopherol is a representative antioxidant naturally present, and α, β, γ, δ homologues exist in vegetable oils (see Table 2).
도 1은 식물성 유지의 탈취 증류물을 전처리하는 과정을 나타낸 것이다.1 shows the process of pre-treatment of deodorizing distillate of vegetable oil.
상기 전처리 단계는, 도 1에 도시된 바와 같이, 메틸에스테르화 반응을 진행하는 단계; 메탄올분해 반응을 진행하는 단계; 결정화, 가압탈수 및 재결정화 과정을 진행하는 단계; 또는 박막 증류 과정을 진행하는 단계를 포함할 수 있다.The pretreatment step, as shown in Figure 1, the step of performing a methyl esterification reaction; performing a methanolysis reaction; performing crystallization, pressure dehydration and recrystallization; Alternatively, it may include performing a thin film distillation process.
전처리 단계의 첫번째 단계로, 메틸에스테르화 반응에 의해 식물성 유지 탈취 증류물에 함유된 유리 지방산이 지방산 메틸 에스테르로 전환될 수 있다. 상기 지방산 메틸 에스테르(Fatty acid methyl ester)는 지방산과 메탄올 사이에 촉매 반응으로 생성되는 물질로, 일반적으로 지방산을 알칼리 촉매하에 메탄올에 반응시켜 에스테르화 반응시켜 얻어진다. 지방산 에스테르는 바이오디젤의 가장 기본적인 분자 구조로, 에스테르 교환에 의해 식물성 기름으로부터 얻어지며, 상기 지방산 메틸에스테르는 후술할 박막 증류 과정에서 박막증류장치를 이용한 증류 과정을 거치 분리하여 바이오디젤로 유용하게 이용될 수 있다. As a first step of the pretreatment step, free fatty acids contained in the vegetable oil deodorizing distillate may be converted into fatty acid methyl esters by methyl esterification. The fatty acid methyl ester (Fatty acid methyl ester) is a material produced by a catalytic reaction between fatty acids and methanol, and is generally obtained by esterification by reacting fatty acids with methanol under an alkali catalyst. Fatty acid ester is the most basic molecular structure of biodiesel, and is obtained from vegetable oil by transesterification, and the fatty acid methyl ester is usefully used as biodiesel by undergoing a distillation process using a thin film distillation device in the thin film distillation process to be described later. can be
본 발명에서는 상기 식물성 유지 탈취 증류물에 메탄올과 촉매를 혼합하여 트랜스에스테르화 반응에 의해 지방산 메틸 에스테르를 생성할 수 있다. 상기 촉매로는 산 촉매를 사용할 수 있으며, 구체적으로 초산, 염산, 질산, 인산, 황산, 붕산, 불화수소산, 브롬화수소산, 젖산, 포름산, 프로피온산 및 이의 혼합물로 이루어진 군에서 선택할 수 있으며, 보다 구체적으로 황산을 사용할 수 있다.In the present invention, a fatty acid methyl ester can be produced by a transesterification reaction by mixing methanol and a catalyst in the vegetable oil and deodorizing distillate. An acid catalyst may be used as the catalyst, and specifically, it may be selected from the group consisting of acetic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, hydrofluoric acid, hydrobromic acid, lactic acid, formic acid, propionic acid, and mixtures thereof, and more specifically Sulfuric acid may be used.
상기 메틸에스테르화 반응이 종료된 후 정치 및 중화 과정을 진행하게 되면, 유상(oil phase)은 상부, 그리고 수상(water phase)은 하부로 분리된다. When the stationary and neutralization process is performed after the methyl esterification reaction is completed, an oil phase is separated into an upper portion and a water phase is separated into a lower portion.
전처리 과정의 두번째 단계로, 상기 메탄올분해 반응에 의해 식물성 유지 탈취 증류물에 함유된 글리세라이드와 스테롤 에스테르가 각각 지방산 메틸 에스테르와 스테롤(sterols)로 전환될 수 있다. As a second step of the pretreatment process, glycerides and sterol esters contained in the vegetable oil deodorization distillate may be converted into fatty acid methyl esters and sterols, respectively, by the methanolysis reaction.
상기 메탄올분해(methanolysis) 반응은 상기 메틸에스테르화 반응이 종료된 후 유상만을 수득한 후 메탄올과 염기성 촉매를 혼합하여 진행될 수 있다. 상기 반응에서 염기성 촉매는 수산화나트륨(NaOH), 탄산나트륨(Na2CO3), 나트륨알콕사이드(Sodium alkoxide), 수산화칼륨(KOH), 탄산칼륨(K2CO3), 및 칼륨알콕사이드(Potassium alkoxide)로 이루어진 군에서 선택될 수 있으며, 구체적으로, 나트륨메톡사이드를 사용할 수 있다. The methanolysis reaction may be performed by mixing methanol and a basic catalyst after obtaining only an oil phase after the methyl esterification reaction is completed. The basic catalyst in the reaction is sodium hydroxide (NaOH), sodium carbonate (Na 2 CO 3 ), sodium alkoxide (Sodium alkoxide), potassium hydroxide (KOH), potassium carbonate (K 2 CO 3 ), and potassium alkoxide (Potassium alkoxide) It may be selected from the group consisting of, specifically, sodium methoxide may be used.
전처리 과정의 세번째 단계로, 결정화, 가압탈수 과정 및 재결정화 과정에 의해 피토스테롤이 분리될 수 있다. As the third step of the pretreatment process, phytosterol can be separated by crystallization, pressure dehydration process and recrystallization process.
