KR20090099939A - Method for manufacturing soysource or soybean paste used chitooligosaccharides - Google Patents

Method for manufacturing soysource or soybean paste used chitooligosaccharides Download PDF

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KR20090099939A
KR20090099939A KR1020080025247A KR20080025247A KR20090099939A KR 20090099939 A KR20090099939 A KR 20090099939A KR 1020080025247 A KR1020080025247 A KR 1020080025247A KR 20080025247 A KR20080025247 A KR 20080025247A KR 20090099939 A KR20090099939 A KR 20090099939A
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solution
chitooligosaccharide
chitosan
soy sauce
soybean paste
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KR1020080025247A
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Korean (ko)
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정특래
허지연
양현필
장지태
황영운
임종민
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정특래
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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
    • A23L27/00Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/50Soya sauce
    • 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
    • A23L11/00Pulses, i.e. fruits of leguminous plants, for production of food; Products from legumes; Preparation or treatment thereof
    • A23L11/50Fermented pulses or legumes; Fermentation of pulses or legumes based on the addition of microorganisms
    • 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
    • A23L2/00Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/70Clarifying or fining of non-alcoholic beverages; Removing unwanted matter
    • A23L2/72Clarifying or fining of non-alcoholic beverages; Removing unwanted matter by filtration
    • A23L2/74Clarifying or fining of non-alcoholic beverages; Removing unwanted matter by filtration using membranes, e.g. osmosis, ultrafiltration
    • 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
    • A23L33/00Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
    • 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
    • A23V2002/00Food compositions, function of food ingredients or processes for food or foodstuffs
    • 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
    • A23V2200/00Function of food ingredients
    • A23V2200/30Foods, ingredients or supplements having a functional effect on health
    • A23V2200/308Foods, ingredients or supplements having a functional effect on health having an effect on cancer prevention
    • 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
    • A23V2200/00Function of food ingredients
    • A23V2200/30Foods, ingredients or supplements having a functional effect on health
    • A23V2200/324Foods, ingredients or supplements having a functional effect on health having an effect on the immune system
    • 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
    • A23V2200/00Function of food ingredients
    • A23V2200/30Foods, ingredients or supplements having a functional effect on health
    • A23V2200/326Foods, ingredients or supplements having a functional effect on health having effect on cardiovascular health
    • 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
    • A23V2200/00Function of food ingredients
    • A23V2200/30Foods, ingredients or supplements having a functional effect on health
    • A23V2200/3262Foods, ingredients or supplements having a functional effect on health having an effect on blood cholesterol
    • 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
    • A23V2250/00Food ingredients
    • A23V2250/28Oligosaccharides
    • 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
    • A23V2300/50Concentrating, enriching or enhancing in functional factors

Abstract

PURPOSE: A method for preparing a soy sauce or soybean paste using chitooligosaccharides is provided to use a chitooligosaccharide solution with molecular weight of 13,000 or less as water. CONSTITUTION: A method for preparing a soy sauce or soybean paste using chitooligosaccharides comprises a step of using a chitooligosaccharide solution as water in a producing process of soy sauces or soybean paste. The average molecular weight of the chitooligosaccharide is 13,000 or less. A method for preparing the chitooligosaccharide solution comprises the following steps of: dissolving chitosan in hydrochloric acid to obtain a chitosan-hydrochloride solution; adding a chitosanase to the chitosan-hydrochloride solution to form a chitosanoligosaccharide; filtering the chitosanoligosaccharide-containing solution to remove unreacted materials and refining with a ultrafiltration membrane; and adding caustic soda to the refined solution to neutralize it and desalting and concentrating the neutralized solution.

Description

체내흡수율이 높은 키토올리고당을 이용한 간장 또는 된장의 제조 방법 {Method for manufacturing soysource or soybean paste used chitooligosaccharides}Method for manufacturing soy sauce or miso using chitooligosaccharide with high body absorption {Method for manufacturing soysource or soybean paste used chitooligosaccharides}

본 발명은 키토올리고당 용액를 이용한 간장 및 된장의 제조방법에 관한 것으로서, 구체적으로 키토산을 효소를 이용하여 분해한 키토올리고당 용액을 한외여과막에 통과시킴으로써 체내 흡수율이 높은 분자량 13,000대 이하의 키토올리고당이 분포된 키토올리고당 용액을 간장 및 된장 제조용 용수로 사용하여, 간장 및 된장을 제조하는 방법에 관한 것이다. The present invention relates to a method for producing soy sauce and soybean paste using a chitooligosaccharide solution. Specifically, a chito oligosaccharide having a molecular weight of 13,000 or less having high molecular weight absorption is distributed by passing a chito oligosaccharide solution decomposed chitosan using an enzyme through an ultrafiltration membrane. The present invention relates to a method for producing soy sauce and miso using chitooligosaccharide solution as water for preparing soy sauce and miso.

