JPS6013000A - Chromatographic separation of sugar liquid - Google Patents
Chromatographic separation of sugar liquidInfo
- Publication number
- JPS6013000A JPS6013000A JP58120982A JP12098283A JPS6013000A JP S6013000 A JPS6013000 A JP S6013000A JP 58120982 A JP58120982 A JP 58120982A JP 12098283 A JP12098283 A JP 12098283A JP S6013000 A JPS6013000 A JP S6013000A
- Authority
- JP
- Japan
- Prior art keywords
- cation exchange
- resin
- content
- sugar solution
- separation
- 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.)
- Granted
Links
- 235000000346 sugar Nutrition 0.000 title claims description 52
- 238000013375 chromatographic separation Methods 0.000 title claims description 21
- 239000007788 liquid Substances 0.000 title description 20
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 77
- 238000000926 separation method Methods 0.000 claims description 66
- 239000003729 cation exchange resin Substances 0.000 claims description 56
- 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 46
- 230000002378 acidificating effect Effects 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 19
- 229930091371 Fructose Natural products 0.000 claims description 17
- 239000005715 Fructose Substances 0.000 claims description 17
- 229940023913 cation exchange resins Drugs 0.000 claims description 15
- 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 14
- 239000008103 glucose Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- 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 claims description 8
- 239000003480 eluent Substances 0.000 claims description 6
- 150000001720 carbohydrates Chemical class 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims 2
- 239000011347 resin Substances 0.000 description 48
- 229920005989 resin Polymers 0.000 description 48
- 230000008961 swelling Effects 0.000 description 14
- 230000002427 irreversible effect Effects 0.000 description 13
- 238000010828 elution Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 150000008163 sugars Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 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 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 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 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
- 229920001542 oligosaccharide Polymers 0.000 description 2
- 150000002482 oligosaccharides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Landscapes
- Saccharide Compounds (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は強酸性陽イオン交換樹脂を充填した分離塔に２
種類以上の糖類を含む糖液を通液し２次いで溶離水を通
水して当該糖液中の各糖類をクロマト分離する処理方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides two
The present invention relates to a treatment method in which a sugar solution containing more than one type of saccharide is passed through, and then elution water is passed through to separate each saccharide in the sugar solution by chromatography.
従来からブドウ糖と果糖の混合糖液、あるいはブドウ糖
とマルトースの混合糖液、あるいはフラクトオリゴ糖と
その他の糖の混合糖液など、少なくとも２種類以上の糖
類を含有する糖液から各糖を分離するにあた９２強酸性
陽イオン交換樹脂を用いるクロマト分離処理が行なわれ
ている。当該クロマト分離はカルシウム形あるいはナト
リウム形などの強酸性陽イオン交換樹脂を充填した分離
塔に一定量の前記糖液を通液し２次いで一定量の溶離水
を通水するもので、このようにすると溶液中の各糖のイ
オン交換樹脂に対する分配の差によシ各糖が分離され、
クロマト的濃度分布を呈して各分離液が流出してくる。Traditionally, each sugar has been separated from a sugar solution containing at least two types of sugars, such as a mixed sugar solution of glucose and fructose, a mixed sugar solution of glucose and maltose, or a mixed sugar solution of fructooligosaccharides and other sugars. A chromatographic separation process using Ata 92 strongly acidic cation exchange resin is carried out. The chromatographic separation involves passing a certain amount of the sugar solution through a separation tower filled with a strongly acidic cation exchange resin such as calcium or sodium type, and then passing a certain amount of eluate water through it. Then, each sugar in the solution is separated due to the difference in distribution to the ion exchange resin.
Each separated liquid flows out with a chromatographic concentration distribution.
たとえばカルシウム形強酸性陽イオン交換樹脂を充填し
た分離塔に、ブドウ糖と果糖を含む一定量の糖液を通液
し１次いで一定量の溶離水を通水すると、その流出液中
には濃度ピークの裾野は多少型なるが最初にブドウ糖の
濃度ピークが生じ２次いで果糖の濃度ピークが生じる。For example, when a certain amount of a sugar solution containing glucose and fructose is passed through a separation column filled with a calcium-type strongly acidic cation exchange resin, and then a certain amount of eluate water is passed through a separation column, a concentration peak is observed in the effluent. Although the shape of the base is somewhat different, the glucose concentration peak occurs first, followed by the fructose concentration peak.
なお当該糖液に少量のオリゴ糖が含まれている場合は、
ブドウ糖の濃度ピークよシ先にオリゴ糖の濃度ピークが
生じる。したがって当該糖液を通液し２次いで溶離水を
通水し、流出液を各フラクション別に採取する操作を繰
り返すとブドウ糖と果糖の混合糖液から比較的高純度の
果糖液を得ることができる。If the sugar solution contains a small amount of oligosaccharide,
The oligosaccharide concentration peak occurs before the glucose concentration peak. Therefore, by repeating the operations of passing the sugar solution through, then passing elution water through, and collecting the effluent separately for each fraction, a relatively highly purified fructose solution can be obtained from the mixed sugar solution of glucose and fructose.
従来から以上のようなりロマト分離の手法を用いてブド
ウ糖と果糖の分離のみならず。Conventionally, the above-mentioned romatoseparation method is used not only to separate glucose and fructose.