상기와 같이 메틸에스테르화 반응과 메탄올분해 반응을 거친 후, 냉각하여 결정화를 진행하고, 원심분리 그리고 가압탈수(filter pressing) 과정을 거치면 고체상의 케이크(cake)로 조스테롤(crude sterol)과 액체상의 지방산 메틸에스테르와 토코페롤이 함유된 여액(filtrate)이 분리되게 생긴다. 여기서 얻은 조스테롤(crude sterol)을 포함하는 케이크(cake)를 에탄올에 용해한 후, 냉각 재결정화와 원심분리를 진행한 후 건조하여 정제된 피토스테롤을 분리할 수 있다. After the methyl esterification reaction and the methanolysis reaction as described above, crystallization is performed by cooling, centrifugation and filter pressing are performed to form a solid cake with crude sterol and liquid phase. A filtrate containing fatty acid methyl ester and tocopherol is separated. After dissolving a cake containing crude sterol obtained here in ethanol, cooling recrystallization and centrifugation are performed, followed by drying to separate purified phytosterol.
전처리 과정의 네번째 단계로, 박막 증류 과정에 의해 지방산 메틸 에스테르와 토코페롤을 포함하는 시료가 분리될 수 있다. As a fourth step of the pretreatment process, a sample containing fatty acid methyl ester and tocopherol may be separated by a thin film distillation process.
전술한 바와 같이, 전처리 과정 중 메틸에스테르화 반응과 메탄분해 반응 후 결정화와 필터 프레스 과정을 거쳐서 분리된 지방산메틸에스테르와 토코페롤이 함유된 여액(filtrate)을 대상으로 220℃에서 박막 증류 과정에 의해 지방산 메틸 에스테르가 분리되어서 농도가 높은 토코페롤을 전처리 시료를 얻게 된다.As described above, the filtrate containing fatty acid methyl ester and tocopherol separated through crystallization and filter press after the methyl esterification reaction and methane decomposition reaction during the pretreatment process was subjected to a thin film distillation process at 220 ° C. The methyl ester is separated to obtain a sample pretreated with a high concentration of tocopherol.
상기와 같이 결정화 및 가압탈수 과정을 거친 후 박막증류장치(thin film evaporator)를 이용한 박막 증류 과정에 의해 지방산 메틸 에스테르가 분리될 수 있으며, 이는 바이오디젤로 이용이 가능하다. After the crystallization and pressure dehydration process as described above, the fatty acid methyl ester can be separated by a thin film distillation process using a thin film evaporator, which can be used as biodiesel.
또한, 위와 같은 전처리 과정을 거치고 나면, 초임계 공정에 주입하는 전처리 과정에서 얻은 전처리 시료(feed materials)를 얻을 수 있게 된다. In addition, after the above pretreatment process, it is possible to obtain pretreatment samples (feed materials) obtained in the pretreatment process injected into the supercritical process.
상기 전처리 과정에서 얻은 전처리 시료는, 상기와 같은 전처리 과정을 거쳐서, 식물성 유지 탈취 증류물에서 유리 지방산, 글리세라이드, 스테롤, 그리고 스테롤 에스테르가 제거되게 되고, 고농도의 토코페롤을 함유하게 된다. The pre-treatment sample obtained in the pre-treatment process, through the pre-treatment process as described above, free fatty acids, glycerides, sterols, and sterol esters are removed from the vegetable oil deodorization distillate, and contains a high concentration of tocopherol.
상기 식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법은 상기 전처리 과정에서 얻은 전처리 시료에 초임계 유체를 혼합하고 토코페롤을 분리하는 단계를 포함한다. The method of separating tocopherol from the deodorized distillate of vegetable oil includes mixing a supercritical fluid with the pretreatment sample obtained in the pretreatment process and separating the tocopherol.
도 2는 식물성 유지의 탈취 증류물을 전처리하여 얻은 전처리 시료를 초임계 유체를 이용하여 토코페롤을 분리하는 초임계 공정을 진행하기 위한 초임계 파일럿(pilot) 설비(100)를 나타낸 것이다. 2 shows a supercritical pilot facility 100 for performing a supercritical process of separating tocopherol using a supercritical fluid from a pretreated sample obtained by pretreating a deodorizing distillate of vegetable oil.
상기 초임계 파일럿 설비(100) (압력 최대 600기압, 온도 최대 100℃)는 주용매(이산화탄소) 저장탱크(1), 보조용매(에탄올) 저장 탱크(2), 주용매(이산화탄소) 공급 펌프(3), 보조용매 공급 펌프(4), 전처리 시료 저장 탱크(5), 전처리 시료 공급 펌프(6), 향류(countercurrent) 컬럼(7), 추잔물(raffinate)(8), 압력조절밸브 1(9), 분리기 1(10), 니들 밸브 1(11), 불순물 배출구(12), 압력조절밸브 2(13), 분리기 2(14), 니들 밸브 2(15), 토코페롤 저장탱크(16), 가스배출구(17), 공정자동제어 컴퓨터(18)를 포함한다. The supercritical pilot facility 100 (pressure up to 600 atm, temperature up to 100° C.) is a main solvent (carbon dioxide) storage tank (1), an auxiliary solvent (ethanol) storage tank (2), a main solvent (carbon dioxide) supply pump ( 3), auxiliary solvent feed pump (4), pretreatment sample storage tank (5), pretreatment sample feed pump (6), countercurrent column (7), raffinate (8), pressure control valve 1 ( 9), separator 1 (10), needle valve 1 (11), impurity outlet (12), pressure control valve 2 (13), separator 2 (14), needle valve 2 (15), tocopherol storage tank (16), It includes a gas outlet (17) and a process automatic control computer (18).
도 2를 참고하면, 주용매(이산화탄소) 저장탱크(1)에 이산화탄소를 저장하고, 보조용매(에탄올) 저장 탱크(2)에 에탄올을 저장한다. 에탄올은 토코페롤을 잘 용해하기 때문에 보조용매로 사용한다. 또한, 전처리 과정을 통해 얻은 전처리 시료를 전처리 시료 저장 탱크(5)에 저장한다. Referring to FIG. 2 , carbon dioxide is stored in a main solvent (carbon dioxide) storage tank 1 , and ethanol is stored in an auxiliary solvent (ethanol) storage tank 2 . Ethanol is used as an auxiliary solvent because it dissolves tocopherol well. In addition, the pretreatment sample obtained through the pretreatment process is stored in the pretreatment sample storage tank 5 .