키토산은 천연 유래의 염기성 다당류로서 키틴이 주원료이다. 키틴은 게,새우와 같은 갑각류의 껍질,곤충의 표피 및 버섯, 균류의 세포벽에 존재하는 천연고분자물질로서, 산업적으로 이용가능한 양이 연간 2백만톤 정도로 추정되는 셀룰로오즈(cellulose)에 버금가는 막대한 생물자원이다. 키토산은 키틴의 탈아세틸화물로서 수처리시의 응집제나 탈수제로 사용했는데 콜레스테롤 저하작용, 장내세 균에 의한 부패물질 생성억제, 면역증강, 혈압강하, 간기능개선 및 혈당저하, 중금속해독작용, 항균작용 등 그 응용범위가 확대되고 있다. 즉 식품첨가제,토량개량제,식물활성제, 천연물농약,화장품소재,의류 및 섬유소재, 인공피부, 담체로서의 개발이 시도되고 있다 (김세권, 식품공업,1997,140:7-32). Chitosan is a basic polysaccharide derived from nature, chitin is the main raw material. Chitin is a natural polymer in the shell of crustaceans such as crabs and shrimps, the epidermis and mushrooms of fungi, and the fungal cell walls. It is an enormous organism that is equivalent to cellulose, which is estimated to be 2 million tons per year. Resource. Chitosan is a deacetylate of chitin and used as a flocculant or a dehydrating agent in water treatment. The application range is expanding. In other words, the development of food additives, soil improvers, plant actives, natural pesticides, cosmetic materials, clothing and textile materials, artificial skin, carriers have been tried (Kim Se-kwon, Food Industry, 1997, 140: 7-32).

키토산올리고당은 갑각류인 새우나 게 껍질 등에 주로 함유된 키틴질을 조원료의 분쇄, 탈염, 단백질 제거, 불순물 제거 등의 공정에 의해 키틴, 키토산으로 분리· 정제하고, 상기의 분리· 정제된 키틴, 키토산을 방선균 기원의 스트렙토마이세스(Streptomyces SP.) 속에서 분리한 키틴 분해효소나 키토산 분해효소를 이용하여 적당히 분해시켜 제조한다. 키토산은 또한 생체활성 물질로서 여러가지의 생체활성을 나타내는 것으로 알려져 있다. 대표적인 생체활성들은 항암효과, 혈중 콜레스테롤 저하효과, 면역강화효과, 항 당료효과, 상처치료 효과, 항균 효과 등을 들 수 있다. In the chitosan oligosaccharide, chitin, which is mainly contained in shellfish, crab shells, and the like, is separated and purified into chitin and chitosan by crushing crude raw materials, desalting, removing proteins, and removing impurities, and separating and purifying chitin and chitosan. Was prepared by appropriately decomposing the chitin or chitosan degrading enzyme isolated from Streptomyces SP. Chitosan is also known to exhibit a variety of bioactivity as a bioactive material. Representative biological activities include anti-cancer effect, blood cholesterol lowering effect, immune enhancing effect, anti-sugar effect, wound healing effect, antibacterial effect.

