KR20020000660A - Pigment extraction of chlorophyll and carotenoid from seaweed, crustacea and echinoderm using supercritical and subcritical CO2 with entrainer - Google Patents

Pigment extraction of chlorophyll and carotenoid from seaweed, crustacea and echinoderm using supercritical and subcritical CO2 with entrainer Download PDF

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KR20020000660A
KR20020000660A KR1020000035638A KR20000035638A KR20020000660A KR 20020000660 A KR20020000660 A KR 20020000660A KR 1020000035638 A KR1020000035638 A KR 1020000035638A KR 20000035638 A KR20000035638 A KR 20000035638A KR 20020000660 A KR20020000660 A KR 20020000660A
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chlorophyll
supercritical
carotenoid
seaweeds
crustacea
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전병수
홍석기
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전병수
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
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    • A23L5/40Colouring or decolouring of foods
    • A23L5/42Addition of dyes or pigments, e.g. in combination with optical brighteners
    • A23L5/43Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives
    • A23L5/44Addition of dyes or pigments, e.g. in combination with optical brighteners using naturally occurring organic dyes or pigments, their artificial duplicates or their derivatives using carotenoids or xanthophylls
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61K35/56Materials from animals other than mammals
    • A61K35/616Echinodermata, e.g. starfish, sea cucumbers or sea urchins
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K36/00Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
    • A61K36/02Algae
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D11/00Solvent extraction
    • B01D11/04Solvent extraction of solutions which are liquid
    • B01D11/0403Solvent extraction of solutions which are liquid with a supercritical fluid
    • B01D11/0411Solvent extraction of solutions which are liquid with a supercritical fluid the supercritical fluid acting as solvent for the solvent and as anti-solvent for the solute, e.g. formation of particles from solutions
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
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    • A23V2200/00Function of food ingredients
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2300/00Processes
    • A23V2300/14Extraction
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2236/00Isolation or extraction methods of medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicine
    • A61K2236/30Extraction of the material
    • A61K2236/37Extraction at elevated pressure or temperature, e.g. pressurized solvent extraction [PSE], supercritical carbon dioxide extraction or subcritical water extraction

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Abstract

PURPOSE: A method for extracting chlorophyll and carotenoid pigments from seaweeds, crustacea and echinodermata using supercritical and subcritical carbon dioxides with an entrainer is provided to prevent loss of valuable constituents by effectively extracting the pigments without using organic solvents. CONSTITUTION: The method for extracting chlorophyll and carotenoid pigments is characterized in that pigments are extracted from liquid or powder type seaweeds and crustacea(crabs and shrimps) and processed byproducts of echinodermata(Ciona intestinalis, starfish, sea urchin, etc.) using 1 to 70%(v/v) of supercritical and subcritical carbon dioxides(CO2), an entrainer of ethanol or a mixture thereof, wherein a temperature of a reactor is in the range of 10 to 80 deg.C, and a pressure of the reactor is in the range of 50 to 500 bars during the extraction by the supercritical and subcritical carbon dioxides, and wherein the chlorophyll and carotenoid pigments are extracted from seaweeds and crustacea(crabs and shrimps) and echinodermata(Ciona intestinalis, starfish, sea urchin, etc.).

Description

초임계 및 아임계 이산화탄소와 보조용매를 이용한 해조류 및 갑각류(게, 새우), 극피동물(유령멍게, 불가사리, 성게 등)로부터 클로로필 및 카로티노이드 색소 추출 방법{Pigment extraction of chlorophyll and carotenoid from seaweed, crustacea and echinoderm using supercritical and subcritical CO2 with entrainer}Pigment extraction of chlorophyll and carotenoid from seaweed, crustacea and supercritical and subcritical carbon dioxide and cosolvents from seaweeds, crustaceans (crabs, shrimps) and echinoderm (ghost sea urchins, starfish, sea urchins) echinoderm using supercritical and subcritical CO2 with entrainer}