주용매(이산화탄소) 공급 펌프(3)와 보조용매 공급 펌프(4)를 가동하여 주용매(이산화탄소)와 보조용매(에탄올)를 향류(countercurrent) 컬럼(7)의 하부(73)에 공급하고, 전처리 시료 저장 탱크(5)에 저장된 전처리 시료를 전처리 시료 공급 펌프(6)를 통해 향류(countercurrent) 컬럼(7)의 상부(top)(71) 또는 중간(medium)(72) 부분에 주입하게 되면, 주용매로 초임계 용매인 이산화탄소와 보조용매(에탄올) 그리고 전처리 시료가 접촉하여 토코페롤을 추출할 수 있게 된다. 향류(countercurrent) 컬럼(7) 내부에는 라시히링(raschig ring)을 충전하여 기체와 액체의 접촉면적을 증가시킬 수 있다. 일정 접촉 시간 경과 후 향류(countercurrent) 컬럼(7) 꼭대기에 토코페롤이 농축된 상태의 흐름(stream)이 생기게 되며, 향류(countercurrent) 컬럼(7) 바닥에 추잔물(raffinate)(8)이 쌓이게 된다. The main solvent (carbon dioxide) supply pump 3 and the auxiliary solvent supply pump 4 are operated to supply the main solvent (carbon dioxide) and the auxiliary solvent (ethanol) to the lower part 73 of the countercurrent column 7, When the pretreatment sample stored in the pretreatment sample storage tank 5 is injected into the top 71 or medium 72 portion of the countercurrent column 7 through the pretreatment sample supply pump 6, , it is possible to extract tocopherol by contacting the supercritical solvent carbon dioxide as the main solvent, the auxiliary solvent (ethanol), and the pretreatment sample. The countercurrent column 7 may be filled with a Raschig ring to increase the contact area between the gas and the liquid. After a certain contact time has elapsed, a stream in which tocopherol is concentrated is generated at the top of the countercurrent column 7, and a raffinate 8 is accumulated at the bottom of the countercurrent column 7 .
이때, 압력조절밸브 1(9)를 감압하여, 분리기 1(separator)(10)의 아래로 불순물이 니들 밸브 1(11)을 통해 불순물 배출구(12)로 배출되게 된다. 또한, 압력조절밸브 2(13)를 감압하게 되면 분리기 2(separator)(14) 아래로 토코페롤이 니들 밸브 2(15)를 통해 토코페롤 저장탱크(16)에 저장되게 되며, 분리기 2(separator)(14)의 오른쪽 측면으로 가스배출구(17)를 통해 이산화탄소와 에탄올 가스 등이 배출되게 된다. At this time, the pressure regulating valve 1 (9) is depressurized, and impurities are discharged to the bottom of the separator 1 (10) through the needle valve 1 (11) to the impurity outlet (12). In addition, when the pressure control valve 2 (13) is reduced, the tocopherol is stored in the tocopherol storage tank 16 through the needle valve 2 (15) under the separator 2 (separator) 14, and the separator 2 (separator) ( 14), carbon dioxide and ethanol gas are discharged through the gas outlet 17 on the right side.
또한, 상기 분리기 1(separator)(10)과 분리기 2(separator)(14) 사이에 추가의 압력조절밸브, 분리기 그리고 니들 밸브를 설치하는 것도 가능하다. In addition, it is also possible to install an additional pressure control valve, a separator and a needle valve between the separator 1 (separator) 10 and the separator 2 (separator) (14).
도 3은 또 다른 실시 태양으로, 식물성 유지의 탈취 증류물을 전처리하여 얻은 전처리 시료를 초임계 유체를 이용하여 토코페롤을 분리하는 초임계 공정을 진행하기 위한 초임계 파일럿(pilot) 설비(200)를 나타낸 것이다. 3 is another embodiment, a supercritical pilot facility 200 for performing a supercritical process of separating tocopherol using a supercritical fluid from a pretreatment sample obtained by pretreating a deodorizing distillate of vegetable oil. it has been shown
도 3과 같이, 초임계 파일럿(pilot) 설비(200)에는 도 2에 도시된 구성 이외에도 구체적으로, 초임계 파일럿(pilot) 설비 향류 컬럼(7) 외부에 히팅재킷(19)을 설치하여 컬럼 내부의 온도를 조절할 수 있다. As shown in FIG. 3 , in the supercritical pilot facility 200 , in addition to the configuration shown in FIG. 2 , specifically, a heating jacket 19 is installed outside the countercurrent column 7 of the supercritical pilot facility to the inside of the column. temperature can be adjusted.
또한, 압력조절밸브 1(9) 상단에 고압기화기(20)를 설치하고, 분리기 2(14) 상단에 저압기화기(21)를 설치할 수 있다. 압력조절밸브 1(9)와 압력조절밸브 2(13)으로 압력을 떨어뜨리면 주울-톰슨 효과에 의해 유체의 온도가 급강하되므로 이를 방지하기 위하여 가열이 가능한 고압기화기(20)와 저압기화기(21)를 설치한다. 아울러, 토코페롤 저장탱크(16)에 저장된 토코페롤의 순도 및 수율을 향상시키기 위하여 환류펌프(REFLUX PUMP)(22)를 가동하여 분리된 토코페롤을 다시 향류 컬럼(7)의 상부(74)나 중간(75) 부분에 주입시킬 수 있다. 또한, 분리기 2(separator)(14)의 상부로부터 가스배출구(17)를 통해 에탄올과 이산화탄소가 배출되는데 에탄올은 보조용매(에탄올) 응축기 1(25)로 응축시켜 보조용매(에탄올) 리시버 1(23)로 회수하고, 이산화탄소는 주용매(이산화탄소) 응축기 2(26)으로 응축시켜 주용매(이산화탄소) 리시버 2(24)로 회수한 다음 냉각기(27)에서 추가 냉각시킨 후 주용매(이산화탄소) 저장 탱크(1)에 보내 재사용하게 된다.In addition, the high-pressure carburetor 20 may be installed at the upper end of the pressure control valve 1 (9), and the low-pressure carburetor 21 may be installed at the upper end of the separator 2 (14). When the pressure is lowered with the pressure control valve 1 (9) and the pressure control valve 2 (13), the temperature of the fluid drops sharply due to the Joule-Thomson effect. to install In addition, in order to improve the purity and yield of tocopherol stored in the tocopherol storage tank 16, a reflux pump 22 is operated to return the separated tocopherol to the upper 74 or middle 75 of the countercurrent column 7 ) can be injected into the In addition, ethanol and carbon dioxide are discharged through the gas outlet 17 from the upper part of the separator 2 (separator) 14, and the ethanol is condensed by the auxiliary solvent (ethanol) condenser 1 (25), and the auxiliary solvent (ethanol) receiver 1 (23) ), and the carbon dioxide is condensed with the main solvent (carbon dioxide) condenser 2 (26), recovered by the main solvent (carbon dioxide) receiver 2 (24), and then further cooled in the cooler 27, and then the main solvent (carbon dioxide) storage tank (1) to be reused.