또한, 키토산을 가수분해하여 키토산올리고당을 제조하는 방법으로는 화학적 방법과 생물학적 방법이 있다. 화학적 분해 방법인 염산 가수분해 방법은 식품 또는 식품 원료의 제조방법으로는 적당하지 않다고 하여 현재 한국식품의약품안전청(KFDA)에서 그 방법의 사용을 규제하고 있기 때문에, 대부분 생물학적방법으로 제조한 키토산올리고당이 시중에 시판되고 있다. 그러나, 생물학적방법으로 제조한 키토산올리고당은 대부분이 분해과정에서 사용한 염을 제거하지 않은 상태에서 염형태의 키토산올리고당으로 시판되고 있는 현실이다. 그러나, 이러한 공정으로 제조된 키토산은 그 분자량이 수십만 내지 수백만의 고분자 물질이기 때문에. 체내 에서의 흡수율이 떨어지는 단점이 있다. In addition, there are a chemical method and a biological method as a method for producing chitosan oligosaccharides by hydrolyzing chitosan. Hydrochloric acid hydrolysis, which is a chemical decomposition method, is not suitable as a food or food ingredient manufacturing method, and the KFDA currently regulates its use. Therefore, chitosan oligosaccharides manufactured by biological methods are mostly used. It is commercially available. However, most of chitosan oligosaccharides prepared by biological methods are commercially available as salt-type chitosan oligosaccharides without removing the salts used in the decomposition process. However, because chitosan produced by this process has a molecular weight of several hundred thousand to millions of polymers. There is a disadvantage that the absorption rate in the body falls.

한편, 종래의 간장 및 된장은 순전히 메주와 소금물로만 제조하기 때문에 고혈압을 유발하는 것으로 알려진 염소 이온의 함량이 높다. 키토산은 염소와 반응하여 이를 흡수 배출하여 혈중 농도를 감소시킴으로써, 그 활성화에 염소 이온을 필요로 하는 혈압조절의 효소인 ACE의 활성을 저하시켜 결과적으로 혈압을 감소시키게 되므로 고혈압에 매우 유용하며, 키토산에 의해 혈중 염소농도가 감소됨으로 인하여 인슐린 과다 분비가 억제되어 비만에 의한 혈압 상승도 억제되는 효과가 있다. On the other hand, conventional soy sauce and soybean paste has a high content of chlorine ions that are known to cause high blood pressure because it is made only purely meju and brine. Chitosan is very useful for hypertension because it reacts with chlorine, absorbs and releases it, and reduces blood concentration, thereby lowering the activity of ACE, an enzyme of blood pressure control that requires chlorine ions for its activation, and thus reducing blood pressure. By reducing the blood chlorine concentration by inhibiting the excessive secretion of insulin has the effect of suppressing the increase in blood pressure due to obesity.

이에 본 발명자들은 상기 종래의 문제점을 해결하기 위하여 광범위한 연구를 수행한 결과, 본 발명에 따라 제조된 생체흡수율이 높은 키토올리고당을 간장과 된장 제조에 이용함으로써 면역력 증간작용 및 세포부활작용에 의한 항암활성, 항균활성, 체내 콜레스테롤 개선작용 및 고혈압 억제 작용 등 다양한 생리활성을 가질 수 있음을 확인하여 본 발명을 완성하였다. Therefore, the present inventors have conducted extensive research to solve the above problems, and as a result, the anti-cancer activity due to the increase in immunity and cell reactivity by using chitooligosaccharide having high bioabsorption rate prepared according to the present invention for the preparation of soy and miso The present invention was completed by confirming that it can have various physiological activities such as antibacterial activity, body cholesterol improving action and hypertension suppressing action.

종래의 비수용성이고 체내 흡수율이 떨어지는 등 키토산의 문제점을 극복하고, 체내 흡수율이 높은 키토산을 물에 용해시킨 키토올리고당 수용액을 이용한 간장 및 된장의 제조 방법을 제공하고자 한다. To overcome the problems of the conventional chitosan, such as water-insoluble and inferior in the body absorption rate, and to provide a method for producing soy and miso using a chitooligosaccharide aqueous solution in which chitosan with high body absorption rate is dissolved in water.

본 발명은 체내 흡수율이 높은 키토올리고당 용액을 간장 또는 된장 제조용 용수로 사용하는 것을 특징으로 하는 간장 또는 된장의 제조 방법에 관한 것이다.The present invention relates to a method for producing soy sauce or soybean paste, characterized by using a chitooligosaccharide solution having high absorption in the body as soy sauce or soybean paste preparation water.

본 발명은 분자량 13,000 이하의 키토올리고당 용액을 제조하여, 이를 간장 제조시의 용수로 사용함으로써, 키토올리고당의 체내 흡수율을 높이고, 면역력 증강 작용 및 항암 활성, 체내 콜레스테롤 개선작용 및 고혈압 억제 작용 등 다양한 생리활성 기능을 가지는 간장 및 된장을 제조할 수 있다. The present invention prepares a solution of chitooligosaccharides having a molecular weight of 13,000 or less, and uses it as water for the preparation of soy sauce, thereby increasing the absorption rate of chitooligosaccharides in the body, enhancing the immune system and anti-cancer activity, improving cholesterol in the body, and inhibiting hypertension. Soy sauce and miso can be prepared.