前記したマルトースあるいはフラクトオリゴ糖などの各
種の糖の分離が工業的規模で実施されているが、従来の
クロマト分離処理においては分離塔に充填した強酸性陽
イオン交換樹脂が使用していく内に不可逆膨潤を起し。The separation of various sugars such as maltose and fructooligosaccharides mentioned above has been carried out on an industrial scale, but in conventional chromatographic separation processing, the strongly acidic cation exchange resin packed in the separation column becomes irreversible as it is used. causing swelling.
このため種々のトラブルが発生している。For this reason, various troubles occur.
これを以下に詳しく説明すると、前述した強酸性陽イオ
ン交換樹脂によるクロマト分離においては、使用する当
該陽イオン交換樹脂の粒子径が同一の場合、架橋度の低
いもの。To explain this in detail below, in the chromatographic separation using the above-mentioned strongly acidic cation exchange resin, if the particle diameter of the cation exchange resin used is the same, the degree of crosslinking is low.
換言すればジビニルベンゼン含有量の少ないものの方が
一般に各糖の分離性能が優れている。しかしながらジビ
ニルベンゼン含有量が少なくなるとそれに比例して当該
陽イオン交換樹脂の物理的強度が低下するので、ジビニ
ルベンゼン含有量のあまり少ないものは使用できず、従
来からジビニルベンゼン含有量４〜−１％の中から被処
理対象糖液に対して分離性能と物理的強度の折合う最も
適当な強酸性陽イオン交換樹脂を一種類選定し、これを
分離塔に充填して用いている。In other words, those containing less divinylbenzene generally have better separation performance for each sugar. However, when the divinylbenzene content decreases, the physical strength of the cation exchange resin decreases in proportion to it, so it is impossible to use one with a very low divinylbenzene content, and conventionally the divinylbenzene content is 4 to -1%. One type of strongly acidic cation exchange resin that is most suitable for the sugar solution to be treated in terms of separation performance and physical strength is selected from among them, and this resin is packed into a separation column for use.
このような分離塔を用いてクロマト分離を続行していく
と、特に強酸性陽イオン交換樹脂層の上層部すなわち糖
液や溶離水が最初に接触する面からそのやや下層に存在
する強酸性陽イオン交換樹脂が、その水分含有率が増加
し、容積が増大するという不可逆膨潤を起こし、はなは
だしいときには樹脂粒子がゼラチン状に膨潤し、このた
め上層部分で非常に大きな圧力損失が生じ、かつ糖液と
溶離水の均一流を妨げ、液の片流れを引起こすため。When chromatographic separation is continued using such a separation column, the strong acid cation exchange resin layer, which exists slightly below the upper layer of the strongly acidic cation exchange resin layer, that is, the surface that first comes into contact with the sugar solution and eluate water, is removed. The ion exchange resin undergoes irreversible swelling as its water content increases and its volume increases, and in extreme cases, the resin particles swell into a gelatinous state, resulting in a very large pressure loss in the upper layer, and the sugar solution and to prevent uniform flow of eluent water and cause one-sided flow of liquid.
分離塔の分離性能を著しく低下させる。当該強酸性陽イ
オン交換樹脂の不可逆膨潤は当該樹脂粒子の三次元構造
を構成する架橋部分（ｃｒｏｓｓ −１ｉｎｋ ）が切
断されることから生じるが、この原因としては糖液と溶
離水が交互に強酸性陽イオン交換樹脂に接触することに
よるイオン交換樹脂の収縮膨潤の反復によるもの、ある
いは重金属が触媒となって溶存酸素による酸化によるも
の、あるいは微生物酸化によるものなどが考えられる。Separation performance of the separation column is significantly reduced. Irreversible swelling of the strongly acidic cation exchange resin occurs because the cross-linked portion (cross-1ink) that constitutes the three-dimensional structure of the resin particles is cut. Possible causes include repeated contraction and swelling of the ion exchange resin due to contact with the cation exchange resin, oxidation by dissolved oxygen catalyzed by heavy metals, or oxidation by microorganisms.
いずれの原因にしても分離塔に充填されている強酸性陽
イオン交換樹脂が不可逆膨潤を起こすと、前述したよう
なトラブルが発生するので適当な時期にクロマト分離操
作を中断し、不可逆膨潤を起した当該陽イオン交換樹脂
を取シ出し、これを新しいものと交換する必要がある。Regardless of the cause, if the strongly acidic cation exchange resin packed in the separation column causes irreversible swelling, the above-mentioned troubles will occur, so stop the chromatographic separation operation at an appropriate time and prevent irreversible swelling. It is necessary to take out the cation exchange resin and replace it with a new one.
しかしながら一般にクロマト分離処理の分離塔に充填さ
れている当該陽イオン交換樹脂の樹脂量は多く、たとえ
その充填量の一部の交換であっても、その経済的負担は
大きく、さらに交換毎に分離操作を中断せねばならず、
かつ充填層の１部分のみを交換するので操作が煩雑であ
る。However, in general, the amount of cation exchange resin packed into a separation tower for chromatographic separation treatment is large, and even if only a portion of the amount is replaced, the economic burden is large, and furthermore, each exchange requires separation. operation must be interrupted,
Moreover, since only a portion of the packed bed is replaced, the operation is complicated.