아울러, 토코페롤의 순도를 보다 높이기 위하여 향류(countercurrent) 컬럼(7)의 높이를 증가시키거나 추가적으로 분자증류기를 이용하여 증류과정을 추가할 수 있다. In addition, in order to further increase the purity of tocopherol, the height of the countercurrent column 7 may be increased or a distillation process may be additionally added using a molecular distiller.
상기 토코페롤 분리 단계는, 전술한 바와 같이, 주용매와 보조용매를 향류(countercurrent) 컬럼 하부에 주입하고, 전처리 과정에서 얻은 전처리 시료는 향류 컬럼 상부 또는 중간 부분에 주입할 수 있다. In the tocopherol separation step, as described above, the main solvent and the auxiliary solvent may be injected into the lower portion of the countercurrent column, and the pretreatment sample obtained in the pretreatment process may be injected into the upper portion or the middle portion of the countercurrent column.
또한, 상기 토코페롤 분리 단계는, 상기 향류(countercurrent) 컬럼 내의 온도는 30~60℃, 압력은 300~600 bar이고, 컬럼 내에서 전처리 과정에서 얻은 전처리 시료의 체류시간은 30~120분일 수 있다.In addition, the tocopherol separation step, the temperature in the countercurrent (countercurrent) column is 30 ~ 60 ℃, the pressure is 300 ~ 600 bar, the retention time of the pretreatment sample obtained in the pretreatment process in the column may be 30 ~ 120 minutes.
상기 토코페롤의 추출 수율과 순도를 증가시키기 위하여, 향류(countercurrent) 컬럼의 온도는 30~60℃, 압력은 300~600 bar로 조절할 수 있고, 컬럼 내에서 전처리 과정에서 얻은 전처리 시료의 체류시간은 30~120분일 수 있다. 더욱 상세하게는 상기 컬럼 내의 온도는 40℃, 압력은 400 bar이고, 컬럼 내에서 전처리 과정에서 얻은 전처리 시료의 체류시간은 90분 일 수 있다. In order to increase the extraction yield and purity of the tocopherol, the temperature of the countercurrent column can be adjusted to 30 to 60° C. and the pressure to 300 to 600 bar, and the retention time of the pretreatment sample obtained during the pretreatment in the column is 30 It can be ~120 minutes. In more detail, the temperature in the column is 40° C., the pressure is 400 bar, and the residence time of the pre-treatment sample obtained in the pre-treatment process in the column may be 90 minutes.
또한, 상기 전처리 과정에서 얻은 전처리 시료와 주용매는 1: 5~30의 중량비, 주용매와 보조용매는 1: 0.05~0.3의 중량비로 주입될 수 있다. 더욱 상세하게는 상기 전처리 과정에서 얻은 전처리 시료와 주용매는 1: 10의 중량비, 주용매와 보조용매는 1: 0.1의 중량비로 주입될 수 있다. 또한 상기 주용매는 초임계 유체로 이산화탄소가 사용될 수 있다. 또한 보조 용매로는 에탄올이 사용될 수 있으며, 상기 보조 용매는 토코페콜의 용해도를 증가시켜 전처리 시료로부터 토코페롤 추출 또는 분리 수율을 증가시키고 순도를 증가시킬 수 있다.In addition, the pretreatment sample and the main solvent obtained in the pretreatment process may be injected in a weight ratio of 1: 5 to 30, and the main solvent and the auxiliary solvent in a weight ratio of 1: 0.05 to 0.3. More specifically, the pretreatment sample and the main solvent obtained in the pretreatment process may be injected in a weight ratio of 1:10, and the main solvent and the auxiliary solvent in a weight ratio of 1:0.1. In addition, carbon dioxide may be used as the main solvent as a supercritical fluid. In addition, ethanol may be used as the auxiliary solvent, and the auxiliary solvent may increase the solubility of tocopherol to increase the extraction or separation yield of tocopherol from the pretreatment sample and increase the purity.
다른 하나의 양태로서, 본 발명은 전술한 바와 같은 식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법에 의해 분리된 토코페롤을 제공한다. In another aspect, the present invention provides tocopherol separated by the method for separating tocopherol from the deodorized distillate of vegetable oil as described above.
본 발명에서 용어 "식물성 유지의 탈취 증류물", "식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법"에 대한 설명은 전술한 바와 같다.In the present invention, the terms "deodorized distillate of vegetable oil" and "method of separating tocopherol from deodorized distillate of vegetable oil" are the same as described above.
본 발명에 따르면, 버려지는 식물성 유지의 탈취 증류물에서 토코페롤을 고효율로 회수가 가능하다. According to the present invention, it is possible to efficiently recover tocopherol from the deodorized distillate of discarded vegetable oils and fats.
이하, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예에 대하여 첨부한 도면을 참고로 하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며 여기에서 설명하는 실시예에 한정되지 않는다. Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.