본 발명은 체내 흡수율이 높은 키토올리고당 용액을 간장 또는 된장 제조용 용수로 사용하는 것을 특징으로 하는 간장 또는 된장의 제조 방법에 관한 것이다. 이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention relates to a method for producing soy sauce or soybean paste, characterized by using a chitooligosaccharide solution having high absorption in the body as soy sauce or soybean paste preparation water. The present invention will be described in more detail as follows.

본 발명은 간장 또는 된장 제조용 용수로서 체내 흡수율이 높은 분자량 13,000 이하인 키토올리고당을 용해시킨 용액을 제공한다. 상기 키토올리고당의 분자량은 1,000 내지 13,000 인 것이 바람직하며, 3,000 내지 8,000 인 것이 더욱 바람직하다.The present invention provides a solution in which chitooligosaccharides having a molecular weight of 13,000 or less having a high water absorption in soy sauce or soybean paste manufacturing water are dissolved. The molecular weight of the chitooligosaccharide is preferably 1,000 to 13,000, more preferably 3,000 to 8,000.

분자량이 13,000을 초과하면 체내흡수율이 높지 않으며, 분자량이 1000 미만일 경우, 흡수는 용이하지만 기질대 효소비율을 높여 제조하여야 하고 최종단계에서 분자량이 1,000인 막으로 여과하여야 하므로 생산단가가 올라가는 문제점이 있다. If the molecular weight exceeds 13,000, the absorption rate in the body is not high, and if the molecular weight is less than 1000, there is a problem in that the production cost increases because the absorption is easy but the substrate-to-enzyme ratio must be increased and the membrane must be filtered with a molecular weight of 1,000 at the final stage. .

본 발명의 일 실시예에 따르면, 키토올리고당의 제조 단계는According to one embodiment of the invention, the step of preparing chitooligosaccharides

(1) 키토산을 용매에 용해하여 키토산 용액을 제조하는 단계;(1) dissolving chitosan in a solvent to prepare a chitosan solution;

(2) 키토산 용액에 키토산분해효소를 첨가하여 키토올리고당을 제조하는 단계;(2) preparing chitooligosaccharide by adding chitosanase to chitosan solution;

(3) 키토올리고당 함유 용액을 여과하여 미반응 물질을 제거하고 한외여과막을 이용하여 정제하는 단계; 및 (3) filtering the chitooligosaccharide-containing solution to remove unreacted material and purifying by using an ultrafiltration membrane; And

(4) 정제된 용액을 중화하고 나노 여과막으로 여과하여 탈염 및 농축하는 단계(4) neutralizing the purified solution and filtering and desalting and concentrating with a nano filtration membrane

를 포함할 수 있다.It may include.

상기 (1) 단계에 있어서, 용매는 염산 등의 산이 사용될 수 있으며, 키토산은 공지된 통상의 키토산을 사용할 수 있다. 바람직하게는 키토산을 염산으로 용 해하여 키토산 염산염을 제조할 수 있다. 키토산의 점도는 7~15cps 인 것이 바람직하며, 더욱 바람직하게는 10cps 이고, 키토산의 농도는 4~6 %(w/v) 인 것이 바람직하며, 5% 가 더욱 바람직하다. 용매인 염산의 농도는 0.2~0.3M 가 바람직하며, 0.23M 가 가장 바람직하다. 그러나, 키토산 염산염 용액의 pH가 5.0~5.5, 더욱 바람직하게는 5.0 정도가 되도록 분해조건을 조절하기만 하면, 이에 한정되지 않는다.In the step (1), an acid such as hydrochloric acid may be used as the solvent, and chitosan may be a known conventional chitosan. Preferably, chitosan hydrochloride can be prepared by dissolving chitosan as hydrochloric acid. The viscosity of chitosan is preferably 7 to 15 cps, more preferably 10 cps, the concentration of chitosan is preferably 4 to 6% (w / v), more preferably 5%. The concentration of hydrochloric acid as a solvent is preferably 0.2 to 0.3 M, most preferably 0.23 M. However, as long as the decomposition conditions are adjusted such that the pH of the chitosan hydrochloride solution is 5.0 to 5.5, more preferably about 5.0, the present invention is not limited thereto.