なお分離塔に充填する強酸性陽イオン交換樹脂としてジ
ビニルベンゼン含有量がたとえば１０係以上のかなシ多
いものを用いれば物理的強度が増加するので、前述した
不可逆膨潤に起因する種々のトラブルを回避することが
できる。しかしながらジビニルベンゼン含有量が増加す
ると、それにともなって糖類の分離性能が低下するので
、現状では前述したごとくジビニルベンゼン含有量が＋
７％以上の強酸性陽イオン交換樹脂は用いられていない
。Furthermore, if a strongly acidic cation exchange resin with a divinylbenzene content of, for example, 10 parts or more is used as the strongly acidic cation exchange resin packed in the separation column, the physical strength will be increased, thereby avoiding the various troubles caused by irreversible swelling mentioned above. can do. However, as the divinylbenzene content increases, the separation performance for sugars decreases, so currently, as mentioned above, the divinylbenzene content is +
A strongly acidic cation exchange resin of 7% or more is not used.
なお前述した強酸性陽イオン交換樹脂の不可逆膨潤は分
離しようとする糖液がブドウ糖と果糖を含む糖液である
場合が最も著しく、果糖の分離工程において特に問題と
なっている。The irreversible swelling of the strongly acidic cation exchange resin described above is most noticeable when the sugar solution to be separated is a sugar solution containing glucose and fructose, and is particularly problematic in the fructose separation process.
本発明はクロマト分離処理における。かかる欠点を解決
し、糖類の分離性能を低下させることなく９分離塔内に
充填されている強酸性陽イオン交換樹脂の不可逆膨潤を
効果的に回避できるクロマト分離処理方法を提供するこ
とを目的とするもので２強酸性陽イオン交換樹脂を充填
した分離塔に２種類以上の糖類を含む糖液を通液し１次
いで溶離水を通水することにより当該糖液中の各糖類を
クロマト分離するにあたり、ジビニルベンゼン含有量の
異なる少なくとも２種類以上の強酸性陽イオン交換樹脂
を、ジビニルベンゼン含有量の多いものから順に少ない
ものへと段階的に充填した分離塔を用い、ジビニルベン
ゼン含有量の多い強酸性陽イオン交換樹脂側から前記糖
液を通液し２次いで溶離水を通水することを特徴とする
糖液のクロマト分離処理方法に関するものである。The present invention relates to chromatographic separation processing. The purpose of the present invention is to provide a chromatographic separation treatment method that solves these drawbacks and can effectively avoid irreversible swelling of the strongly acidic cation exchange resin packed in the 9-separation column without reducing the separation performance of sugars. A sugar solution containing two or more types of saccharides is passed through a separation tower filled with two strongly acidic cation exchange resins, and each saccharide in the sugar solution is chromatographically separated by first passing elution water. In this process, a separation column is used in which at least two types of strongly acidic cation exchange resins with different divinylbenzene contents are filled in stages from the one with the highest divinylbenzene content to the one with the lowest divinylbenzene content. The present invention relates to a method for chromatographic separation of a sugar solution, characterized in that the sugar solution is passed through the strongly acidic cation exchange resin side, and then elution water is passed through the resin.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
本発明は従来の分離塔において、不可逆膨潤を起こす強
酸性陽イオン交換樹脂は上層部すなわち糖液や溶離水が
最初に接触する面からそのやや下層の範囲が顕著である
こと、およびこの部分のみにジビニルベンゼン含有量（
以下、 ＤＶＢ含有量という）が多い強酸性陽イオン交
換樹脂を充填しても充填層全体の分離性能はほとんど低
下しないことなどの知見に基づくもので、基本的にはＤ
ＶＢ含有量の異なる少なくとも２種類以上の強酸性陽イ
オン交換樹脂を、 ＤＶＢ含有量の多いものから順に少
ないものへと段階的に充填した分離塔を用い、 ＤＶＢ
含有量の多い強酸性陽イオン交換樹脂側から糖液および
溶離水を流入するところにある。The present invention is based on the fact that in conventional separation columns, the strongly acidic cation exchange resin that causes irreversible swelling is noticeable in the upper layer, that is, the area slightly below the surface where the sugar solution and eluate water first come into contact, and that only this portion Divinylbenzene content (
This is based on the knowledge that the separation performance of the entire packed bed hardly deteriorates even if a strongly acidic cation exchange resin with a high DVB content (hereinafter referred to as DVB content) is packed.
Using a separation column filled with at least two or more types of strongly acidic cation exchange resins with different VB contents in stages from the one with the highest DVB content to the one with the lowest DVB content, DVB
This is where the sugar solution and eluate water are introduced from the strongly acidic cation exchange resin side, which has a high content.
第１図は本発明に用いる分離塔の実施態様の一例の説明
図であシ、単基からなる分離塔にＤＶＢ含有量の異なる
３種類の強酸性陽イオン交換樹脂を複層状に充填したも
のである。FIG. 1 is an explanatory diagram of an embodiment of the separation column used in the present invention, in which a separation column consisting of a single unit is filled with three types of strongly acidic cation exchange resins having different DVB contents in a multi-layered manner. It is.