실험예 1. 콩기름 탈취 증류물의 조성 분석Experimental Example 1. Analysis of composition of soybean oil deodorization distillate
콩기름 탈취공정에서 발생하는 콩기름 탈취 증류물(Deodorized Distillate, DOD)의 산가, 검화가, 그리고 조성을 분석하였다. 표 1은 산가와 검화가를 분석한 결과이다. 산가는 유지 1g 중에 함유된 유리지방산을 중화하는 데 필요한 KOH의 mg 수로, 지방산이 glyceride로서 결합형태로 있지 않은 유리 지방산의 양을 측정하는 것이다. 산가가 높으면 유지가 변패된 것을 의미한다. Acid value, saponification, and composition of soybean oil deodorized distillate (DOD) generated in the soybean oil deodorization process were analyzed. Table 1 shows the results of analyzing acid value and saponification value. Acid value is the number of mg of KOH required to neutralize free fatty acids contained in 1 g of fat and oil, and measures the amount of free fatty acids in which fatty acids are not in a bound form as glycerides. If the acid value is high, it means that the fats and oils have deteriorated.
그리고 검화(비누화)가는 유지 1g을 완전히 검화시키는 데 필요한 KOH의 mg 수이다. 검화가는 유지의 구성 지방산의 분자량에 반비례하므로 저급지방산 함량이 많은 유지는 검화가가 크고, 고급 지방산 함량이 많은 유지는 검화가가 작다. And the saponification (saponification) number is the number of mg of KOH required to completely saponify 1 g of fat. Since the saponification value is inversely proportional to the molecular weight of the constituent fatty acids of the fats and oils, fats with a high content of lower fatty acids have a large saponification value, and oils and fats with a high content of higher fatty acids have a low saponification value.
파라미터(parameter)parameter 값(value)value
산가(acid value, AV)acid value (AV) 103.5 mg KOH/g103.5 mg KOH/g
검화가(saponification value, SV)saponification value (SV) 144.2 mg KOH/g144.2 mg KOH/g
상기 콩기름 탈취 증류물의 조성 분석 결과는 표 2와 같다. 총 100% 중에 유리 지방산(free fatty acids, FFA) 52.2%, 글리세라이드(glycerides, Gly) 21.4%, 스쿠알렌(squalene) 3.11%, 토코페롤(tocopherol) 9.23%, 스테롤(sterol) 5.47%, 그리고 불순물 8.59%를 포함하였다. 그리고 상기 불순물에는 장쇄 파라핀(long chain paraffins), 스테롤 에스테르(sterol esters), 색소(pigment)와 왁스(wax) 등이 있었다.The composition analysis result of the soybean oil deodorization distillate is shown in Table 2. Of the total 100%, free fatty acids (FFA) 52.2%, glycerides (Gly) 21.4%, squalene 3.11%, tocopherol 9.23%, sterols 5.47%, and impurities 8.59 % was included. And the impurities included long chain paraffins, sterol esters, pigments and waxes.
또한, 토코페롤 9.23% 중에는 α-토코페롤 13.1%, β-토코페롤과 γ-토코페롤이 50.2%, δ-토코페롤이 36.7%였다. 그리고 스테롤 5.47% 중에는 캠프스테롤 30%, 스티그마스테롤, 베타-시토스테롤 41.2%를 차지하였다. Also, among 9.23% of tocopherols, 13.1% of α-tocopherol, 50.2% of β-tocopherol and γ-tocopherol, and 36.7% of δ-tocopherol. And among 5.47% of sterols, campsterol accounted for 30%, stigmasterol, and beta-sitosterol 41.2%.
조성Furtherance 중량 (%)weight (%)
유리 지방산free fatty acids 52.252.2
글리세라이드glycerides 21.421.4
스쿠알렌squalene 3.113.11
토코페롤tocopherol 9.239.23
스테롤sterols 5.475.47
불순물impurities 8.598.59
총합total 100 %100%
실험예 2. 콩기름 탈취 증류물의 전처리 공정 진행Experimental Example 2. Pre-treatment process of soybean oil deodorization distillate
2-1. 메틸에스테르화 반응 진행2-1. Methyl esterification reaction proceeds
반응기에 콩기름 탈취 증류물(DOD) 2,100kg, 메탄올 1,300kg, 황산 42kg을 투입하여 70℃에서 4시간 환류(reflux)시키면서 메틸에스테르화 반응(methyl esterification)을 진행하였다. 상기 메틸에스테르 반응(methyl esterification)을 통하여 콩기름 탈취 증류물(DOD)에 함유된 유리 지방산이 지방산 메틸 에스테르(Fatty acid methyl esters, FAMEs)으로 전환되게 된다.2,100 kg of soybean oil deodorizing distillate (DOD), 1,300 kg of methanol, and 42 kg of sulfuric acid were put into the reactor, and methyl esterification was performed while refluxing at 70° C. for 4 hours. The free fatty acids contained in the soybean oil deodorizing distillate (DOD) are converted into fatty acid methyl esters (FAMEs) through the methyl esterification.
2-2.메탄올분해 반응 진행2-2. Progression of methanolysis
또한, 상기 메틸에스테르 반응이 종료된 후 정치 및 중화 과정을 진행하여 유상(oil phase)은 상부, 그리고 수상(water phase)은 하부로 분리되었다. 이후 유상만을 수득한 후 메탄올 570kg, 나트륨메톡사이드(NaOCH3) 25kg을 주입하고 70℃에서 120분간 환류(reflux)시키면서 메탄올분해 반응(methanolysis)을 진행하였다. 상기 메탄올분해 반응을 통해 콩기름 탈취 증류물(DOD)에 함유된 글리세라이드와 스테롤 에스테르(sterol esters)이 각각 지방산 메틸 에스테르(Fatty acid methyl esters, FAMEs)와 스테롤(sterols)로 전환되게 된다. In addition, after the completion of the methyl ester reaction, a stationary and neutralization process was performed to separate the oil phase into the upper part and the water phase into the lower part. After obtaining only an oil phase, methanol 570 kg and sodium methoxide (NaOCH 3 ) 25 kg were injected and refluxed at 70° C. for 120 minutes, followed by methanolysis (methanolysis). Through the methanolysis reaction, glycerides and sterol esters contained in soybean oil deodorizing distillate (DOD) are converted into fatty acid methyl esters (FAMEs) and sterols, respectively.
