KR920008387B1 - Method for producing oligo-saccharide - Google Patents

Method for producing oligo-saccharide Download PDF

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KR920008387B1
KR920008387B1 KR1019900018895A KR900018895A KR920008387B1 KR 920008387 B1 KR920008387 B1 KR 920008387B1 KR 1019900018895 A KR1019900018895 A KR 1019900018895A KR 900018895 A KR900018895 A KR 900018895A KR 920008387 B1 KR920008387 B1 KR 920008387B1
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soybean
soln
filtrate
oligosaccharide
brix
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KR920009990A (en
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정상철
전영중
현형환
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제일제당 주식회사
김정순
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    • CCHEMISTRY; METALLURGY
    • C13SUGAR INDUSTRY
    • C13BPRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00Purification of sugar juices
    • C13B20/14Purification of sugar juices using ion-exchange materials

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  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

A soybean oligosaccharide is prepd. by (a) diluting soybean whey to 20-50 Brix, (b) ultra-fitrating the diluted soybean whey wih cellulose- or ceramic membrane, (c) decoloring the ultrafiltrated soln., (d) desalting the decolored soln. and djusting the obtd. soln. to pH 7.0 at the same time, and (e) concentrating the soln. to obtain the finalproduct. The obtd. soybean oligosaccharide has a good taste.

Description

대두올리고당의 제조방법Manufacturing method of soy oligosaccharide

본 발명은 식품원료용의 대두단백 생산시 부산물로 나오는 대두훼이(Whey)에 함유된 당류를 순수하게 분리·정제하는 방법에 관한 것이다.The present invention relates to a method for purely separating and purifying sugars contained in soybean whey, which is a by-product when producing soy protein for food ingredients.

대두올리고당은 주성분이 스타키오스(Stachyose), 라피노스(Raffinose) 및 설탕(Sucrose)으로 대두내에 약 5-10% 정도 함유되어 있으며, 유사한 기능을 가진 것으로 알려진 프락토올리고당, 말토올리고당 등에 비해 내산성, 내열성이 우수하며 장내 유용균인 비피듀스(Bifidus)균의 증식효과도 뛰어난 주로 음료 및 기타 식품첨가용 건강감미료로서 각광를 받고 있다. 또한 효소법으로 제조되는 올리고당과 달리 대두올리고당은 천연물에서 추출하는 것으로서 그 안전성면에서도 유사제품에 비해서 높이 평가되고 있다.Soy oligosaccharides are composed of stachyose, raffinose and sugar, containing about 5-10% of soybeans, and are resistant to acid and heat compared to fructooligosaccharides and malto oligosaccharides known to have similar functions. It is excellent and has a proliferation effect of Bifidus, which is an enteric useful bacterium. In addition, unlike oligosaccharides produced by the enzyme method, soy oligosaccharides are extracted from natural products and are highly evaluated in terms of their safety.

종래의 대두올리고당 분리, 정제방법은 일특공개소 59-179064 및 소60-66978에 공지되어 있는데, 대두훼이에 산을 첨가하여 단백질을 침전시키고 그 상등액을 염화칼슘과 수산화칼슘으로 pH를 7-10으로 조정한후 가열공정을 가쳐 잔존 단백질을 제거하는 방법이 제안되어 있다. 그러나 이 제조방법은 가열공정시 아미노산과 당류가 반응하여 당류화합물이 분해되어 수율이 떨어질 뿐만 아니라 공정전체가 복잡하여 공업적 생산에 어려움이 많다. 한편 일특공개소62-155082에 의한 제조방법은 탈지대두를 원료로하여 20-60V/V%의 에탄올이나 메탄올 등을 첨가하여 올리고당을 추출하는 방법이다. 그러나 이 제조방법 역시 원료로 사용되는 탈지대두내에는 다량의 단백질이 포함되어 상대적으로 올리고당 함량이 적은 단점이 있고 다량의 알콜사용으로 인한 공정상의 문제점 및 추출공정시 올리고당외에 색소성분의 추출로 인한 후속공정인 탈색에 어려움이 있다.Conventional soybean oligosaccharide separation and purification methods are known in Japanese Patent Application Publications 59-179064 and 60-66978, and the acid is added to soybean husks to precipitate proteins and the supernatant is adjusted to pH 7-10 with calcium chloride and calcium hydroxide. There has been proposed a method of removing residual protein by a post heating step. However, this manufacturing method is difficult to industrial production because the amino acid and sugar react during the heating process, the sugar compounds are decomposed and the yield is lowered, and the whole process is complicated. On the other hand, the production method according to Japanese Patent Application No. 62-155082 is a method of extracting oligosaccharides by adding 20-60 V / V% of ethanol, methanol, or the like using skim soybean as a raw material. However, this manufacturing method also has a disadvantage that relatively high oligosaccharide content is contained in the degreased soybean, which is used as a raw material. There is difficulty in discoloration which is fair.