상기 (2) 단계에 있어서, 바람직한 키토산 분해효소로는 Bacillus sp. 미생물 유래의 endo-type chitosanase등이 있다. 키토산 분해효소를 5% 키토산 용액에 대해 대략 효소 10단위, 또는 동일한 조건하에서 키토산분해효소를 기질 대 효소비율을 약 1:2 비율로 첨가하여 키토올리고당을 제조한다. 반응온도는 40℃, 반응시간은 약 36시간 정도가 바람직하다. In the step (2), preferred chitosan degrading enzyme Bacillus sp. Endo-type chitosanases derived from microorganisms. Chitooligosaccharides are prepared by adding chitosanase to approximately 5 units of a 5% chitosan solution, or chitosanase at about a 1: 2 ratio of substrate to enzyme ratio under the same conditions. The reaction temperature is preferably 40 ° C. and the reaction time is about 36 hours.

상기 (3) 단계에 있어서, 여과시의 필터는 prefilter 및 Zeta filter 등을 사용할 수 있다. 상기 필터의 기공 사이즈는 prefilter의 경우 1 ㎛, Zeta filter는 0.7 ㎛ 인 것이 가장 바람직하다. 상기 필터로 단계적으로 여과하여 미반응물질을 제거하고 한외여과막(ultrafiltration membrane)을 이용하여 키토올리고산 용액을 정제한다. 한외여과막은 막의 구멍 통과하는 분자량 크기인 분자량한계범위(MWCO; Molecular weight cut-off)에 의하여 막의 규격이 결정되는데, 바람직하게는 MWCO가 약 30,000 정도인 한외여과막을 사용하는 것이 바람직하다. 한외여과막을 이용한 정제 단계는 1회 또는 필요에 따라 수회 반복 실시될 수 있다. 반복하여 정제하는 과정에서 상기 한외여과막의 막 사이즈를 다르게 조절함으로써 키토올리고당을 원하는 분자량으로 얻을 수 있다.In the step (3), the filter at the time of filtration may be used a prefilter, Zeta filter and the like. The pore size of the filter is most preferably 1 μm for the prefilter and 0.7 μm for the Zeta filter. Filtering step by step to remove the unreacted material and purified chitooligoic acid solution using an ultrafiltration membrane (ultrafiltration membrane). The size of the membrane is determined by the molecular weight limit (MWCO; Molecular weight cut-off), which is the size of the molecular weight passing through the pores of the membrane. Preferably, it is preferable to use an ultrafiltration membrane having an MWCO of about 30,000. The purification step using the ultrafiltration membrane may be performed once or several times as necessary. By repeatedly adjusting the membrane size of the ultrafiltration membrane in the process of purification can be obtained a chitooligosaccharide at a desired molecular weight.

상기 (4) 단계에 있어서, 용액의 중화를 위하여 염기성 용액을 사용하는 것이 가능하며, 가성소다 용액을 사용하는 것이 가장 바람직하다. 중화된 용액은 나노여과막으로 농축하고, 정제수를 반복 첨가하면서 탈염한다. 상기 나노여과막의 MWCO는 300 정도가 가장 바람직하다. 나노여과막을 이용한 탈염은 필요에 따라 반복실시하는 것이 바람직하다. 탈염된 용액은 20-25 BriX까지 농축하여 고온 단시간 살균법으로 살균하고 건조하여 고순도의 키토올리고당을 제조할 수 있다.In step (4), it is possible to use a basic solution for the neutralization of the solution, and most preferably a caustic soda solution. The neutralized solution is concentrated with a nanofiltration membrane and desalted with repeated addition of purified water. MWCO of the nanofiltration membrane is most preferably about 300. It is preferable to repeat desalination using a nanofiltration membrane as needed. The desalted solution can be concentrated to 20-25 BriX, sterilized by high temperature and short time sterilization, and dried to produce high purity chitooligosaccharides.