2-3. 결정화 및 가압탈수(filter press) 과정 진행2-3. Crystallization and pressure dehydration (filter press) process proceeds
다음으로, 상기 2-1과 2-2의 반응 과정을 진행 한 후, 20℃에서 7시간 30분 동안 냉각하여 결정화를 진행하였으며, 15rpm에서 원심분리하였다. 이후 10시간 30분 동안 가압탈수(filter pressing) 과정을 진행하여 고체상의 케이크(cake)로 조스테롤(crude sterol)과 액체상의 지방산메틸에스테르와 토코페롤이 함유된 여액(filtrate)을 얻었다. Next, after performing the reaction processes of 2-1 and 2-2, crystallization was performed by cooling at 20° C. for 7 hours and 30 minutes, followed by centrifugation at 15 rpm. Thereafter, a filter pressing process was performed for 10 hours and 30 minutes to obtain a filtrate containing crude sterol, liquid fatty acid methyl ester, and tocopherol as a solid cake.
2-4. 재결정화 과정 진행을 통한 정제 피토스테롤 분리2-4. Separation of purified phytosterol through recrystallization process
2-3 과정에서 얻어진 조스테롤(crude sterol) 200kg에 에탄올 1,400kg을 넣고 70℃에서 2시간 용해한 후, 25℃에서 6시간 냉각 결정화를 진행하고 원심분리를 진행하였다. 또한 시간당 20kg을 건조하여 순도 93~97%로 정제된 피토스테롤(phytosterols) 얻었다.1,400 kg of ethanol was added to 200 kg of crude sterol obtained in step 2-3, dissolved at 70° C. for 2 hours, cooled and crystallized at 25° C. for 6 hours, followed by centrifugation. In addition, 20 kg per hour was dried to obtain purified phytosterols with a purity of 93 to 97%.
2-5. 박막증류장치를 이용한 박막 증류 과정을 이용한 FAMEs 및 토코페롤을 포함하는 FEED MATERIALS 분리2-5. Separation of FEED MATERIALS containing FAMEs and tocopherols using thin film distillation using thin film distillation equipment
2-3의 결정화 및 가압탈수(filter press) 과정을 거친 후 지방산 메틸에스테르와 토코페롤이 함유된 여액을 박막 증류장치(thin film evaporator)를 이용하여 220℃에서 시간당 150kg을 처리하여 지방산메틸에스테르(Fatty acid methyl esters, FAMEs)를 분리시켜 최종적으로 유리지방산, 글리세라이드, 스테롤, 그리고 스테롤 에스테르가 제거되고, 토코페롤 함량이 증가된 전처리 시료(FEED MATERIALS)을 얻었다.After crystallization and dehydration under pressure (filter press) of 2-3, the filtrate containing fatty acid methyl ester and tocopherol was treated with 150 kg per hour at 220° C. using a thin film evaporator to obtain fatty acid methyl ester (Fatty). acid methyl esters, FAMEs) were finally removed, free fatty acids, glycerides, sterols, and sterol esters were removed, and a pretreatment sample (FEED MATERIALS) with an increased tocopherol content was obtained.
실험예 3. FEED MATERIALS을 이용한 초임계 추출Experimental Example 3. Supercritical Extraction Using FEED MATERIALS
초임계 pilot 설비(압력 최대 600기압, 온도 최대 100℃)를 이용하였으며, 향류 컬럼(countercurrent column) (직경 60mm, 높이 4m)을 이용하였으며, 컬럼 내부에는 라시히링(raschig ring)을 충전하였다. pilot test는 압력 200~500기압, 온도 30℃~80℃ 범위에서, 전처리 시료와 용매를 1:10의 중량비, 용매와 보조용매를 1:0.1의 중량비, 컬럼내 체류시간을 30분에서 120분으로 변화시켜 진행하였다.A supercritical pilot facility (pressure up to 600 atm, temperature up to 100° C.) was used, and a countercurrent column (diameter 60 mm, height 4 m) was used, and a raschig ring was filled inside the column. The pilot test was conducted at a pressure of 200 to 500 atm, and a temperature in the range of 30°C to 80°C, with a weight ratio of 1:10 for the pretreatment sample and solvent, 1:0.1 for the solvent and co-solvent, and a retention time in the column of 30 to 120 minutes. was changed to .
구체적으로, 이산화탄소(용매) 및 에탄올(보조용매)을 상기 향류 컬럼 하부에 주입하고, 전처리 공정에서 얻은 전처리 시료(FEED MATERIALS)을 컬럼의 상부, 중간부분에 주입하였다. 가동 시간이 경과되면서 컬럼의 꼭대기 부분에 토코페롤이 농축된 흐름(stream)이 생겼고, 바닥 부분에는 추잔물이 쌓였다. 또한, 압력 조절 밸브로 감압(depressurization)하여 불순물을 분리기(separator 1) 아래에 분리하였으며, 압력 조절밸브를 추가 감압하여 분리기(separator 2) 아래에 토코페롤을 분리하였다.Specifically, carbon dioxide (solvent) and ethanol (co-solvent) were injected into the lower portion of the countercurrent column, and the pretreatment sample (FEED MATERIALS) obtained in the pretreatment process was injected into the upper and middle portions of the column. As the operating time elapsed, a stream enriched in tocopherol was formed at the top of the column, and raffinate was accumulated at the bottom. In addition, impurities were separated under the separator (separator 1) by depressurization with a pressure control valve, and tocopherol was separated under the separator (separator 2) by further depressurizing the pressure control valve.