일반적으로 해조류 및 수산가공부산물이라 함은 해조류를 채취하여 자연건조, 열풍건조, 냉풍건조 등의 방법을 통하여 가식부분을 상품화하고 남은 잔사물질 즉, 폐기되는 부분을 일컸는다. 그러나 이 페기되는 해조류 및 수산가공부산물에는 알긴산, 토코페롤, 지방산, 색소, 키토산 등의 활용 가능한 성분이 다량 함유되어 있어서 활용에 따라서는 매우 다양하게 이용될 수 있다. 그럼에도 불구하고 해조류 및 수산가공부산물은 다른 식품소재 또는 기타 산업에 소재로서 사용이 활발하지못하다. 그 이유는 해조류 및 수산가공 부산물의 활용 가능한 성분에 대한 인식도의 저하와 해조류 및 수산가공품의 이용 범위의 제한성, 생산시기의 제한성 때문이다. 한편 기존에 알려진 추출 방법인 유기용매 추출 법을 이용하여 유용성분들을 추출할 경우 불순물의 혼입이 많고 유해물질인 용매의 회수가 불가능함으로 제품의 품질에 대한 문제가 야기되고 있으며 몇 단계의 공정을 거치므로 공정이 복잡할 뿐 아니라 유용한 성분도 유실될 수가 있으며 화학약품에 의한 이물질의 혼입도 있을 수 있다. 이러한 문제점을 보완하기 위해 초임계 및 아임계 이산화탄소(CO2)와 보조용매를 이용하여 해조류 및 수산가공부산물로부터 클로로필 및 카로티노이드 색소 성분을 추출하기 위한 연구를 시도하여 본 발명에서 해조류 및 수산가공 부산물로부터 천연 색소를 얻을 수가 있었다.In general, seaweeds and fish processing by-products are used to collect the seaweed and commercialize the decorated part through natural drying, hot air drying, and cold air drying, and the remaining residues, that is, discarded parts. However, these discarded seaweeds and fish processing by-products contain a large amount of usable ingredients such as alginic acid, tocopherol, fatty acids, pigments, chitosan and the like, and can be used in various ways depending on the application. Nevertheless, seaweed and fish processing by-products are not actively used as materials in other food materials or other industries. The reason for this is the decrease in awareness of the available components of seaweed and fish processing by-products, the limitation of the use range of the seaweed and seafood processing products, and the timing of production. On the other hand, when useful components are extracted by using organic solvent extraction method, which is a known extraction method, there are many impurities, and it is impossible to recover harmful solvents. Therefore, not only is the process complicated, but also useful components may be lost and foreign substances may be mixed by chemicals. In order to solve this problem, a study for extracting chlorophyll and carotenoid pigment components from seaweeds and fishery by-products using supercritical and subcritical carbon dioxide (CO2) and cosolvents has been attempted. I could get a pigment.

이에 본 발명에서는 액상 및 분말상의 해조류와 수산 가공 부산물을 초임계 및 아임계 이산화탄소(CO2) 반응기에 넣고 압력, 온도 및 이산화탄소(CO2)와 보조용매의 유량을 조절하여 해조류 및 갑각류(게, 새우), 극피동물(유령멍게, 불가사리, 성게 등)로부터 클로로필 및 카로티노이드 색소를 추출하는 것이다. 본 발명은 기존에 알려진 열수 추출법과 중성염 추출 법이 용매의 회수에 대한 어려움이 따른다는 것과 그 외의 다른 용매 추출 법 또한 얻고자하는 순도의 제품 및 용매회수를 높이기 어려운 단점이 있는데 초임계 및 아임계 추출 법은 여러 단계의 공정을 거치지 않을 뿐 아니라, 원료의 상태를 유지하면서 효과적으로 색소를 추출하는 공정이기에 유용성분의 유실을 막을 수가 있는 장점을 가지고 있다. 초임계 및 아임계 이산화탄소(CO2)를 이용한 분리공정은 천연물질로부터 유용한 성분을 선택적으로 추출함으로서 기존의 재래식 추출 방법에서 야기되는 어려움을 해결할 수 있으므로 해조류 및 갑각류(게, 새우), 극피동물(유령멍게, 불가사리, 성게 등)로부터 색소 성분을 회수하여 식품 및 첨가물 산업분야에 적극 활용할 수 있을 것으로 예상된다.Therefore, in the present invention, the liquid and powdery seaweeds and fishery by-products are put in supercritical and subcritical carbon dioxide (CO2) reactors, and the pressure, temperature, and the flow rate of carbon dioxide (CO2) and the cosolvent are adjusted to control algae and crustaceans (crabs and shrimps). , Chlorophyll and carotenoid pigments are extracted from eukaryotic animals (ghost sea urchins, starfish, sea urchins, etc.). The present invention has the disadvantages that the known hot water extraction method and neutral salt extraction method has difficulty in recovering the solvent and other solvent extraction methods also have difficulty in increasing the purity of the product and solvent recovery to obtain. The critical extraction method does not go through several steps but also has the advantage of preventing the loss of useful components because it is a process of effectively extracting the pigment while maintaining the state of the raw material. Separation process using supercritical and subcritical carbon dioxide (CO2) solves the difficulties caused by conventional extraction methods by selectively extracting useful components from natural substances, so seaweeds, crustaceans (crabs, shrimps) and echinoderm (ghosts) It is expected to recover the pigment components from sea squirts, starfish, sea urchins, etc., and to utilize them in the food and additive industries.

