JPH0614880B2 - Method for producing high-purity maltose - Google Patents
Method for producing high-purity maltoseInfo
- Publication number
- JPH0614880B2 JPH0614880B2 JP1102186A JP10218689A JPH0614880B2 JP H0614880 B2 JPH0614880 B2 JP H0614880B2 JP 1102186 A JP1102186 A JP 1102186A JP 10218689 A JP10218689 A JP 10218689A JP H0614880 B2 JPH0614880 B2 JP H0614880B2
- Authority
- JP
- Japan
- Prior art keywords
- maltose
- content
- fraction
- purity
- sugar solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 title claims description 120
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 title claims description 120
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000011347 resin Substances 0.000 claims description 35
- 229920005989 resin Polymers 0.000 claims description 35
- 229920002472 Starch Polymers 0.000 claims description 26
- 235000019698 starch Nutrition 0.000 claims description 26
- 239000008107 starch Substances 0.000 claims description 26
- 239000008103 glucose Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 12
- 239000003729 cation exchange resin Substances 0.000 claims description 12
- 229920001353 Dextrin Polymers 0.000 claims description 10
- 239000004375 Dextrin Substances 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 235000019425 dextrin Nutrition 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 45
- 238000000034 method Methods 0.000 description 17
- 238000005194 fractionation Methods 0.000 description 16
- 239000013078 crystal Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000003957 anion exchange resin Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 4
- 229940088598 enzyme Drugs 0.000 description 4
- 150000002692 maltoses Chemical class 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 235000012907 honey Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 Alkali metal salt Chemical class 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 108010019077 beta-Amylase Proteins 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 210000002196 fr. b Anatomy 0.000 description 2
- 210000000540 fraction c Anatomy 0.000 description 2
- 229940079826 hydrogen sulfite Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- 208000007976 Ketosis Diseases 0.000 description 1
- GXCLVBGFBYZDAG-UHFFFAOYSA-N N-[2-(1H-indol-3-yl)ethyl]-N-methylprop-2-en-1-amine Chemical compound CN(CCC1=CNC2=C1C=CC=C2)CC=C GXCLVBGFBYZDAG-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001323 aldoses Chemical class 0.000 description 1
- 108090000637 alpha-Amylases Proteins 0.000 description 1
- 102000004139 alpha-Amylases Human genes 0.000 description 1
- 229940024171 alpha-amylase Drugs 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 210000003918 fraction a Anatomy 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002584 ketoses Chemical class 0.000 description 1
- 235000010449 maltitol Nutrition 0.000 description 1
- 239000000845 maltitol Substances 0.000 description 1
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 description 1
- 229940035436 maltitol Drugs 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
Landscapes
- Saccharide Compounds (AREA)
Description
【発明の詳細な説明】 本発明は、高純度マルトースの製造方法に関する。The present invention relates to a method for producing high-purity maltose.
近年、マルトースの持つ長所が次々と見いだされ、その
用途は飲食物、医薬などに急速に拡大されてきた。In recent years, the advantages of maltose have been found one after another, and the uses thereof have been rapidly expanded to foods and drinks, medicines and the like.
それにつれて、高純度マルトースに対する要望は非常に
高まってきた。Along with this, the demand for high-purity maltose has greatly increased.
従来、マルトースは、液化澱粉に麦芽酵素を作用させ
て、マルトース含有量が固形物当り約40〜50W/W
%(以下、特にことわらない限り、含有量%は、固形物
当りW/W%を意味する)の澱粉糖化物として供給され
てきた。近年になって、澱粉糖化方法の研究開発が進
み、例えば、澱粉枝切酵素とβ−アミラーゼとの併用に
より澱粉からマルトース含有量50%以上の澱粉糖化物
も比較的容易に得られるようになってきた。Conventionally, maltose has a maltose content of about 40 to 50 W / W per solid by allowing malt enzyme to act on liquefied starch.
% (Hereinafter, unless otherwise specified, the content% means W / W% per solid matter), has been supplied as a starch saccharified product. In recent years, research and development of a starch saccharification method have progressed, and, for example, a starch saccharification product having a maltose content of 50% or more can be relatively easily obtained from starch by the combined use of starch debranching enzyme and β-amylase. Came.
しかし、これらの澱粉糖化方法によっても、澱粉からマ
ルトース含有量90%以上の高純度マルトースを直接製
造することは経済的、技術的にかなり困難がともなって
いる。However, even by these saccharification methods of starch, it is economically and technically considerably difficult to directly produce high-purity maltose having a maltose content of 90% or more from starch.
最近、高純度マルトースを製造する方法として、マルト
ースを含有する澱粉糖液をアニオン交換樹脂を充填した
カラムに通液する方法が開示されている。Recently, as a method for producing high-purity maltose, a method has been disclosed in which a starch sugar solution containing maltose is passed through a column packed with an anion exchange resin.