すなわち分離塔ｌの上層部に高ＤＶＢ含有量樹脂Ａを充
填し、その下部に中ＤＶＢ含有量樹脂Ｂを充填し、さら
にその下部に低ＤＶＢ含有量樹脂Ｃを充填したものであ
る。なお２は糖液および溶離水の流入管であり、３は分
離液の集液管、４は底板である。一般にクロマト分離処
理を行なう分離塔の樹脂層高は５ｍ〜１０ｍとするが、
たとえば第１図における全樹脂層高が６ｍの場合は、高
ＤＶＢ含有量樹脂ＡとしてＤＶＤ含有量１０チの強酸性
陽イオン交換樹脂を１ ｔｎ ｒ中ＤＶＤ含有量樹脂Ｂ
としてＤＶＤ含有量６％の強酸性陽イオン交換樹脂をｌ
ｍ 、低ＤＶＢ含有量樹脂ＣとしてＤＶＢ含有量５％
の強酸性陽イオン交換樹脂を４ｍというように。That is, the upper part of the separation column 1 is filled with high DVB content resin A, the lower part is filled with medium DVB content resin B, and the lower part is filled with low DVB content resin C. Note that 2 is an inflow pipe for the sugar solution and eluate water, 3 is a collection pipe for the separated liquid, and 4 is a bottom plate. Generally, the height of the resin layer in the separation tower that performs chromatographic separation treatment is 5 m to 10 m.
For example, when the total resin layer height in Figure 1 is 6 m, a strong acidic cation exchange resin with a DVD content of 10 cm is used as the high DVB content resin A in 1 tn r of the DVD content resin B.
Strongly acidic cation exchange resin with DVD content of 6% as l
m, 5% DVB content as low DVB content resin C
4m of strongly acidic cation exchange resin.
流入管２側から見て、 ＤＶＤ含有量の多いものから順
に少ないものへと段階的に充填する。When viewed from the inflow pipe 2 side, the DVD contents are filled in stages from those with the highest content to those with the lowest content.
なお流入管２が下部に、集液管３が上部にある上昇流式
の分離塔においては前述した樹脂Ａ、Ｂ、Ｃの配列が全
く逆になることは云うまでもない。また前述したように
不可逆膨潤を起こす部分は糖液や溶離水が最初に接触す
る面からそのやや下層が顕著なので、高ＤＶＢ含有量樹
脂Ａおよび中ＤＶＢ含有量樹脂Ｂの樹脂層高をあまり高
くする必要がない。逆に高ＤＶＢ含有量樹脂Ａの樹脂層
高をあまり高くすると分離塔全体の糖の分離性能が低下
するので好ましくない。It goes without saying that in an upflow type separation tower in which the inflow pipe 2 is at the bottom and the liquid collection pipe 3 is at the top, the arrangement of the resins A, B, and C described above is completely reversed. In addition, as mentioned above, the part where irreversible swelling occurs is noticeable in the layer slightly below the surface that is first in contact with the sugar solution and eluent water, so the resin layer height of high DVB content resin A and medium DVB content resin B is not set too high. There's no need to. On the other hand, if the resin layer height of the high DVB content resin A is made too high, the sugar separation performance of the entire separation column will deteriorate, which is not preferable.
第２図は本発明に用いる分離塔の他の実施態様を示した
説明図であり、単基からなる分離塔にＤＶＢ含有量の異
なる２種類の強酸性陽イオン交換樹脂を離間して充填し
たものである。すなわち分離塔１の中間部より上方に支
持板５を付設し、当該支持板５の上部に高ＤＶＢ含有量
樹脂Ａを充填し下部に低ＤＶＢ含有量樹脂Ｃを充填する
。なお第２図において２は流入管、３は集液管であシ、
高ＤＶＢ含有量樹脂Ａ側の集液管３′と低ＤＶＢ含有量
樹脂Ｃ側の流入管２′を連通管６で連通ずる。たとえば
第２図の場合高ＤＶＤ含有量樹脂ＡとしてはＤＶＤ含有
量８％の強酸性陽イオン交換樹脂を２ ｍ ＋および低
ＤＶＢ含有量樹脂ＣとしてはＤＶＢ含有量５係の強酸性
陽イオン交換樹脂を４ｍというように充填する。また第
３図は分離塔を２塔とし、それぞれの分離塔にＤＶＢ含
有量の異なる２種類の強酸性陽イオン交換樹脂を別々に
充填したもので、前段の分離塔ｌに高ＤＶＢ含有量樹脂
Ａを充填し、後段の分離塔１に低ＤＶＢ含有量樹脂Ｃを
充填したものである。なお前段の分離塔ｌの集液管３′
と後段の分離塔１の流入管２′を連通管６で連通ずるこ
とは云うまでもない。さらに第４図は分離塔を２塔とし
、当該２塔の分離塔にＤＶＢ含有量の異なる３種類の強
酸性陽イオン交換樹脂を充填したものであり、前段の分
離塔ｌの支持板５の上部に高ＤＶＢ含有量樹脂Ａを、ま
た前段の分離塔ｌの支持板５の下部に中ＤＶＢ含有量樹
脂Ｂを、さらに後段の分離塔１に低ＤＶＢ含有量樹脂Ｃ
をそれぞれ充填したものである。なおそれぞれ対応する
集液管３′と流入管２′を連通管６で連通ずることは第
２図、第３図と同様である。FIG. 2 is an explanatory diagram showing another embodiment of the separation column used in the present invention, in which two types of strongly acidic cation exchange resins having different DVB contents are packed spaced apart in a separation column consisting of a single unit. It is something. That is, a support plate 5 is attached above the middle part of the separation column 1, and the upper part of the support plate 5 is filled with high DVB content resin A, and the lower part is filled with low DVB content resin C. In addition, in Fig. 2, 2 is an inflow pipe, 3 is a liquid collection pipe,