상기 방법으로 분자량이 13,000 이하이므로 체내 흡수율이 높은 고분자 수용성 키토산을 제조할 수 있다. 이러한 키토올리고당은 체내 흡수율을 향상시켜 키토산의 효능이 증진될 수 있도록 할 뿐 아니라, 체내의 지방산의 흡수를 저해시켜 중성 지방의 양을 조절하고, 혈중 콜레스테롤 수치를 낮추는 작용을 한다. 또한 체내에 흡수되어 면역체계를 활성화시켜 신체의 면역력을 증가시키는 면역력 증강기능, 미생물의 세포막과 결합하여 미생물의 증식을 억제함으로써 항균작용을 나타내는 항균기능 등에 매우 탁월한 효과를 가짐이 밝혀졌다Since the molecular weight is 13,000 or less by the above method, a high molecular weight water-soluble chitosan in the body can be produced. These chitooligosaccharides improve the absorption rate in the body to enhance the efficacy of chitosan, as well as inhibit the absorption of fatty acids in the body to regulate the amount of triglycerides, and lowers blood cholesterol levels. In addition, it has been found that it has an excellent effect on the enhancement of immunity to increase the body's immunity by activating the immune system and to inhibit the proliferation of microorganisms by inhibiting the proliferation of microorganisms.

본 발명은 상기 방법으로 제조된 키토올리고당 수용액을 간장 또는 된장의 제조용 용수로 사용한 간장 또는 된장의 제조 방법을 제공한다.The present invention provides a method for producing soy sauce or miso using the chitooligosaccharide aqueous solution prepared by the above method as water for preparing soy sauce or miso.

종래의 키토산은 비수용성이므로 장류 등의 식품 제조시, 제조용 용수로서 사용될 수 없고, 분말로서 첨가하였다. 따라서, 최종 생산된 식품의 키토산의 체내흡수율이 낮았다. 그러나, 본 발명에 따른 키토올리고당은 물에 쉽게 용해되어 키토올리고당 수용액을 제조하는 것이 가능하므로, 간장 또는 된장의 제조시 제조용 용수로 사용함으로써, 최종 생산된 식품에 함유된 키토산의 체내 흡수율을 높일 수 있다.Since conventional chitosan is water-insoluble, it cannot be used as preparation water for preparing foods such as enteric foods, and is added as powder. Therefore, the absorption rate of chitosan in the final produced food was low. However, since the chitooligosaccharide according to the present invention can be easily dissolved in water to prepare an aqueous solution of chitooligosaccharide, the absorption rate of the chitosan contained in the final food product can be increased by using it as a preparation water during the preparation of soy or miso. .

본 발명에 따른 키토올리고당 수용액을 이용한 간장 또는 된장의 제조 방법은 당업자에게 공지된 통상의 방법을 포함한다.Methods for preparing soy sauce or miso using the aqueous solution of chitooligosaccharide according to the present invention include conventional methods known to those skilled in the art.

[실시예]EXAMPLE

하기의 실시예는 본 발명의 내용을 구체적으로 설명하기 위한 것이며, 이에 의하여 본 발명의 범위가 결코 한정되어 해석될 수 없다.The following examples are intended to specifically describe the contents of the present invention, whereby the scope of the present invention is never limited and can be interpreted.