例えば、昭和52年特許出願公告第46290号公報に
は、澱粉から主としてマルトースとデキストリンとから
なるマルトース含有量約65%の澱粉糖液を製造し、こ
の糖液をOH型アニオン交換樹脂に通液し、マルトース
を選択的に吸着させ、デキストリンを分別除去する方法
により高純度マルトースを得ようとしている。しかしな
がら、この方法では、マルトースをOH型イオン交換樹
脂に吸着させるため、その処理量が少ないだけでなく、
異性化を防ぐために、できるだけ低温望ましくは20℃
以下で通液しなければならず、糖液の粘度上昇及び微生
物汚染を受け易く、工業的に実施することは極めて困難
である。For example, in Japanese Patent Application Publication No. 46290 of 1977, a starch sugar solution having a maltose content of about 65% mainly composed of maltose and dextrin is produced from starch, and the sugar solution is passed through an OH type anion exchange resin. However, it is attempting to obtain high-purity maltose by a method of selectively adsorbing maltose and fractionally removing dextrin. However, in this method, since maltose is adsorbed on the OH-type ion exchange resin, not only the treatment amount is small, but also
As low as possible, preferably 20 ° C to prevent isomerization
The liquid must be passed through the following, and the sugar solution is liable to increase in viscosity and microbial contamination, and it is extremely difficult to carry out industrially.
また、昭和54年特許出願公告第20579号公報に
は、マルトースとグルコースとを含有する澱粉糖液を、
亜硫酸型または亜硫酸水素型アニオン交換樹脂に通液
し、マルトースとグルコースとを分別して高純度マルト
ースを得ようとしている。しかしながら、この方法は、
アニオン交換樹脂から亜硫酸または亜硫酸水素がはずれ
やすく、高純度マルトースの大量生産方法としては不適
当である。Further, Japanese Patent Application Publication No. 20579 of 1979 discloses a starch sugar solution containing maltose and glucose,
The solution is passed through a sulfite type or hydrogen sulfite type anion exchange resin to separate maltose and glucose to obtain high-purity maltose. However, this method
Sulfurous acid or hydrogen sulfite is easily released from the anion exchange resin, which is unsuitable as a mass production method of high-purity maltose.
本発明者らは、上述のような欠点を有するアニオン交換
樹脂を避け、カチオン交換樹脂、なかでもアルカリ金属
型またはアルカリ土類金属型強酸性カチオン交換樹脂を
用いる高純度マルトースの製造方法を鋭意研究した。The present inventors have diligently studied a method for producing high-purity maltose using a cation exchange resin, especially an alkali metal type or alkaline earth metal type strongly acidic cation exchange resin, while avoiding the anion exchange resin having the above-mentioned drawbacks. did.
その結果、原料の澱粉糖液(以下、単に原糖液と略称す
る。)をマルトース含有量70%以上の澱粉糖液とし、
これをアルカリ金属型またはアルカリ土類金属型強酸性
カチオン交換樹脂を樹脂層の全長を7m以上に充填した
カラムに流し、次いで水で溶出し、デキストリン高含有
画分、デキストリン・マルトース高含有画分、マルトー
ス高含有画分、マルトース・グルコース高含有画分及び
グルコース高含有画分の順になるように複数の画分、通
常5乃至100、望ましくは5乃至30画分に分画し
て、このうちマルトース高含有画分を採取することによ
り、容易に高純度マルトースが製造されることを見いだ
した。As a result, the raw starch sugar solution (hereinafter simply referred to as the raw sugar solution) was changed to a starch sugar solution having a maltose content of 70% or more,
This is flown through a column in which an alkali metal type or alkaline earth metal type strongly acidic cation exchange resin is packed with a resin layer having a total length of 7 m or more, and then eluted with water to give a dextrin-rich fraction and a dextrin-maltose-rich fraction. , A maltose-rich fraction, a maltose / glucose-rich fraction, and a glucose-rich fraction in this order are fractionated into a plurality of fractions, usually 5 to 100, preferably 5 to 30 fractions. It was found that high-purity maltose can be easily produced by collecting the maltose-rich fraction.
また、原料糖をカラムに流して分画するに際し、既に得
られているデキストリン・マルトース高含有画分及びマ
ルトース・グルコース高含有画分とともに流して分画
し、マルトース高含有画分を採取し、同時に得られるデ
キストリン・マルトース高含有画分及びマルトース・グ
ルコース高含有画分を更に次回の原糖液とともに流す方
式を採用することにより目的とする高純度マルトースを
高濃度、高収率で繰り返し安定して製造し得ることを見
いだし、本発明を完成した。Further, when the raw sugar is flowed through the column for fractionation, the dextrin / maltose high content fraction and the maltose / glucose high content fraction that have already been obtained are fractionated by flow, and the maltose high content fraction is collected, By adopting a method in which the dextrin / maltose-rich fraction and the maltose / glucose-rich fraction obtained at the same time are flowed together with the next raw sugar solution, the target highly pure maltose can be repeatedly stabilized at high concentration and high yield. The present invention has been completed by discovering that it can be manufactured by
本発明に用いる原糖液は、マルトース含有量が70%以
上で、実質的にケトースを含有しない澱粉質由来のアル
ドース混合物含有液であり、本発明によってマルトース
含有量90%以上、望ましくはマルトース含有量93%
以上の高純度マルトースが高収率で採取できるものであ
ればよく、例えば、澱粉にα−アミラーゼ、β−アミラ
ーゼ、澱粉枝切酵素などの澱粉分解酵素を作用させて得
られるマルトース含有量70%以上の澱粉糖化液であっ
ても、また、マルトース含量70%以上を含有する市販
の澱粉糖化物溶液であってもよい。The raw sugar liquid used in the present invention is a starch-containing aldose mixture-containing liquid having a maltose content of 70% or more and substantially no ketose, and a maltose content of 90% or more, preferably maltose-containing according to the present invention. 93%
It suffices that the above-mentioned high-purity maltose can be collected in a high yield. For example, a maltose content of 70% obtained by allowing starch-degrading enzymes such as α-amylase, β-amylase, and starch debranching enzyme to act on starch. The above-mentioned starch saccharification solution may be a commercially available starch saccharification solution containing a maltose content of 70% or more.