이하 본 발명을 상세히 설명하면 다음과 같다. 본 발명은 액상 및 분말상인 해조류 및 갑각류(게, 새우), 극피동물(유령멍게, 불가사리, 성게 등)로부터 초임계 및 아임계 이산화탄소(CO2)와 보조용매를 이용한 클로로필 및 카로티노이드 색소 추출 방법에 관한 것이다. 본 발명에 따르면 액상 및 분말상의 해조류 및 갑각류(게, 새우), 극피동물(유령멍게, 불가사리, 성게 등)를 초임계 및 아임계 반응기에 투입한 후, 일정한 압력(50-500bar)으로 이산화탄소(CO2)를 통과시키면서 보조용매를 일정량[1-70%(v/v)]사용하여, 색소성분인 클로로필(Chlorophyll)과 카로티노이드-(Carotenoid)를 추출하는 것이다. 본 발명에서는 이산화탄소(CO2)를 추출용매로, 에탄올을 보조용매로 사용하였는데, 이산화탄소(CO2)는 추출 종료 후 곧 바로 휘발되기 때문에 제품 중에 잔존하지 않는 것이 용매로서의 큰 장점이며, 에탄올은 일반적인 방법으로 쉽게 제거할 수가 있다.이하 실시 예를 통하여 본 발명을 구체적으로 설명하고자하나, 다음의 실시 예에 의하여 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail. The present invention relates to a chlorophyll and carotenoid pigment extraction method using supercritical and subcritical carbon dioxide (CO2) and co-solvent from liquid and powdered seaweeds and crustaceans (crabs, shrimps), echinoderm (ghost sea urchins, starfish, sea urchins, etc.) will be. According to the present invention, liquid and powdered seaweeds and crustaceans (crabs, shrimps), echinoderm (ghost sea urchins, starfish, sea urchins, etc.) are introduced into supercritical and subcritical reactors, and then, at a constant pressure (50-500 bar), carbon dioxide ( CO2) is used to extract chlorophyll and carotenoids (Carotenoid), which are pigments, by using a certain amount of co-solvent [1-70% (v / v)]. In the present invention, carbon dioxide (CO2) was used as an extraction solvent and ethanol as a co-solvent, but since carbon dioxide (CO2) is volatilized immediately after the end of extraction, it does not remain in the product, which is a great advantage as a solvent, and ethanol is a general method. Although the present invention will be described in detail with reference to the following examples, the present invention is not limited to the following examples.