표 3은 압력, 온도에 따른 초임계 추출방법을 이용하여 토코페롤 순도와 추출 수율을 비교한 것이다. 그 결과, 표 3에 나타난 바와 같이, 압력 400기압, 온도 40℃에서 토코페롤 추출 수율과 순도가 가장 높았으며, 컬럼 내 체류 시간이 90분이었을 때, 토코페롤 추출 수율과 순도가 가장 높았다. Table 3 compares tocopherol purity and extraction yield using the supercritical extraction method according to pressure and temperature. As a result, as shown in Table 3, the tocopherol extraction yield and purity were the highest at a pressure of 400 atmospheres and a temperature of 40°C, and when the residence time in the column was 90 minutes, the tocopherol extraction yield and purity were the highest.
NONO 압력(bar)pressure (bar) 온도(℃)Temperature (℃) 추출수율(%)Extraction yield (%) 순도(중량%)Purity (wt%)
NO 1NO 1 200200 3030 4141 3232
NO 2 NO 2 4040 4545 3535
NO 3 NO 3 5050 4343 3434
NO 4 NO 4 6060 4141 3232
NO 5 NO 5 7070 3939 3030
NO 6 NO 6 8080 3535 2626
NO 7 NO 7 300300 3030 6464 5959
NO 8 NO 8 4040 7070 6565
NO 9 NO 9 5050 6868 6262
NO 10 NO 10 6060 6262 6262
NO 11 NO 11 7070 6060 6060
NO 12 NO 12 8080 5757 5353
NO 13 NO 13 400400 3030 8282 8888
NO 14 NO 14 4040 9090 9595
NO 15 NO 15 5050 8686 9191
NO 16 NO 16 6060 8181 8888
NO 17 NO 17 7070 7575 8181
NO 18 NO 18 8080 7070 7676
NO 19 NO 19 500500 3030 7777 8383
NO 20 NO 20 4040 8282 9090
NO 21 NO 21 5050 7474 8282
NO 22 NO 22 6060 7373 8181
NO 23NO 23 7070 6969 7575
NO 24 NO 24 8080 6161 7171
압력 400기압, 온도 40℃에서 컬럼 내 체류 시간이 90분이었을 때, 분리된 토코페롤을 HPLC(High Performance Liquid Chromatography)를 이용하여 분석하고 그 결과를 도 4에 나타내었다. Shimadzu SPD-10A detector 295nm(UV length)와 silica-gel column을 사용하였으며 이동상(mobile phase)는 n-hexane : propanol (99:1, v/v), 표준물질로 DL-알파-tocopherol 사용하여 계산하였다.When the residence time in the column was 90 minutes at a pressure of 400 atmospheres and a temperature of 40° C., the separated tocopherol was analyzed using high performance liquid chromatography (HPLC), and the results are shown in FIG. 4 . Shimadzu SPD-10A detector 295 nm (UV length) and silica-gel column were used. The mobile phase was calculated using n-hexane: propanol (99:1, v/v) and DL-alpha-tocopherol as a standard material. did
그 결과 도 4에 도시된 바와 같이, 다양한 타입의 토코페롤이 분리된 것을 확인하였다. As a result, as shown in FIG. 4, it was confirmed that various types of tocopherols were separated.
또한, 콩기름 탈취 증류물(Deodorized Distillate, DOD)에 토코페롤이 약 10% 정도가 함유되어 있는데 본 발명의 전처리 과정과 초임계 공정을 이용하여 수율 80% 이상 추출가능하였다.In addition, about 10% of tocopherol is contained in soybean oil deodorized distillate (DOD), and it was possible to extract at a yield of 80% or more using the pretreatment process and supercritical process of the present invention.
이상에서 본 발명의 바람직한 실시예에 대하여 상세하게 설명하였지만 본 발명의 권리범위는 이에 한정되는 것은 아니고 다음의 청구범위에서 정의하고 있는 본 발명의 기본 개념을 이용한 당업자의 여러 변형 및 개량 형태 또한 본 발명의 권리범위에 속하는 것이다.Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims are also provided. is within the scope of the

Claims (16)

  1. 식물성 유지의 탈취 증류물을 전처리 하는 단계; 및 Pre-treating the deodorizing distillate of vegetable oil; and
    상기 전처리 과정에서 얻은 전처리 시료에 초임계 유체를 혼합하고 토코페롤을 분리하는 단계;를 포함하는,Including; mixing the supercritical fluid with the pretreatment sample obtained in the pretreatment process and separating tocopherol
    식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법.A method for isolating tocopherols from deodorized distillates of vegetable oils.
  2. 제1항에 있어서,According to claim 1,
    상기 식물성 유지는 콩기름, 옥수수기름, 채종유, 미강유, 참기름, 들기름, 홍화유, 해바라기유, 목화씨기름, 땅콩기름, 올리브유, 팜유류, 야자유 및 고추씨기름으로 이루어진 군에서 선택되는,The vegetable oil is selected from the group consisting of soybean oil, corn oil, rapeseed oil, rice bran oil, sesame oil, perilla oil, safflower oil, sunflower oil, cottonseed oil, peanut oil, olive oil, palm oil, palm oil and red pepper seed oil,
    식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법.A method for isolating tocopherols from deodorized distillates of vegetable oils.
  3. 제1항에 있어서,According to claim 1,
    상기 전처리 단계는,The pre-processing step is
    메틸에스테르화 반응을 진행하는 단계;performing a methyl esterification reaction;
    메탄올분해 반응을 진행하는 단계;performing a methanolysis reaction;
    결정화, 가압탈수 및 재결정화 과정을 진행하는 단계; 또는performing crystallization, pressure dehydration and recrystallization; or
    박막 증류 과정을 진행하는 단계를 포함하는 것인, Which comprises the step of proceeding with a thin film distillation process,
    식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법.A method for isolating tocopherols from deodorized distillates of vegetable oils.