また、本発明で使用されるアルカリ金属型またはアルカ
リ土類金属型強酸性カチオン交換樹脂には、例えば、ス
ルホン酸基を結合したスチレン−ジビニルベンゼン架橋
共重合体樹脂のNa+型、K+型などのアルカリ金属塩
型またはCa++型、Mg++型などのアルカリ土類金属塩
型の1種または2種以上が適宜使用され、市販品として
は、例えば、ダウケミカル社製造の商品名ダウエックス
50W×2、ダウエックス50W×4、ダウエックス5
0W×8、ロース&ハース社製造の商品名アンバーライ
トCG−120、東京有機化学工業社製造の商品名XT
−1022E、三菱化成工業社製造の商品名ダイヤイオ
ンSK1B、ダイヤイオンSK102、ダイヤイオンS
K104などがある。これらの樹脂は、マルトース高含
有画分の分画に優れているだけでなく、耐熱性、耐摩耗
性にも優れ、高純度マルトースの大量生産に極めて有利
である。Further, the alkali metal type or alkaline earth metal type strongly acidic cation exchange resin used in the present invention includes, for example, Na + type and K + type of styrene-divinylbenzene cross-linked copolymer resin having a sulfonic acid group bonded thereto. Alkali metal salt type such as or Ca ++ type, alkaline earth metal salt type such as Ca ++ type, Mg ++ type or the like is appropriately used, and examples of commercially available products include, for example, trade names manufactured by Dow Chemical Company. Dowex 50W x 2, Dowex 50W x 4, Dowex 5
0W × 8, product name Amberlite CG-120 manufactured by Loose & Haas Company, product name XT manufactured by Tokyo Organic Chemical Industry Co., Ltd.
-1022E, product name manufactured by Mitsubishi Kasei Co., Ltd. Diaion SK1B, Diaion SK102, Diaion S
For example, K104. These resins are excellent not only in the fractionation of the maltose-rich fraction but also in heat resistance and abrasion resistance, and are extremely advantageous for mass production of high-purity maltose.
本発明では、通常、0.01〜0.5mm程度の粒径の
樹脂をカラムに充填して使用すればよい。カラム内に充
填する樹脂層の長さは全長で7m以上が望ましく、この
際1本のカラムで7m以上にしても、また、2本以上の
カラムを直列に連結して7m以上にしてもよい。In the present invention, a resin having a particle size of about 0.01 to 0.5 mm may be usually used after being packed in a column. The total length of the resin layer packed in the column is preferably 7 m or more. At this time, one column may be 7 m or more, or two or more columns may be connected in series to be 7 m or more. .
カラムの材質、形状は、本発明の目的が達成できる限り
自由に選択できる。その材質は、例えば、ガラス、プラ
スチック、ステンレスなどが利用でき、その形状は充填
した樹脂層内を液ができるだけ層流になる、例えば、円
筒状、角柱状などが適宜利用できる。The material and shape of the column can be freely selected as long as the object of the present invention can be achieved. The material can be, for example, glass, plastic, stainless steel, or the like, and its shape can be appropriately used, for example, a cylindrical shape, a prismatic shape, or the like, in which the liquid is as laminar as possible in the filled resin layer.
以下、本発明の実施方法をより具体的に述べる。Hereinafter, the method for carrying out the present invention will be described more specifically.
アルカリ金属型またはアルカリ土類金属型強酸性カチオ
ン交換樹脂を水に懸濁してカラムに充填して樹脂層の全
長が7m以上になるようにし、このカラム内の温度を通
常45℃〜85℃に維持しつつ、これに濃度約10〜7
0W/W%の原糖液を樹脂に対して約1〜60V/V%
を加え、これに水をSV約0.1〜2.0の流速で上昇
法または下降法により流して溶出し、原糖液をデキスト
リン高含有画分、デキストリン・マルトース高含有画
分、マルトース高含有画分、マルトース・グルコース高
含有画分及びグルコース高含有画分に分画し、このマル
トース高含有画分を採取すればよい。The alkali metal type or alkaline earth metal type strongly acidic cation exchange resin is suspended in water and packed in a column so that the total length of the resin layer becomes 7 m or more, and the temperature in this column is usually 45 ° C to 85 ° C. While maintaining this, a concentration of about 10-7
Approximately 1 to 60 V / V% of 0 W / W% raw sugar solution to resin
Water is added to the solution to elute it by flowing up or down at a flow rate of about 0.1 to 2.0 SV, and the raw sugar solution is eluted with a high dextrin-rich fraction, dextrin-maltose-rich fraction, and maltose-rich fraction. The maltose-glucose-rich fraction and the glucose-rich fraction may be fractionated, and the maltose-rich fraction may be collected.