실시 예 >Example>

기장 소재 해조류 가공회사로부터 제공받은 해조류 가공 부산물을 수분함량 10% 이하로 건조하여 초임계 추출기(국내제작, 일신엔지니어링) 반응기내에 30g을 넣고 이하의 방법으로 해조류 가공부산물 중에 잔존하는 클로로필 색소를 추출하였다. 클로로필 색소의 추출 조건은 반응기 내의 온도가 30-45℃, 압력이 1500-2500psi 였다. 이때 클로로필 색소의 추출 및 이취 성분을 효과적이고 신속하게 제거하기 위하여 보조용매를 1-5ml/min으로 조정하였다. 이와 같은 조건으로 처리된 해조류 가공 부산물은 이취가 없는 원형 그대로를 유지하고 있었다.The seaweed processing by-products provided by Gijang-based seaweed processing company were dried to 10% or less of water, and 30 g of the supercritical extractor (domestic production, Ilshin Engineering) reactor was put into the reactor to extract the remaining chlorophyll pigments from the seaweed processing by-products as follows. . The extraction conditions of the chlorophyll pigment | dye were 30-45 degreeC and pressure 1500-1500psi in the reactor. At this time, the co-solvent was adjusted to 1-5ml / min to effectively and quickly remove the chlorophyll pigment extraction and off-flavor components. Seaweed processing by-products treated under these conditions remained intact without odor.

도면 1은 초임계 이산화탄소를 이용하여 클로로필 색소를 추출하여 UV 스펙트럼으로 분석한 결과를 나타내었다. 이때 분석의 조건은 다음과 같다.Figure 1 shows the results of chlorophyll pigment extraction by using a supercritical carbon dioxide analysis by UV spectrum. The conditions of the analysis are as follows.

UV-spectrophotometer 분석조건UV-spectrophotometer analysis conditions

항목Item 조건Condition 제조사manufacturer UVIKON(독일)UVIKON (Germany) Wave lengthWave length 665nm665 nm samplesample 1ml1ml

전술한 바와 같이 본 발명의 방법으로 제조한 해조류 및 갑각류(게, 새우), 극피동물(유령멍게, 불가사리, 성게 등)의 천연 색소는 그 활용도가 매우 높을 것으로 판단된다. 해조류 및 갑각류(게, 새우), 극피동물(유령멍게, 불가사리, 성게 등)로부터 추출한 천연 색소를 화장품 또는 기타 제품에 첨가제로 사용하거나 식품에 천연 색소를 첨가하여 그 제품의 상품성을 높일 수가 있을 것으로 예상되며 해조류 가공 부산물에서 색소와 같이 추출된 해조 추출물도 첨가제로서 사용될 것으로 생각된다.As described above, natural pigments of algae and crustaceans (crabs, shrimps) and echinoderms (ghost sea urchins, starfish, sea urchins, etc.) prepared by the method of the present invention are considered to have high utility. Natural pigments extracted from seaweeds, crustaceans (crabs, shrimps) and echinoderms (ghost sea urchins, starfish, sea urchins, etc.) may be used as additives in cosmetics or other products, or natural pigments may be added to foods to enhance the product's marketability. It is anticipated that seaweed extracts, such as pigments, extracted from seaweed processing by-products will also be used as additives.

Claims (3)

액상 및 분말형태의 해조류 및 갑각류(게, 새우), 극피동물(유령멍게, 불가사리, 성게 등) 가공부산물로부터 초임계 및 아임계 이산화탄소(CO2)와 보조용매인 에탄올을 단독 또는 혼합[1-70%(v/v)]하여 이용하는 것을 특징으로 하는 클로로필 및 카로티노이드 색소 추출 방법.Supercritical and subcritical carbon dioxide (CO2) and co-solvent ethanol, alone or mixed, from liquid and powdered seaweeds and crustaceans (crabs, shrimps), echinoderm (ghost sea urchins, starfish, sea urchins, etc.) [1-70 % (v / v)] chlorophyll and carotenoid pigment extraction method characterized by using. 제 1 항에 있어서, 초임계 및 아임계 이산화탄소에 의한 추출 시 반응기의 온도를 10-80℃, 압력을 50-500bar로 하는 것을 특징으로 하는 클로로필 및 카로티노이드 색소 추출 방법.The method for extracting chlorophyll and carotenoid pigments according to claim 1, wherein the temperature of the reactor during extraction with supercritical and subcritical carbon dioxide is 10-80 ° C., and the pressure is 50-500 bar. 청구항 1과 청구항 2의 방법으로 제공하는 것을 특징으로 하는 해조류 및 갑각류(게, 새우), 극피동물(유령멍게, 불가사리, 성게 등)로부터 추출한 클로로필 및 카로티노이드 색소.Chlorophyll and carotenoid pigments extracted from seaweeds and crustaceans (crabs and shrimps) and echinoderms (ghost sea urchins, starfish, sea urchins, etc.) characterized by the method of claim 1 and 2.
KR1020000035638A 2000-06-27 2000-06-27 Pigment extraction of chlorophyll and carotenoid from seaweed, crustacea and echinoderm using supercritical and subcritical CO2 with entrainer KR20020000660A (en)