  4. 제1항에 있어서,According to claim 1,
    상기 메틸에스테르화 반응에 의해 식물성 유지 탈취 증류물에 함유된 유리 지방산이 지방산 메틸 에스테르로 전환되는 것인, By the methyl esterification reaction, the free fatty acids contained in the vegetable oil deodorizing distillate are converted into fatty acid methyl esters,
    식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법.A method for isolating tocopherols from deodorized distillates of vegetable oils.
  5. 제1항에 있어서,According to claim 1,
    상기 메탄올분해 반응에 의해 식물성 유지 탈취 증류물에 함유된 글리세라이드와 스테롤 에스테르가 각각 지방산 메틸 에스테르와 스테롤(sterols)로 전환되는 것인, The glycerides and sterol esters contained in the deodorizing distillate of vegetable oil by the methanolysis reaction are converted into fatty acid methyl esters and sterols, respectively,
    식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법.A method for isolating tocopherols from deodorized distillates of vegetable oils.
  6. 제1항에 있어서,According to claim 1,
    상기 결정화, 가압탈수 과정 및 재결정화 과정에 의해 피토스테롤이 분리되는 것인, Phytosterol is separated by the crystallization, pressure dehydration process and recrystallization process,
    식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법.A method for isolating tocopherols from deodorized distillates of vegetable oils.
  7. 제1항에 있어서,According to claim 1,
    상기 박막 증류 과정에 의해 지방산 메틸 에스테르가 분리되는 것인, The fatty acid methyl ester is separated by the thin film distillation process,
    식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법.A method for isolating tocopherols from deodorized distillates of vegetable oils.
  8. 제1항에 있어서,According to claim 1,
    상기 전처리 과정에서 얻은 전처리 시료는,The pretreatment sample obtained in the pretreatment process is,
    식물성 유지 탈취 증류물에서 유리 지방산, 글리세라이드, 스테롤, 그리고 스테롤 에스테르가 제거된 것인, Free fatty acids, glycerides, sterols, and sterol esters are removed from vegetable oil deodorizing distillate,
    식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법.A method for isolating tocopherols from deodorized distillates of vegetable oils.
  9. 제1항에 있어서,According to claim 1,
    상기 토코페롤 분리 단계는,The tocopherol separation step,
    주용매와 보조용매를 향류(countercurrent) 컬럼 하부에 주입하고, 전처리 과정에서 얻은 전처리 시료는 향류 컬럼 상부 또는 중간부분에 주입하는 것인,The main solvent and the auxiliary solvent are injected into the lower part of the countercurrent column, and the pretreatment sample obtained in the pretreatment process is injected into the upper or middle part of the countercurrent column,
    식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법.A method for isolating tocopherols from deodorized distillates of vegetable oils.
  10. 제9항에 있어서,10. The method of claim 9,
    상기 토코페롤 분리 단계는,The tocopherol separation step,
    상기 컬럼 내의 온도는 30~60℃, 압력은 300~600 bar이고, 컬럼 내에서 전처리 과정에서 얻은 전처리 시료의 체류시간은 30~120분인 것인, The temperature in the column is 30-60 ° C, the pressure is 300-600 bar, and the retention time of the pre-treatment sample obtained in the pre-treatment process in the column is 30-120 minutes,
    식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법.A method for isolating tocopherols from deodorized distillates of vegetable oils.
  11. 제10항에 있어서,11. The method of claim 10,
    상기 토코페롤 분리 단계는,The tocopherol separation step,
    상기 컬럼 내의 온도는 40℃, 압력은 400 bar이고, 컬럼 내에서 전처리 과정에서 얻은 전처리 시료의 체류시간은 90분인 것인, The temperature in the column is 40 ℃, the pressure is 400 bar, the retention time of the pretreatment sample obtained in the pretreatment process in the column is 90 minutes,
    식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법.A method for isolating tocopherols from deodorized distillates of vegetable oils.
  12. 제9항에 있어서,10. The method of claim 9,
    상기 전처리 과정에서 얻은 전처리 시료와 주용매는 1: 5~30의 중량비, 주용매와 보조용매는 1: 0.05~0.3의 중량비로 주입되는 것인,The pretreatment sample and the main solvent obtained in the pretreatment process are injected in a weight ratio of 1: 5-30, and the main solvent and auxiliary solvent are injected in a weight ratio of 1: 0.05-0.3,
    식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법.A method for isolating tocopherols from deodorized distillates of vegetable oils.
  13. 제12항에 있어서,13. The method of claim 12,
    상기 주용매는 이산화탄소, 상기 보조용매는 에탄올인 것인, The main solvent is carbon dioxide, the auxiliary solvent is ethanol,
    식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법.A method for isolating tocopherols from deodorized distillates of vegetable oils.
  14. 제1항에 있어서,According to claim 1,
    상기 토코페롤의 분리 단계 이후에,After the separation of tocopherol,
    토코페롤의 순도 및 수율을 향상시키기 위하여 환류펌프(REFLUX PUMP)를 가동하여 분리된 토코페롤을 다시 향류 컬럼의 상부나 중간 부분에 주입하는 것인,In order to improve the purity and yield of tocopherol, the reflux pump is operated to inject the separated tocopherol into the upper or middle part of the countercurrent column again,
    식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법.A method for isolating tocopherols from deodorized distillates of vegetable oils.
  15. 제14항에 있어서,15. The method of claim 14,
    상기 토코페롤의 순도를 향상시키기 위하여 추가적으로 분자증류기를 사용하는 것인, In order to improve the purity of the tocopherol additionally using a molecular distiller,
    식물성 유지의 탈취 증류물에서 토코페롤을 분리하는 방법.A method for isolating tocopherols from deodorized distillates of vegetable oils.
  16. 제1항 내지 제15항 중 어느 한 항의 토코페롤을 분리하는 방법에 의해 분리된 토코페롤.Tocopherol isolated by the method for separating the tocopherol of any one of claims 1 to 15.
PCT/KR2021/010502 2020-08-10 2021-08-09 Method for separating tocopherols from vegetable oil deodorizer distillate WO2022035159A1 (en)

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