この際、溶出液の採取は、通常、使用樹脂に対して約1
〜20V/V%毎に行われるが、これを自動化し、前記
画分に振り分けることも容易である。At this time, the eluate is usually collected about 1 to the resin used.
It is performed every ˜20 V / V%, but it is also easy to automate this and distribute to the above-mentioned fractions.
また、原糖液をカラムに流して分画するに際し、既に得
られているデキストリン・マルトース高含有画分及びマ
ルトース・グルコース高含有画分を原糖液の前後に、ま
たは原糖液とともに流すことにより分画に要する使用水
量を減少させ、原糖液中のマルトースを高純度、高濃
度、高回収率で採取できるので好都合である。In addition, when the raw sugar solution is applied to the column for fractionation, the dextrin / maltose-rich fraction and the maltose / glucose-rich fraction that have already been obtained should be flown before or after the raw sugar solution or together with the raw sugar solution. This is advantageous because the amount of water used for fractionation can be reduced and maltose in the raw sugar solution can be collected with high purity, high concentration and high recovery rate.
一般的には、既に得られているデキストリン・マルトー
ス高含有画分を流した後に原糖液を流し、次いで既に知
られているマルトース・グルコース高含有画分を流すと
いう順序を採用するのが好ましい。In general, it is preferable to adopt a sequence in which the already-obtained dextrin-maltose-rich fraction is allowed to flow, then the raw sugar solution is allowed to flow, and then the already-known maltose-glucose-rich fraction is allowed to flow. .
また、本発明で使用される分画法は、固定床方式、移動
床方式、擬似移動床方式のいずれであってもよい。The fractionation method used in the present invention may be a fixed bed method, a moving bed method, or a simulated moving bed method.
このようにして分画し、採取されたマルトース高含有画
分を、そのままで用いることもできるが、必要ならば、
常法に従って、例えば、濾過、脱色、脱塩、精製した
後、例えば、濃縮してシラップとするか、さらに晶出さ
せてマスキットとし、これを噴霧乾燥して含蜜結晶粉末
とするか、または晶出させたマスキットを分蜜してさら
に高純度のマルトース結晶を採取することも自由であ
る。The maltose-rich fraction collected by fractionation in this manner can be used as it is, but if necessary,
According to a conventional method, for example, after filtering, decolorizing, desalting, and purifying, for example, it is concentrated to give syrup, or further crystallized to give a musket, which is spray-dried to give a nectar-containing crystal powder, or It is also possible to separate the crystallized musket to collect higher purity maltose crystals.
マスキットの調製方法は、通常30〜70℃の比較的高
温の過飽和マルトース溶液を助晶缶により、これに種晶
を望ましくは0.1〜20%共存せしめて、ゆっくり攪
拌しつつ除冷し、晶出を促がせばよい。マスキットを噴
霧乾燥する場合は、通常、濃度70〜80%、晶出率2
5〜60%程度のマスキットを高圧ポンプでノズルから
噴霧するか、回転円板などを利用して噴霧し、結晶粉末
が溶融しない温度、例えば60〜100℃の熱風で乾燥
し、次いで30〜60℃の温風で約1〜20時間熟成す
れば、非吸湿性又は難吸湿性の含蜜結晶が容易に製造で
きる。また、ブロック粉砕方法の場合は、通常、水分7
〜15%、晶出率10〜60%程度のマスキットを0.
5〜7日間静置して全体をブロック状に晶出固化させ、
これを粉砕または切削などの方法によって粉砕し、乾燥
すれば、非吸湿性又は難吸湿性の含蜜結晶が容易に製造
できる。更には、分蜜方法の場合は、マスキットをバス
ケット型遠心分離機にかけ、結晶と蜜とに分離する方法
で、必要により、該結晶に小量の冷水をスプレーして洗
浄することも容易であり、より高純度の結晶マルトース
を製造するのに好都合である。The method for preparing the musket is usually a relatively high temperature supersaturated maltose solution of 30 to 70 ° C., which is allowed to coexist with a seed crystal in an amount of 0.1 to 20%, and slowly cooled with stirring. All you have to do is promote crystallization. When spray-drying the musket, the concentration is usually 70 to 80% and the crystallization rate is 2
About 5 to 60% of the mass kit is sprayed from a nozzle with a high-pressure pump, or sprayed by using a rotating disk, etc., and dried with hot air at a temperature at which the crystal powder does not melt, for example, 60 to 100 ° C, and then 30 to 60. By aging with warm air of ℃ for about 1 to 20 hours, non-hygroscopic or hardly hygroscopic honey-containing crystals can be easily produced. In the case of the block crushing method, the water content is usually 7
-15% and a crystallization rate of about 10-60%, and a mass kit of 0.