따라서, 본 발명자들은 기존의 제조법에서 발생되는 문제점을 해결하고 전체공정을 간편화기키며, 올리고당의 회수율을 높이기 위한 새로운 분리, 정제 방법을 연구하게 되었다.Therefore, the present inventors have studied new separation and purification methods to solve the problems caused by the existing manufacturing method, simplify the whole process, and increase the recovery of oligosaccharides.

본 발명은 농축대두단백 생산시 생기는 부산물인 대두훼이를 원료로 사용하는데 대두훼이는 아직 용도개발이 미진하여 값싸게 얻을 수 있는 원로이며, 폐기성 자원의 재활용 측면에서 그 의미가 있다. 이 대두훼이는 처리하기 적당한 농도인 브릭스(Brix, 중량기준 총고형분농도) 2-50, 바람직하기로는 브릭스 30-40으로 희석시킨 다음 재질이 셀루로즈나 세라킥계열인 한외여과막을 사용하여 원료액중의 단백질이나 기타 고분자 불순물을 제거하는 방법으로서 종래의 방법보다 다음과 같은 장점을 가지고 있다.The present invention uses soybean fry as a raw material, which is a by-product of the production of concentrated soybean protein, and soybean fry is a raw material that can be obtained inexpensively due to insufficient development of its use. The soybean husk was diluted with Brix (weight by weight total solids concentration) 2-50, preferably Brix 30-40 which is a suitable concentration, and then the raw material solution was prepared using an ultrafiltration membrane made of cellulose or ceracic. As a method of removing protein and other polymer impurities in the water, it has the following advantages over the conventional method.

첫째, 종래의 공정이 최소한 3-4단위 공정을 필요로하는 반면에 본 발명에 따른 공정은 한 단계로써 소기의 목적을 달성할 수 있으므로, 공정고성면에서 훨씬 간단하다.First, while the conventional process requires at least 3-4 unit processes, the process according to the present invention is much simpler in terms of process rigidity since it can achieve the desired purpose in one step.

돌째, 본 발명에 따른 공정은 상온에서 작업함으로써 가열시 생기는 당화합물의 분해를 방지하여 줌으로써 올리고당의 회수율을 높일 수 있다. 실제 종래의 방법과 비교해 본 결과 일특소59-179064 및 소60-66978의 방법에 따른 경우 올리고당 의 수율은 74%였고 일특소62-155082의 공정에 의한 올리고당 수율은 82%인 반면 본 발명에 의한 공정을 적용할 경우에는 무려 98%의 올리고당 수율을 얻을 수 있었다.Second, the process according to the present invention can increase the recovery rate of oligosaccharides by preventing the decomposition of the sugar compound generated during heating by working at room temperature. In comparison with the conventional method, the yield of oligosaccharide was 74% and the yield of oligosaccharide was 82% according to the method of 62-155082. When the process was applied, an oligosaccharide yield of 98% was obtained.

셋째, 한외여과분리시 수용성 고분자 불순물이나 일부 색소성분도 동시에 제거되기 때문에 후속공정인 탈염 및 탈색시의 부담이 감소되는 장점을 가지고 있다.Third, since the ultrafiltration separation of the water-soluble polymer impurities and some pigment components are also removed at the same time, the burden of desalting and decolorization, which is a subsequent process, is reduced.

넷째, 종래의 방법이 가열과 냉각을 되풀이 하거나 다량의 알콜회수를 필요로하여 에너지의 소비량이 많으나 본 발명에 따른 공정에는 막분리시 압력을 가하기 위한 펌프에서만 전력을 필요로하므로 에너지 절감의 장점을 가지고 있다.Fourth, the conventional method requires a lot of energy consumption by repeated heating and cooling or a large amount of alcohol recovery, but the process according to the present invention requires the power only in the pump to apply pressure in the membrane separation, the energy saving advantages Have.