The liquid collection pipe 3' on the high DVB content resin A side and the inlet pipe 2' on the low DVB content resin C side are communicated through a communication pipe 6. For example, in Figure 2, the high DVD content resin A is a strongly acidic cation exchange resin with a DVD content of 8%, and the low DVB content resin C is a strongly acidic cation exchange resin with a DVB content of 5%. Fill with resin to a depth of 4 m. In addition, in Figure 3, there are two separation columns, each of which is filled with two types of strongly acidic cation exchange resins with different DVB contents, and the former separation column 1 is filled with a high DVB content resin. A was filled, and the latter separation column 1 was filled with a low DVB content resin C. In addition, the liquid collecting pipe 3' of the separation column 1 in the upper stage
Needless to say, the inlet pipe 2' of the separation column 1 in the latter stage is communicated with the inlet pipe 2' through the communication pipe 6. Furthermore, in FIG. 4, there are two separation towers, and the two separation towers are filled with three types of strongly acidic cation exchange resins with different DVB contents. High DVB content resin A is placed in the upper part, medium DVB content resin B is placed in the lower part of the support plate 5 of the preceding separation column 1, and low DVB content resin C is placed in the subsequent separation column 1.
filled with each. Note that the corresponding liquid collecting pipe 3' and inflow pipe 2' are communicated with each other through the communicating pipe 6, as in FIGS. 2 and 3.
、 本発明においては第１図ないし第４図に示したごと
（、ＤＶＢ含有量の異なる少なくとも２種類以上の強酸
性陽イオン交換樹脂を。In the present invention, at least two or more types of strongly acidic cation exchange resins having different DVB contents are used as shown in FIGS. 1 to 4.
ＤＶＢ含有量の多いものから順に少ないものへと段階的
に充填した分離塔を用いるが、第２図、第３図に示した
ように、 ＤＶＢ含有量の異なる２種の当該陽イオン交
換樹脂を用いれば本発明の目的を充分に達成することが
できる。A separation column is used that is packed in stages from high to low DVB content, but as shown in Figures 2 and 3, two types of cation exchange resins with different DVB contents are used. If used, the purpose of the present invention can be fully achieved.
もちろん第１図、第４図に示したごとく３種類以上の当
該陽イオン交換樹脂を用いることもでき、何種類の当該
陽イオン交換樹脂を用いるかは情況に応じて決定すると
よい。なお高ＤＶＢ含有量樹脂ＡとしてはＤＶＤ含有量
が８〜１０チのものを用いることが好ましく、その樹脂
層高はすくなくとも０．５ｍ以上とすることが望ましい
。Of course, three or more types of cation exchange resins can be used as shown in FIGS. 1 and 4, and how many types of cation exchange resins to use may be determined depending on the situation. As the high DVB content resin A, it is preferable to use one having a DVD content of 8 to 10 inches, and the height of the resin layer is preferably at least 0.5 m or more.
また分離塔にＤＶＢ含有量の異なる強酸性陽イオン交換
樹脂を充填する場合、第１図に示したごとく複層状にし
てもさしつかえないが。In addition, when the separation column is filled with strongly acidic cation exchange resins having different DVB contents, it may be arranged in a multi-layered structure as shown in FIG.
複層状に充填した場合はそれぞれの樹脂を別別に取り出
す際に若干不便であり、またたとえば逆洗をした場合、
各樹脂が混合することもあるので、第２図、第３図、第
４図に示したごと＜ ＤＶＢ含有量の異なる樹脂を離間
して充填することが望ましい。When filled in multiple layers, it is somewhat inconvenient to take out each resin separately, and when backwashing is performed, for example,
Since each resin may be mixed, it is desirable to fill the resins with different DVB contents separately as shown in FIGS. 2, 3, and 4.
また分離塔の集散機構は２通常、第５図に示したように
分離塔ｌの横断面に対して多数の集液管３＋（３’）を
平行に並設し、当該集液管３、（３’）の一端にヘッダ
ー管７を連通したものを用いるが、 −
；妄；苓；第６図に示したごとく底板４あるいは支持板
５を波形とし、波形の頂部を間で形成される窪み部に各
集液管’ｓ ＋ （３’）を付設することが好ましい。In addition, the collection and dispersion mechanism of the separation tower 2 usually has a large number of liquid collection pipes 3+ (3') arranged in parallel to the cross section of the separation tower 1, as shown in FIG. A header pipe 7 is connected to one end of (3'), but as shown in Fig. 6, the bottom plate 4 or support plate 5 is corrugated, and the top of the corrugation is formed between. It is preferable to attach each liquid collecting pipe 's + (3') to the recessed part.