Allow to stand for 5 to 7 days to crystallize and solidify the whole in a block,
If this is crushed by a method such as crushing or cutting and dried, a non-hygroscopic or hardly hygroscopic honey-containing crystal can be easily produced. Further, in the case of the syrup method, a method in which a musket is subjected to a basket type centrifuge to separate crystals and honey, and if necessary, it is easy to wash the crystals by spraying a small amount of cold water. , Which is convenient for producing higher purity crystalline maltose.
このようにして製造される高純度マルトースは、飲食
物、医薬など、更には、マルチトール結晶粉末の原料な
ど各種用途に対して有利に利用できる。The high-purity maltose thus produced can be advantageously used for various purposes such as food and drink, medicines, and raw materials for maltitol crystal powder.
以下、本発明を実験で詳細に説明する。Hereinafter, the present invention will be described in detail by experiments.
実験1.原糖液の比較 原糖液は、第1表に示した林原株式会社製造の各種澱粉
糖商品を濃度45W/W%水溶液にして使用した。Experiment 1. Comparison of raw sugar liquid As the raw sugar liquid, various starch sugar products manufactured by Hayashibara Co., Ltd. shown in Table 1 were used as aqueous solutions having a concentration of 45 W / W%.
樹脂は、アルカリ金属型強酸性カチオン交換樹脂(ダウ
ケミカル社製造、商品名ダウエックス50W×4、Na
+型)を使用し、これを水懸濁液として内径5.4cm
のジャケット付ステンレス性カラム1本に樹脂層長が1
0mになるように充填した。The resin is an alkali metal strongly acidic cation exchange resin (manufactured by Dow Chemical Co., trade name Dowex 50W × 4, Na
+ Type) is used as an aqueous suspension and has an inner diameter of 5.4 cm.
The length of the resin layer is 1 for one stainless steel column with a jacket
It was filled to 0 m.
カラム内温度を75℃に維持しつつ、原糖液を樹脂に対
して5V/V%加え、これに75℃の温水をSV0.4の
流速で流して分画し、マルトース含有量93%以上のマ
ルトース高含有画分を採取した。結果は第2表に示し
た。While maintaining the temperature in the column at 75 ° C, the raw sugar solution was added to the resin at 5V / V%, and hot water at 75 ° C was flowed at a flow rate of SV0.4 to fractionate the maltose content to 93% or more. The maltose-rich fraction of was collected. The results are shown in Table 2.
第2表の結果から明らかなように、原糖液の糖組成とし
てマルトース含有量を70%以上にすれば、マルトース
含有量93%以上のマルトース高含有画分中にマルトー
スが原糖液マルトースに対して80%以上の高収率で採
取できることが判明した。 As is clear from the results shown in Table 2, when the maltose content of the sugar composition of the raw sugar solution was 70% or more, maltose was converted to maltose in the high maltose content fraction having a maltose content of 93% or more. On the other hand, it was found that the sample could be collected with a high yield of 80% or more.
実験2.樹脂層長の比較 実験1と同様にして、アルカリ金属型強酸性カチオン交
換樹脂をカラムの1本または2本に充填し、その樹脂層
の全長を1〜20mとした。Experiment 2. Comparison of Resin Layer Lengths Similar to Experiment 1, one or two columns of the alkali metal type strongly acidic cation exchange resin were packed, and the total length of the resin layers was set to 1 to 20 m.
これら樹脂層長の異なる各カラムに、カラム内温度を7
5℃に維持しつつ、マルトース含有量85.0%の澱粉
糖(商品名サンマルト)を濃度45W/W%水溶液とし
た原糖液を樹脂に対して5V/V%加え、75℃の温水
をSV0.4の流速で流して各画分に分画し、マルトー
ス含有量93%以上のマルトース高含有画分を採取し
た。結果は第3表に示した。For each column with a different resin layer length,
While maintaining the temperature at 5 ° C, a starch sugar solution having a maltose content of 85.0% (trade name Sanmalto) at a concentration of 45 W / W% was added to the resin at 5 V / V%, and hot water at 75 ° C was added. It was flowed at a flow rate of SV 0.4 to fractionate each fraction, and a maltose-rich fraction having a maltose content of 93% or more was collected. The results are shown in Table 3.
第3表の結果から明らかなように、樹脂層の全長を7m
以上にすれば、マルトース含有量93%以上のマルトー
ス高含有画分中にマルトースが原糖液マルトースに対し
て80%以上にも達し、樹脂層の全長が6m以下の場合
と比較して極めて高収率に採取できることが判明した。 As is clear from the results in Table 3, the total length of the resin layer is 7 m.
According to the above, maltose reaches 80% or more with respect to the raw sugar solution maltose in the maltose-rich fraction having a maltose content of 93% or more, which is extremely higher than that in the case where the total length of the resin layer is 6 m or less. It turned out that it can be collected in a yield.