다섯째, 종래의 공정에는 모두 고형분의 침전을 위한 원심분리 공정이 포함되어 있어 연속공정화 하기가 어려운 반면 본 발명의 막분리법은 연속공정이므로 운전이 간편한 장점을 가지고 있다.Fifth, all the conventional processes include a centrifugation process for precipitation of solids, so that it is difficult to continuously process the membrane, but the membrane separation method of the present invention has an advantage of easy operation because it is a continuous process.

한외여과막의 재질로는 폴리설폰(Polysulfone), 나일론(Nylon), 개질셀루로즈 및 세라믹(Ceramic)등 여러 종류를 검토하여 본 결과 개질 셀루로즈계열과 세라믹계열이 여과유속면에서 가장 우수함을 알 수 있었다.As a result of examining various types of ultrafiltration membranes such as polysulfone, nylon, modified cellulose and ceramic, the modified cellulose series and ceramic series showed the best in terms of filtration flow rate. there was.

이와 같이 전처리된 원료액은 다이아이온은 PA408,PA406 등의 강염기성 음이온 교환수지탑을 통과시킴으로써 탈색을 하고 강산성 양이온 교환수지인 다이아이온 SK1B나 엠버라이트 1R-120, 듀오라이트 C-20등과 강염기성 음이온 교환수지인 다이아이온 PA408이나 SA20AP 등을 작당한 비율로 혼합한 혼상탑을 통과시킴으로써 탈염을 하고 동시에 pH를 중심으로 조정시켜 줌으로써 정제된 용액을 얻게된다. 이 액을 농축관에서 브릭스 70-76의 시럽상으로 농축한 후 자외선 살균을 실시함으로써 대두올리고당 제품을 제조하게 된다.The pre-treated raw liquid is decolorized by passing through strong base anion exchange resin tower such as PA408, PA406, etc., and strong acid cation exchange resin, such as diion SK1B, Amberlite 1R-120, Duolite C-20, and strong base Deionization is carried out by passing through a mixed column in which aion exchange resins, such as diion PA408 or SA20AP, are mixed at a reasonable ratio, and at the same time, a purified solution is obtained by adjusting the pH. The soy oligosaccharide product is prepared by concentrating this solution in a syrup of Brix 70-76 in a condenser tube and performing ultraviolet sterilization.

이하에서 실시예를 들어 본 발명을 좀 더 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.

[실시예 1]Example 1

대두훼이를 적당히 희석시켜 브릭스 30-50, pH7롤 맞춘 다음 온도 40℃, 여과압력 20psi에서 몇가지 막재질별 여과유속을 측정하여 보았으며, 그 결과는 표 1과 같다.After diluting soybean hues properly, Brix 30-50 was adjusted to pH7, and the filtration flow rates of several membrane materials were measured at a temperature of 40 ° C. and a filtration pressure of 20 psi. The results are shown in Table 1 below.

[표 1]TABLE 1

막재질에 따른 여과유속 비교Comparison of Filtration Flow Rate by Membrane Material

[실시예 2]Example 2

표 2와 같은 조성을 가진 대두훼이를 133g을 원료로하여 브릭스 30-40으로 희석시킨 다음 액의 pH를 7로 맞춘 후 분자량 10,000이상의 물질을 제거할 수 있는 셀루로즈계 재질의 막을 사용하여 온도 30-40℃, 운압력 10psi에서 초기 희석액이 2배 농축될때까지 여액을 회수한 다음 여액의 유속과 같은 속도로 증류수를 공급하여 최종여액의 부피가 초기원료희석액 부피의 1.5배가 되게 여액을 회수하여 원료중 올리고당 98%이상 회수하였다. 최종 여액 부피에 따른 올리고당의 회수율은 표3에서와 같이 초기 원료희석액에 부피의 1.5배 정도의 여액을 회수하는 것이 적당하였다. 이렇게 회수된 여액은 다량의 색소와 염의 및 대두취를 함유하고 있기 때문에 강염기성 음이온 교환수지 다이아이온 PA408을 사용하여 탈색하고 다이아이온 SK1B와 SA20AP를 1 : 1.5-2부피로 충진한 혼상탑을 이용하여 탈염한 다음 농축공정을 거쳐 제품조성이 표4와 같은 무 색, 무취의 시럽상 대두올리고당 46.4g을 얻었다.Dilute soybean whey with the composition as shown in Table 2 to Briggs 30-40 using 133 g of raw material, adjust the pH of the solution to 7, and then use a cellulose-based membrane that can remove substances with a molecular weight of 10,000 or more. The filtrate was recovered until the initial dilution was doubled at 40 ° C and a working pressure of 10 psi, and then distilled water was supplied at the same rate as the flow rate of the filtrate. The filtrate was recovered so that the final filtrate was 1.5 times the volume of the initial raw material diluent. More than 98% of the oligosaccharides were recovered. As for the recovery rate of oligosaccharide according to the final filtrate volume, it was appropriate to recover the filtrate about 1.5 times the volume to the initial raw material diluent as shown in Table 3. Since the recovered filtrate contains a large amount of dye, salt and soybean odor, it is decolorized using a strong base anion exchange resin DIION PA408 and a mixed phase column filled with 1: 1.5-2 volumes of DIION SK1B and SA20AP is used. After desalting, the product composition was obtained 46.4g of colorless and odorless syrup-like soy oligosaccharide as shown in Table 4.