실시예Example 1 One

교반기가 장착된 효소반응기에 정제수 2,800L, 점도 10cps인 키토산(주식회사 태훈바이오) 150 kg 을 넣고 반응기 온도를 40 ℃를 유지하면서 2시간 정도 교반속도 150 rpm 으로 교반하여 팽윤시킨 후 염산 60 L를 첨가하여 키토산을 용해하였다. 키토산 용액의 pH가 5.0 부근인 것을 확인하고 키토산분해효소인 endo-type chitosanase ((주)아미코젠) 300,000units (8.571g, 효소활성; 35,000 units/g)을 정제수 500ml에 용해하여 첨가하고 30분 정도 방치한 후 교반속도를 120 rpm 으로 낮추어 36시간 동안 가수분해시켰다. 상기 용액을 20 inch prifilter(1 ㎛), Zeta filter(0.7 ㎛)의 순으로 여과하여 미반응물질을 제거하고 500L/hr 유출속도의 한외여과막(ultrafiltration membrane; MWCO 30,000, 삼호 S&T)으로 정제하였다. 정제dodr을 1.5 톤/시간 의 유출속도를 가진 나노여과막(MWCO 300)으로 용액이 15BX가 될 때까지 농축하고 1M 가성소다용액을 pH 7.2가 될 때까지 첨가한 후 막(MWCO 300)으로 농축하면서 막 통과액의 전기전도도가 0.1ms/cm이하일 때까지 정제수를 반복 첨가하면서 탈염한 후 농축하여 고온단시간살균법으로 살균하고 건조(Spray Dryer)하여 약 142 kg (95% 수율)로 고순도 키토올리고당을 얻었다. 150 kg of chitosan (Tahoon Bio Co., Ltd.) with purified water 2,800L and viscosity of 10cps was added to the enzyme reactor equipped with a stirrer, followed by swelling at 150 rpm for 2 hours while maintaining the reactor temperature at 40 ° C. To dissolve chitosan. Check that the pH of the chitosan solution is around 5.0, and add 300,000 units (8.571g, enzyme activity; 35,000 units / g) of chitosanase (Ami-Kogen) in 500 ml of purified water After standing about, the stirring speed was lowered to 120 rpm and hydrolyzed for 36 hours. The solution was filtered in the order of 20 inch prifilter (1 μm), Zeta filter (0.7 μm) to remove unreacted material and purified by ultrafiltration membrane (MWCO 30,000, Samho S & T) at 500 L / hr flow rate. The purified dodr was condensed with a nanofiltration membrane (MWCO 300) with an outflow rate of 1.5 ton / hour until the solution reached 15BX, 1M caustic soda solution was added until pH 7.2, and then condensed with the membrane (MWCO 300). Purified water was repeatedly added until the electrical conductivity of the membrane passing liquid was 0.1 ms / cm or less, then desalted, concentrated, sterilized by high temperature and short time sterilization, and dried (Spray Dryer) to obtain high purity chitooligosaccharide at about 142 kg (95% yield). Got it.

<분자량 측정><Molecular weight measurement>

상기 제조된 고순도 키토올리고당의 평균분자량(Average Molecular Weight, Mw)은 점도법 원리에 의한 자동분자량 측정기(Viscotek corp. Model Y-500)로 측정하였다. 0.1M AcOH-0.2M NaCl 혼합용매에 1.2g/dL~0.04g/dL의 용액을 제조하여 분석한 결과, 제조된 키토산 올리고당의 평균분자량(Mw)은 5,600이었다.Average Molecular Weight (Mw) of the prepared high purity chitooligosaccharide was measured by an automatic molecular weight measuring instrument (Viscotek corp. Model Y-500) based on the viscosity method principle. As a result of preparing and analyzing a solution of 1.2 g / dL to 0.04 g / dL in a 0.1 M AcOH-0.2 M NaCl mixed solvent, the average molecular weight (Mw) of the prepared chitosan oligosaccharide was 5,600.

제조예Production Example 1 One

실시예 1의 방법에 따라 제조된 키토올리고당 용액을 간장의 용수로 사용하여 간수를 제거한 천일염으로 17 내지 20 중량% 를 용해한 후 메주를 17 내지 25중 량% 띄워 45 내지 60일 동안 발효 후 고형분과 액상을 분리하여 액상을 다시 60일 이상 숙성하여 간장을 제조하였다. The chitooligosaccharide solution prepared according to the method of Example 1 was used as soy water to dissolve 17 to 20% by weight with sun salt, which was then removed. Soy sauce was prepared by further aging the liquid phase for 60 days or more.

제조예Production Example 2 2

실시예 1의 방법에 따라 제조된 키토올리고당 분말을 1~5 중량 %로 정제수에 용해하여 제조한 키토올리고당 용액을 간장의 용수로 사용하여 간수를 제거한 천일염으로 17 내지 20 중량% 로 용해한 후 메주를 17 내지 25중량% 띄워 45 내지 60일 동안 발효 후 고형분과 액상을 분리하여 액상을 다시 60일 이상 숙성하여 간장을 제조하였다.The chitooligosaccharide powder prepared according to the method of Example 1 was dissolved in purified water at 1 to 5% by weight in soy water, and the soy water was used to dissolve the salt in 17 to 20% by weight with natural salt. After fermentation for 25 to 25% by weight, the solids and the liquid were separated after fermentation for 45 to 60 days, and the liquid phase was further aged for 60 days to prepare soy sauce.