実験3.分画時の温度の比較 実験1と同様にして、アルカリ金属型強酸性カチオン交
換樹脂を樹脂層長が10mになるように充填し、このカ
ラムに実験2と同様にして調整した原糖液を加え、カラ
ム内温度を35〜95℃に変えた以外は、実験2と同様
に分画して、マルトース含有量93%以上のマルトース
高含有画分を採取した。Experiment 3. Comparison of temperature during fractionation In the same manner as in Experiment 1, the alkali metal type strongly acidic cation exchange resin was packed to a resin layer length of 10 m, and the raw sugar solution prepared in the same manner as in Experiment 2 was packed in this column. In addition, fractionation was performed in the same manner as in Experiment 2 except that the temperature in the column was changed to 35 to 95 ° C., and a maltose-rich fraction having a maltose content of 93% or more was collected.
結果は第4表に示した。The results are shown in Table 4.
第4表の結果から明らかなように、分画温度を45〜8
5℃の範囲内にすれば、糖の褐変着色を懸念することも
なく、マルトース含有量93%以上のマルトース高含有
画分中にマルトースが原糖液マルトースに対して80%
以上の高収率で採取できることが判明した。 As is clear from the results in Table 4, the fractionation temperature was 45 to 8
Within the range of 5 ° C., there is no concern about browning and coloring of sugar, and maltose contained in the maltose-rich fraction having a maltose content of 93% or more contained 80% of maltose as a raw sugar solution.
It was found that the sample could be collected with the above high yield.
以下、2〜3の実施例を述べる。Hereinafter, a few examples will be described.
実施例1 マルトース含有量76.8%の澱粉糖液(林原株式会社
製造、商品名HM−75)を濃度45W/W%水溶液に
して原糖液とした。樹脂は、アルカリ金属型強酸性カチ
オン交換樹脂(東京有機化学工業社製造、商品名XT−
1022E、Na+型)を使用し、内径5.4cmのジ
ャケット付ステンレス製カラム水懸濁液状で充填した。
この際、樹脂層長5mのカラム4本に充填し、その液が
直列に流れるようにカラム4本を連結して樹脂層全長を
20mとした。Example 1 A starch sugar solution having a maltose content of 76.8% (manufactured by Hayashibara Co., Ltd., trade name HM-75) was made into a 45 W / W% aqueous solution to give a raw sugar solution. The resin is an alkali metal type strong acid cation exchange resin (manufactured by Tokyo Organic Chemical Industry Co., Ltd., trade name XT-
1022E, Na + type) was used, and a column made of stainless steel with a jacket and having an inner diameter of 5.4 cm was filled in the form of a water suspension.
At this time, four columns each having a resin layer length of 5 m were packed, and the four columns were connected so that the liquid flowed in series, so that the total resin layer length was 20 m.
カラム内温度を55℃に維持しつつ、原糖液を樹脂に対
して5V/V%加え、これに55℃の温水をSV0.1
3の流速で流して分画し、マルトース含有量93%以上
のマルトース高含有画分を採取した。このマルトース高
含有画分には、マルトースが808.2g含まれ、原糖
液マルトースに対して84.3%の高収率であった。While maintaining the temperature in the column at 55 ° C, 5% V / V% of the raw sugar solution was added to the resin, and warm water at 55 ° C was added to the SV0.1
Fractionation was carried out at a flow rate of 3, and a maltose-rich fraction having a maltose content of 93% or more was collected. This maltose-rich fraction contained 808.2 g of maltose and had a high yield of 84.3% based on the raw sugar solution maltose.
実施例2 マルトース含有量85.0%の澱粉糖粉末(林原株式会
社製造、商品名サンマルト)を濃度60W/W%水溶液
にして原糖液とした。樹脂は、実施例1に用いたものを
K+型に変えた後使用し、内径2.2cmのジャケット
付ステンレス製カラム1本に樹脂層長が10mになるよ
うに充填した。Example 2 Starch sugar powder having a maltose content of 85.0% (manufactured by Hayashibara Co., Ltd., trade name Sanmalto) was made into a 60 W / W% aqueous solution to give a raw sugar solution. The resin used in Example 1 was changed to the K + type and then used, and one stainless steel column with a jacket having an inner diameter of 2.2 cm was filled so that the resin layer length was 10 m.
カラム内温度を60℃に維持しつつ、原糖液を樹脂に対
して3V/V%加え、これに60℃の温水をSV0.2
の流速で流して分画し、マルトース含有量93%以上の
マルトース高含有画分を採取した。このマルトース高含
有画分にはマルトースが65.7g含まれ、原糖液マル
トースに対して88.3%の高収率であった。While maintaining the column temperature at 60 ° C, the raw sugar solution was added to the resin at 3V / V%, and warm water at 60 ° C was added to the SV0.2.
Was fractionated by flowing at a flow rate of 3 to obtain a maltose-rich fraction having a maltose content of 93% or more. This maltose-rich fraction contained 65.7 g of maltose, which was a high yield of 88.3% based on the raw sugar solution maltose.