なお第７図に示したごとく底板４あるいは支持板５は波
形板８と平板９で構成するが、各集散管３．（３’）の
下部に集液孔あるいは集液スリットからなる集水部１０
を設けることにより２分離液は波形板８の面に沿って矢
印線のごとく流れ、これによシ底板４あるいは支持板５
と各集液管３゜（３′）の間に液が滞留するデッドスペ
ースが生じることなく、糖の腐敗を効果的に防止できる
とともに１分離曲線のシャープな各分離液を得ることが
できる。As shown in FIG. 7, the bottom plate 4 or support plate 5 is composed of a corrugated plate 8 and a flat plate 9, and each collector tube 3. Water collection part 10 consisting of a liquid collection hole or liquid collection slit at the bottom of (3')
2, the separated liquid flows along the surface of the corrugated plate 8 in the direction of the arrow line, and thereby the bottom plate 4 or the support plate 5
Since there is no dead space in which the liquid accumulates between the liquid collecting tube 3° (3') and the liquid collecting pipe 3', it is possible to effectively prevent sugar spoilage and to obtain each separated liquid with a sharp one-separation curve.
本発明は以上説明したような分離塔を用い。The present invention uses a separation column as described above.
たとえばブドウ糖と果糖を含有する糖液をクロマト分離
処理する場合は以下のようにして行なう。すなわち常法
により全樹脂量に対して０．１−ｏ、ｚＬ／ｌの当該糖
液を流入管２から流入し１次いで０−１５〜０・２５
ｔ ／ｌの溶離水を流入し、各樹脂層を通過させること
によりクロマト分離を行ない、その流出液を集麻管３か
ら流出せしめ、流出液をフンクション別に採取し、ブド
ウ糖液と果糖液に分離し、この糖液と溶離水の流入と、
流出液をフラクション別に採取する操作とを繰り返して
行なう。For example, when a sugar solution containing glucose and fructose is subjected to chromatographic separation, it is carried out as follows. That is, by a conventional method, the sugar solution of 0.1-o, zL/l based on the total amount of resin was injected from the inflow pipe 2, and then 0-15 to 0.25
chromatographic separation is performed by injecting t/l of elution water and passing it through each resin layer, and the effluent is allowed to flow out from the hemp collection tube 3. The effluent is collected by function and divided into glucose solution and fructose solution. Separate this sugar solution and the inflow of eluate water,
The operation of collecting the effluent by fraction is repeated.
本発明においては糖液あるいは溶離水が最初に接触する
部分に、 ＤＶＢ含有量の多い強酸性陽イオン交換樹脂
を用いているので、従来の分離塔で生じていたような当
該部分の強酸性陽イオン交換樹脂が不可逆膨潤を起すこ
となく、さらに不可逆膨潤が起らないような部分には分
離性能の優れたＤＶＢ含有量の少ない強酸性陽イオン交
換樹脂を用いているので分離塔全体としての分離性能は
ほとんど低下することなく、長期間安定してクロマト分
離処理を行なうことができる。なお使用する樹脂のＤＶ
Ｂ含有量が同じ場合、その粒子径が小さいもの程、糖の
分離性能が上昇する傾向にあるので１本発明においては
圧力損失があまり大きくならない程度に、 ＤＶＤ含有
量の多い樹脂中程その粒子径を小さくすることによシ。In the present invention, a strongly acidic cation exchange resin with a high DVB content is used in the part that first comes into contact with the sugar solution or eluate water, so that the strong acid cation exchange resin in this part, which occurs in conventional separation columns, is eliminated. The ion exchange resin does not cause irreversible swelling, and strong acidic cation exchange resins with low DVB content and excellent separation performance are used in areas where irreversible swelling does not occur, allowing for separation as a whole in the separation column. Chromatographic separation can be performed stably for a long period of time with almost no deterioration in performance. Furthermore, the DV of the resin used
When the B content is the same, the smaller the particle size, the higher the sugar separation performance. Therefore, in the present invention, the particles in the middle of the resin with a high DVD content are adjusted to the extent that the pressure loss does not become too large. By reducing the diameter.
ＤＶＤ含有量の多い樹脂部分の分離性能の低下を粒子径
を小さくすることによりカバーすることもでき、このよ
うにすれば分離塔全体の分離性能の低下をより完壁に防
止することができる。The decrease in separation performance of the resin portion with a high DVD content can be compensated for by reducing the particle size, and in this way, the decrease in separation performance of the entire separation column can be more completely prevented.
以下に本発明の効果をより明確にするために実施例を説
明する。Examples will be described below to make the effects of the present invention more clear.
参考例
ＤＶＢ含有量５％、６％、８％、１０％の強酸性陽イオ
ン交換樹脂をそれぞれカルシウム形とし。Reference Examples Strongly acidic cation exchange resins with DVB contents of 5%, 6%, 8%, and 10% were each made into calcium form.