제조예Production Example 3 3

실시예 1의 방법에 따라 제조된 키토올리고당 용액을 간장의 용수로 사용하여 간수를 제거한 천일염으로 17 내지 20 중량%를 용해한 후 메주를 17 내지 25중량% 띄워 45 내지 60일 동안 발효 후 고형분과 액상을 분리하여 고형분을 다시 6개월 이상 숙성하여 된장을 제조하였다. The chitooligosaccharide solution prepared according to the method of Example 1 was used as soy water to dissolve 17 to 20% by weight with sun salt from which the water was removed, followed by 17 to 25% by weight of meju, followed by fermentation for 45 to 60 days. After separation, the solids were aged for 6 months or longer to prepare miso.

제조예Production Example 4 4

실시예 1의 방법에 따라 제조된 키토올리고당분말을 1~5 중량 %로 정제수에 용해하여 제조한 키토올리고당 용액을 간장의 용수로 사용하여 간수를 제거한 천일염으로 17 내지 20 중량%를 용해한 후 메주를 17 내지 25 중량% 띄워 45 내지 60일 동안 발효 후 고형분과 액상을 분리하여 고형분을 다시 6개월 이상 숙성하여 간장을 제조하였다.The chitooligosaccharide powder prepared according to the method of Example 1 was dissolved in purified water at 1 to 5% by weight in soy water, and then 17 to 20% by weight of natural salt was removed using natural salt to remove the meju. Flour to 25 to 25% by weight, after the fermentation for 45 to 60 days to separate the solids and liquid phase was aged for more than 6 months to prepare soy sauce.

Claims (3)

체내 흡수율이 높은 키토올리고당 용액을 간장 또는 된장 제조용 용수로 사용하는 것을 특징으로 하는 간장 또는 된장의 제조 방법.A method for producing soy sauce or soybean paste, characterized by using a chitooligosaccharide solution having high absorption in the body as soy sauce or soybean paste preparation water. 제 1항에 있어서, 키토올리고당의 평균 분자량은 13,000 이하인 것을 특징으로 하는 간장 또는 된장의 제조 방법.The method for producing soy sauce or miso according to claim 1, wherein the average molecular weight of chitooligosaccharide is 13,000 or less. 제 1항에 있어서, 키토올리고당 용액은 The method of claim 1, wherein the chitooligosaccharide solution (1) 키토산을 염산으로 용해하여 키토산염산염 용액을 제조하는 단계;(1) dissolving chitosan with hydrochloric acid to prepare a chitoate solution; (2) 키토산염산염 용액에 키토산분해효소를 첨가하여 키토올리고당을 제조하는 단계;(2) preparing chito-oligosaccharides by adding chitosanase to chitosan solution; (3) 키토올리고당 함유 용액을 필터로 여과하여 미반응 물질을 제거하고 한외여과막을 이용하여 정제하는 단계; 및 (3) filtering the chitooligosaccharide-containing solution with a filter to remove unreacted substances and purifying by using an ultrafiltration membrane; And (4) 정제된 용액에 가성소다 용액을 첨가하여 중화하고 나노 여과막으로 탈염 및 농축하는 단계(4) neutralizing by adding caustic soda solution to the purified solution, desalting and concentrating with a nanofiltration membrane 로 제조되는 것을 특징으로 하는 간장 또는 된장의 제조 방법.Method for producing soy sauce or miso characterized in that it is manufactured with.
KR1020080025247A 2008-03-19 2008-03-19 Method for manufacturing soysource or soybean paste used chitooligosaccharides KR20090099939A (en)

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KR20180043598A (en) 2016-10-20 2018-04-30 대우조선해양 주식회사 Welding robot including flexible joint
KR20230045888A (en) 2021-09-29 2023-04-05 농업회사법인 안동제비원전통식품(주) Manufacturing Method for Soysauce Containing Hemp seed and Soysauce Thereof

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WO2011049319A2 (en) 2009-10-20 2011-04-28 알피니언메디칼시스템 주식회사 Method and apparatus for manufacturing a passive component for an acoustic transducer
KR20180043598A (en) 2016-10-20 2018-04-30 대우조선해양 주식회사 Welding robot including flexible joint
KR20230045888A (en) 2021-09-29 2023-04-05 농업회사법인 안동제비원전통식품(주) Manufacturing Method for Soysauce Containing Hemp seed and Soysauce Thereof

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