[표 2]TABLE 2

대두훼이 조성표Soybean Huay Composition Table

[표 3]TABLE 3

막분리에서 최종 여액부피에 따른 올리고당의 회수율Recovery of Oligosaccharides by Final Filtrate Volume in Membrane Separation

[표 4]TABLE 4

제품 분석치Product analysis

[실시예 3]Example 3

대두훼이 9.38㎏을 원료로하여 브릭스(Brix) 30-40으로 희석시켜 pH7.0으로 조정한 후 분자량 10,000이상의 물질을 제거할 수 있는 세라믹 재질의 막을 이용하여 온도 40㎏, 압력 3.5Bar로 운전하여 희석액이 2배 농축될때까지 여액을 회수한 다음 최종여액 부피가 실시예 2의 조건과 같이 되게 여액을 회수하여 음이온 교환수지 다이아이온 PA408을 사용하여 탈색한 후 다이아이온 SK1B와 SA20APFMF 1:1.5부피비로 충진한 혼상탑을 이용하여 탈염한 다음 통축공정을 거쳐 시럽상의 대두올리고당 2.3㎏을 얻었다.Using soybean husk as a raw material, diluted to Brix 30-40, adjusted to pH7.0, and then operated at a temperature of 40㎏ and a pressure of 3.5Bar using a ceramic membrane to remove substances with molecular weight of 10,000 or more. The filtrate was recovered until the diluent was concentrated twice, and then the filtrate was recovered to the final filtrate volume as in Example 2 and bleached using anion exchange resin DIION PA408, followed by diion SK1B and SA20APFMF 1: 1.5 volume ratio. After desalting using a packed mixed column, 2.3 kg of syrup-like soy oligosaccharide was obtained through a condensation process.

[실시예 4]Example 4

실시예 3과 같은 재질의 막을 이요하여 온도 30-40℃, 압력 20psi에서 브릭스 30-40의 희석원료액의 pH별 여액의 분리속도를 표5에 표시하였다.Table 5 shows the separation rate of the filtrate for each pH of the diluted raw material of Briggs 30-40 at a temperature of 30-40 ° C. and a pressure of 20 psi using a membrane made of the same material as in Example 3.

[표 5]TABLE 5

희석원료액 pH별 여액 분리속도Separation rate of filtrate by pH

[실시예 5]Example 5

실시예 3과 같은 조건에서 한외여과막 운전압력별 여액의 분리속도를 표6에 표시하였다.Table 6 shows the separation rate of the filtrate by operating pressure of the ultrafiltration membrane under the same conditions as in Example 3.

[표 6]TABLE 6

한외여과 운전압력에 따른 여액 분리속도Filtrate Separation Rate According to Ultrafiltration Operating Pressure

Claims (2)

농축대두단백 생산시 부산물로 나오는 대두훼이(Whey)를 브릭스 20-50으로 희석한 후 한외여과막을 사용하고 고분자 불순물을 제거하는 것을 특징으로 하는 대두올리고당 제조방법.Soybean oligosaccharide manufacturing method characterized in that the dilution of soybean whey (Whey) as a by-product in the production of concentrated soybean protein with Brix 20-50 and using an ultrafiltration membrane to remove polymeric impurities. 제1항에 있어서, 한외여과막의 재질로는 개질셀루로즈계열이나 세라믹계열을 사용하는 것을 특징으로 하는 제조방법.The method according to claim 1, wherein a modified cellulose series or a ceramic series is used as the material of the ultrafiltration membrane.
KR1019900018895A 1990-11-21 1990-11-21 Method for producing oligo-saccharide KR920008387B1 (en)

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