実施例3 マルトース含有量85.0%の澱粉糖粉末(商品名サン
マルト)を濃度45W/W%水溶液にして原糖液とし
た。樹脂は、アルカリ土類金属型強酸性カチオン交換樹
脂(ダウケミカル社製造、商品名ダウエックス50W×
4、Mg++型)を使用し、実施例1と同じカラムに樹脂
層の全長が15mになるように充填した。カラム内温度
を75℃に維持しつつ原糖液を樹脂に対して6.6V/
V%加え、これに75℃の温水をSV0.13の流速で
流して分画し、マルトース含有量93%以上のマルトー
ス高含有画分を採取した。このマルトース高含有画分に
はマルトースが913.7g含まれ、原糖液マルトース
に対して87.1%の高収率であった。Example 3 Starch sugar powder (trade name: Sanmalto) having a maltose content of 85.0% was made into a 45 W / W% aqueous solution to give a raw sugar solution. The resin is an alkaline earth metal type strong acid cation exchange resin (manufactured by Dow Chemical Co., product name Dowex 50W ×
4, Mg ++ type) was used and the same column as in Example 1 was packed so that the total length of the resin layer was 15 m. The raw sugar solution was added to the resin at 6.6 V /
V% was added, and hot water at 75 ° C. was flown at a flow rate of SV of 0.13 to fractionate the fraction, and a maltose-rich fraction having a maltose content of 93% or more was collected. This maltose-rich fraction contained 913.7 g of maltose, which was a high yield of 87.1% based on the raw sugar solution maltose.
実施例4 まず、第1回目の分画に際して、原糖液を樹脂に対して
20V/V%使用した以外は、実施例3と同様にして分
画した。分画品の溶出パターンを図に示した。Example 4 First, in the first fractionation, fractionation was performed in the same manner as in Example 3 except that the raw sugar solution was used at 20 V / V% with respect to the resin. The elution pattern of the fractionated product is shown in the figure.
図で、Aはデキストリン高含有画分を示し、Bはデキス
トリン・マルトース高含有画分を示し、Cはマルトース
高含有画分を示し、Dはマルトース・グルコース高含有
画分を示し、Eはグルコース高含有画分を示す。その溶
出順序はA、B、C、D、Eの順であった。In the figure, A represents a dextrin-rich fraction, B represents a dextrin-maltose-rich fraction, C represents a maltose-rich fraction, D represents a maltose-glucose-rich fraction, and E represents glucose. A high content fraction is shown. The elution order was A, B, C, D, E.
分画品C(マルトース高含有画分)は採取し、分画品A
及びEは除去した。Fraction C (fraction containing high maltose) was collected and fraction A
And E were removed.
第2回目以降の分画は同じカラムに分画品B、樹脂に対
して約10V/V%の原糖液及び分画品Dの順に加え、
更に75℃の温水を実施例3と同様に流してマルトース
含有量94%のマルトース高含有画分を採取した。第2
回目以降の分画操作を延べ30回繰り返して1回当りの
平均結果を求めたところ、マルトース高含有画分にはマ
ルトースが1483g含まれ、原糖液マルトースに対し
て93.3%の高収率であった。For the second and subsequent fractions, the fraction B was added to the same column in the order of about 10 V / V% raw sugar solution and the fraction D to the resin,
Further, warm water at 75 ° C. was caused to flow in the same manner as in Example 3 to collect a maltose-rich fraction having a maltose content of 94%. Second
The fractionation operation from the second time onward was repeated 30 times in total, and the average result per one time was obtained. The maltose-rich fraction contained 1483 g of maltose, which was 93.3% higher than that of the raw sugar solution maltose. It was a rate.
実施例5 マルトース含有量91.5%の澱粉糖粉末(林原株式会
社製造、商品名マルトースH)を濃度45W/W%水溶
液にして原糖液とした。樹脂は、アルカリ土類金属型強
酸性カチオン交換樹脂(ローム&ハース社製造、商品名
アンバーライトCG−120、Ca++型)を使用し、実
施例1で使用したカラムに、樹脂層の全長が10mにな
るように充填した。カラム内温度を80℃に維持しつつ
原糖液を樹脂に対して第1回目の分画に際しては20V
/V%加え、これに80℃の温水をSV0.6の流速で
流し分画した。Example 5 A starch sugar powder having a maltose content of 91.5% (manufactured by Hayashibara Co., Ltd., trade name Maltose H) was made into a 45 W / W% aqueous solution to give a raw sugar solution. As the resin, an alkaline earth metal type strong acid cation exchange resin (manufactured by Rohm & Haas Co., trade name Amberlite CG-120, Ca ++ type) is used, and the full length of the resin layer is applied to the column used in Example 1. Was filled so as to be 10 m. 20 V for the first fractionation of the raw sugar solution against the resin while maintaining the column temperature at 80 ° C.
/ V% was added, and warm water at 80 ° C. was flown at a flow rate of SV of 0.6 for fractionation.