当該４種類の樹脂層々２０ｒｒｔｌをカラムに充填し、
当該カラムに６０℃の条件下で５ｏｔｗｌのブドウ糖５
２％、果糖４３係、Ｂｘ４５の糖液、および５０１１ｔ
ｌの溶離水を交兄に通液し、糖液と溶離水の１回の通液
を１サイクルとした場合、これを２，０００サイクル行
ない、その後の各樹脂の水分含有率の増加を測定したと
ころ、第１表のごとくなった。Fill a column with 20rrtl of the four types of resin layers,
5 otwl of glucose was added to the column at 60°C.
2%, fructose 43, Bx45 sugar solution, and 5011t
1 of eluent water is passed through the exchange tube, and one cycle is defined as passing the sugar solution and eluent water once. This is repeated 2,000 times, and the increase in water content of each resin is then measured. The result was as shown in Table 1.
第１表 以上の結果により、水分含有率の増加率。Table 1 Based on the above results, the increase rate of moisture content.
換言すれば不可逆膨潤率はＤＶＢ含有量が多くなればな
る程、小さくなることが解る。In other words, it can be seen that the larger the DVB content, the smaller the irreversible swelling rate.
実施例
内径４’ｉ’、５１１１１１１．長さ１．７ｍのジャケ
ット付アクリル製カラム４本を１組とし、これらを４組
用い、 （１） ２本のカラムにＤＶＢ含有量１０％の
強酸性陽イオン交換樹脂を充填し、のこシの２本のカラ
ムにＤＶＤ含有量６％の強酸性陽イオン交換樹脂を充填
し、 ＤＶＢ含有量の多い順から４本直列に配置したも
の、 （２） １本のカラムにＤＶＢ含有量１りの強酸
性陽イオン交換樹脂を充填し、のこり３本のカラムにＤ
ＶＢ含有量６慢の強酸性層イオン交換樹脂を充填し。Example inner diameter 4'i', 5111111. A set of four jacketed acrylic columns with a length of 1.7 m was used. (1) Two columns were filled with strongly acidic cation exchange resin with a DVB content of 10%, and the (2) Two columns filled with strongly acidic cation exchange resin with a DVD content of 6% and four columns arranged in series in descending order of DVB content. (2) One column with a DVB content of 1 Fill the remaining three columns with strong acidic cation exchange resin and
Filled with strong acid layer ion exchange resin with VB content of 6.
ＤＶＢ含有量の多い順から４本直列に配置したもの、（
３１’４本のカラム全部にＤＶＤ含有量６％の強酸性陽
イオン交換樹脂を充填し、４本直列に配置したもの、
（４１４本のカラム全部にＤＶＤ含有量１０％の強酸性
陽イオン交換樹脂を充填し、４本直列に配置したものの
４組の多段からなる分離カラムを構成し、これら４紐の
分離カシム各々について以下のクロマト分離処理を行な
った。なお全てのカラムの１本あたりの樹脂層高は１．
５ｍとし、樹脂は全て果糖４３％を含むＢｘ ４５の糖
液を用い、当該糖液を３．８５を通液した後、溶離水を
６．４２４通水し、最初の流出液ｃ、３ｔを捨て、以後
の流出液をＡ７ラクシヨン２．４６ｔ、Ｅフラクション
２．４６ｔ、Ｃフラクション１＋８２ｔ、 Ｄフラクシ
ョン１．６１４ 、 Ｅフラクション１．９３７に分取
し。Four wires arranged in series in descending order of DVB content, (
31' All four columns were filled with strong acidic cation exchange resin with a DVD content of 6%, and the four columns were arranged in series.
(All 414 columns are filled with a strong acidic cation exchange resin with a DVD content of 10%, and 4 columns are arranged in series to form a separation column consisting of 4 sets of multistages. The following chromatographic separation treatment was performed.The resin layer height per column for all columns was 1.
5 m, all of the resin used was a Bx 45 sugar solution containing 43% fructose, and after passing 3.85 ml of the sugar solution, 6.424 ml of elution water was passed through the resin, and the first effluent c, 3 t was The resulting effluent was divided into A7 fraction 2.46t, E fraction 2.46t, C fraction 1+82t, D fraction 1.614, and E fraction 1.937.
Ａフラクションをブドウ糖液、Ｄフラクションを果糖液
として系外に採取し２次いでＢフラクション（２・４６
７）、糖液（１，ｔｌｔ ） 、 ｃフラクション（ｌ
・８２７）、Ｂフラクション（ｘ、９３ｚ）。The A fraction was collected as a glucose solution, the D fraction was collected as a fructose solution, and then the B fraction (2.46
7), sugar solution (1, tlt), c fraction (l
・827), B fraction (x, 93z).
溶離水（２，３５ｔ）の順に通液し、再びＡ 、、 Ｂ
。Eluent water (2,35t) was passed in this order, and then A, B
.
Ｃ，Ｄ、Ｅのフラクションに分取して、同じようにＡフ
ラクションとＤフラクションをブドウ糖液、果糖液とし
て系外に採取するというような常法の循環通液によるク
ロマト分離処理を行なった。このクロマト分離処理の７
゜８ 、９ 、１０サイクルにおけるＤフラクションの
果糖液の平均分析値は第２表の通シであった。A conventional chromatographic separation process was carried out by separating the C, D, and E fractions, and similarly collecting the A and D fractions as a glucose solution and a fructose solution from the system. 7 of this chromatographic separation process
The average analytical values of the fructose solution of the D fraction in cycles 8, 9, and 10 were as shown in Table 2.