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KR20030061118A (en) * 2002-01-10 2003-07-18 주식회사 고센크리텍 Method extracting pigment from seawood,crustacea and echinoderm using supercritical and subcritical fluid
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KR101024491B1 (en) * 2008-12-31 2011-03-31 인성실업(주) The Method of Extracting Lipids from Marine Animals
RU2469732C1 (en) * 2011-07-05 2012-12-20 Федеральное государственное бюджетное учреждение науки Тихоокеанский институт биоорганической химии им. Г.Б. Елякова Дальневосточного отделения Российской академии наук (ТИБОХ ДВО РАН) Method of obtaining carotinoid complex from starfish
KR101351185B1 (en) * 2012-01-17 2014-01-15 인제대학교 산학협력단 Cosmetic compositions for moisturizing effect on the skin comprising lactic acid extract of Chionoeoets japonicus
KR101528299B1 (en) * 2013-09-13 2015-06-11 주식회사 에코마인 Dyeing method for artificial wig using the seaweed pigments thereby
RU2568604C1 (en) * 2014-12-11 2015-11-20 Федеральное государственное бюджетное учреждение науки Тихоокеанский институт биоорганической химии им. Г.Б. Елякова Дальневосточного отделения Российской академии наук (ТИБОХ ДВО РАН) Method for producing 2,3,7-trioxyjuglone (spinochrome b)
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Publication number Priority date Publication date Assignee Title
KR20030061118A (en) * 2002-01-10 2003-07-18 주식회사 고센크리텍 Method extracting pigment from seawood,crustacea and echinoderm using supercritical and subcritical fluid
KR100725999B1 (en) * 2005-09-20 2007-06-11 주식회사 에어화인 Duct for air ventilation system
KR100712446B1 (en) * 2006-03-07 2007-05-02 한우정 Carrying apparatus for a steam kettle
KR100766190B1 (en) * 2006-10-27 2007-10-10 부경대학교 산학협력단 Process for oligosaccharides having various the degree of polymerization using subcritical water
KR100928314B1 (en) * 2007-08-24 2009-11-25 영남제분주식회사 The raw noodles prepared by adding supercritical treatment and salt soluble protein extract of general anchovy
KR101024491B1 (en) * 2008-12-31 2011-03-31 인성실업(주) The Method of Extracting Lipids from Marine Animals
RU2469732C1 (en) * 2011-07-05 2012-12-20 Федеральное государственное бюджетное учреждение науки Тихоокеанский институт биоорганической химии им. Г.Б. Елякова Дальневосточного отделения Российской академии наук (ТИБОХ ДВО РАН) Method of obtaining carotinoid complex from starfish
KR101351185B1 (en) * 2012-01-17 2014-01-15 인제대학교 산학협력단 Cosmetic compositions for moisturizing effect on the skin comprising lactic acid extract of Chionoeoets japonicus
KR101528299B1 (en) * 2013-09-13 2015-06-11 주식회사 에코마인 Dyeing method for artificial wig using the seaweed pigments thereby
RU2568604C1 (en) * 2014-12-11 2015-11-20 Федеральное государственное бюджетное учреждение науки Тихоокеанский институт биоорганической химии им. Г.Б. Елякова Дальневосточного отделения Российской академии наук (ТИБОХ ДВО РАН) Method for producing 2,3,7-trioxyjuglone (spinochrome b)
WO2020009422A1 (en) * 2018-07-06 2020-01-09 주식회사 에이블 Method for preparing chlorophyll-containing extract
CN113648681A (en) * 2021-08-27 2021-11-16 湖南华康生物科技股份有限公司 Method for extracting and separating ginsenoside from Korean ginseng

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