実施例4の場合と同様に分画品C(マルトース高含有画
分)は、採取し、分画品A及びEは除去した。第2回目
以降の分画は同じカラムに分画品B、樹脂に対して約1
0V/V%の原糖液、及び分画品Dの順に加え、更に8
0℃の温水をSV0.6の流速で流してマルトース含有
量96%以上のマルトース高含有画分を採取した。As in the case of Example 4, the fraction C (maltose-rich fraction) was collected, and the fractions A and E were removed. Fractions from the second time onward are about 1 for fraction B and resin on the same column.
Add 0 V / V% raw sugar solution and Fraction D in this order, and add 8
Warm water at 0 ° C. was caused to flow at a flow rate of SV0.6 to collect a maltose-rich fraction having a maltose content of 96% or more.
第2回目以降の分画操作を延べ100回繰り返して1回
当りの平均結果を求めたところ、マルトース高含有画分
にはマルトースが1084g含まれ、原糖液マルトース
に対して95%の高収率であった。The second and subsequent fractionation operations were repeated a total of 100 times, and the average result per one time was determined. The maltose-rich fraction contained 1084 g of maltose, which was a high yield of 95% with respect to the raw sugar solution maltose. It was a rate.
図は、原糖液の溶出パターンの一例を示す図である。図
中の符号Aはデキストリン高含有画分、Bはデキストリ
ン・マルトース高含有画分、Cはマルトース高含有画
分、Dはマルトース・グルコース高含有画分、及びEは
グルコース高含有画分を示す。The figure is a diagram showing an example of the elution pattern of the raw sugar solution. In the figure, reference symbol A represents a dextrin-rich fraction, B represents a dextrin-maltose-rich fraction, C represents a maltose-rich fraction, D represents a maltose-glucose-rich fraction, and E represents a glucose-rich fraction. .
Claims (4)
の澱粉糖液を、アルカリ金属型又はアルカリ土類金属型
強酸性カチオン交換樹脂を樹脂層の全長を7m以上に充
填したカラムに流し、次いで水で溶出し、テキストリン
高含有画分、デキストリン・マルトース高含有画分、マ
ルトース含有量が固形物当り93%以上のマルトース高含
有画分、マルトース・グルコース高含有画分及びグルコ
ース高含有画分の順に分画し、このマルトース高含有画
分を採取してマルトース含有量が固形物当り93%以上の
高純度マルトースを澱粉糖液中のマルトースに対し80%
以上の収率で得ることを特徴とする高純度マルトースの
製造方法。1. Maltose content is 70-91.5% based on solids.
The starch-sugar solution of No. 1 is poured into a column in which an alkali metal type or alkaline earth metal type strongly acidic cation exchange resin is packed with a resin layer having a total length of 7 m or more, and then eluted with water to give a high textrin content fraction, dextrin. Fraction with high maltose content, high maltose content with maltose content of 93% or more per solid, maltose / glucose high content fraction and glucose high content fraction are collected in this order, and the high maltose content fraction is collected. The high-purity maltose with a maltose content of 93% or more based on the solid content is 80% based on the maltose in the starch sugar solution.
A method for producing high-purity maltose, which is obtained in the above yield.
ことを特徴とする特許請求の範囲第1項記載の高純度マ
ルトースの製造方法。2. The method for producing high-purity maltose according to claim 1, wherein the column temperature is maintained in the range of 45 to 85 ° C.
分画したマルトース高含有画分を濃縮し、マルトースを
晶出させる工程を含むことを特徴とする特許請求の範囲
第1項又は第2項記載の高純度マルトースの製造方法。3. A step of collecting a maltose-rich fraction,
The method for producing high-purity maltose according to claim 1 or 2, further comprising a step of concentrating the fraction having a high maltose content and crystallizing maltose.
ことを特徴とする特許請求の範囲第3項記載の高純度マ
ルトースの製造方法。4. The method for producing high-purity maltose according to claim 3, wherein the high-purity maltose obtained is a powder product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1102186A JPH0614880B2 (en) | 1989-04-22 | 1989-04-22 | Method for producing high-purity maltose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1102186A JPH0614880B2 (en) | 1989-04-22 | 1989-04-22 | Method for producing high-purity maltose |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56121725A Division JPS5823799A (en) | 1981-08-03 | 1981-08-03 | Production of high purity maltose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02139000A JPH02139000A (en) | 1990-05-28 |
| JPH0614880B2 true JPH0614880B2 (en) | 1994-03-02 |
Family
ID=14320637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1102186A Expired - Lifetime JPH0614880B2 (en) | 1989-04-22 | 1989-04-22 | Method for producing high-purity maltose |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0614880B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080049924A (en) * | 2006-12-01 | 2008-06-05 | 주식회사 신동방씨피 | Method for preparing high purity crystal powder maltitol |
| CN110938714B (en) * | 2019-12-03 | 2023-08-15 | 山东福田药业有限公司 | Production method of high-purity crystalline maltose |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4109075A (en) | 1976-06-09 | 1978-08-22 | Cpc International Inc. | Separation of saccharides by exclusion chromatography |
-
1989
- 1989-04-22 JP JP1102186A patent/JPH0614880B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4109075A (en) | 1976-06-09 | 1978-08-22 | Cpc International Inc. | Separation of saccharides by exclusion chromatography |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02139000A (en) | 1990-05-28 |
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