第２表
第２表に見られるとと（ＤＶＢ含有量１０チの強酸性陽
イオン交換樹脂金てを用いた分離カラムは果糖含有率が
小さく分離性能が低下しているが９本発明における（１
） 、 （２１においてはＤＶＢ含有量ｌＯ％の強酸性
陽イオン交換樹脂を用いているにもかかわらず、 ＤＶ
Ｂ含有量６％の強酸性陽イオン交換樹脂をその下部に有
しているので、それ程分離性能が低下しておらず、特に
本発明の（２）においては、その分離性能は全てのカラ
ムにＤＶＢ含有量６係の強酸性陽イオン交換樹脂を用い
た（３）のそれとほぼ同様である。As shown in Table 2, the separation column using a strongly acidic cation exchange resin with a DVB content of 10% has a low fructose content and has poor separation performance; 1
), (Despite using a strongly acidic cation exchange resin with a DVB content of 10% in 21, DV
Since it has a strongly acidic cation exchange resin with a B content of 6% in its lower part, the separation performance does not deteriorate that much, and especially in (2) of the present invention, the separation performance is superior to all columns. This is almost the same as that of (3) using a strongly acidic cation exchange resin with a DVB content of 6.
第１図ないし第７図はいずれも本発明の実施態様を示す
もので、第１図は本発明に用いる分離塔の説明図であり
、第２図、第３図。
第４図はいずれも本発明に用いる分離塔の他図であシ、
さらに第７図は集液機構の拡大縦断面図である。
１・・・分離塔 ２・・・流入管
３・・・集液管 ４・・・底板
５１９．支持板 ６・・・連通管
７・・・ヘッダー管 ８・・・波形板
９・・・平板 ｌＯ・・・集水部
Ａ・・・高ＤＶＢ含有量樹脂
Ｂ・・・中ＤＶＢ含有量樹脂
Ｃ・・・低ＤＶＢ含有量樹脂 −
七・・・頂部
第１図 第２図
第３図
第４図
第５図1 to 7 all show embodiments of the present invention, with FIG. 1 being an explanatory diagram of a separation column used in the present invention, and FIGS. 2 and 3. Figure 4 shows other views of the separation tower used in the present invention.
Furthermore, FIG. 7 is an enlarged longitudinal sectional view of the liquid collection mechanism. 1... Separation tower 2... Inflow pipe 3... Liquid collection pipe 4... Bottom plate 519. Support plate 6...Communication pipe 7...Header pipe 8...Corrugated plate 9...Flat plate lO...Water collection part A...High DVB content resin B...Medium DVB content resin C...Low DVB content resin - Seven...Top Figure 1 Figure 2 Figure 3 Figure 4 Figure 5
Claims (1)
をクロマト分離するにあたシ。 ジビニルベンゼン含有量の異なる少なくとも２種類以上
の強酸性陽イオン交換樹脂を。 ジビニルベンゼン含有量の多いものから順に少ないもの
へと段階的に充填した分離塔を用い、ジビニルベンゼン
含有量の多い強酸性陽イオン交換樹脂側から前記糖液を
通液し２次いで溶離水を通水することを特徴とする糖液
のクロマト分離処理方法 （２）ジビニルベンゼン含有量の異なる強酸性陽イオン
交換樹脂を離間して充填した分離塔を用いる特許請求の
範囲第１項記載の糖液のクロマト分離処理方法 （３）糖液が少なくともブドウ糖と果糖を含む糖液であ
る特許請求の範囲第１項および第２項記載の糖液のクロ
マト分離処理方法[Claims] Next, each saccharide in the sugar solution is chromatographically separated by passing eluent water through it. At least two types of strongly acidic cation exchange resins with different divinylbenzene contents. Using a separation column filled in stages from high to low divinylbenzene content, the sugar solution is passed through from the side of the strongly acidic cation exchange resin containing the highest divinylbenzene content, and then the eluate water is passed through. (2) A method for chromatographic separation of a sugar solution, characterized in that the sugar solution is water-treated. Chromatographic separation processing method (3) The chromatographic separation processing method for a sugar solution according to claims 1 and 2, wherein the sugar solution is a sugar solution containing at least glucose and fructose.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58120982A JPS6013000A (en) | 1983-07-05 | 1983-07-05 | Chromatographic separation of sugar liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58120982A JPS6013000A (en) | 1983-07-05 | 1983-07-05 | Chromatographic separation of sugar liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6013000A true JPS6013000A (en) | 1985-01-23 |
| JPH0513639B2 JPH0513639B2 (en) | 1993-02-23 |
Family
ID=14799850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58120982A Granted JPS6013000A (en) | 1983-07-05 | 1983-07-05 | Chromatographic separation of sugar liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6013000A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63231262A (en) * | 1987-03-19 | 1988-09-27 | Sekisui Chem Co Ltd | Method for changing liquid composition in column and column supporting device |
-
1983
- 1983-07-05 JP JP58120982A patent/JPS6013000A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63231262A (en) * | 1987-03-19 | 1988-09-27 | Sekisui Chem Co Ltd | Method for changing liquid composition in column and column supporting device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0513639B2 (en) | 1993-02-23 |
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