JPH0311094A - Fractionation of sorbose - Google Patents

Abstract

PURPOSE:To effectively separate and recover sorbose and utilize the heretofore discarded effective components by subjecting a sorbose-containing solution to a chromatographic treatment using a salt-type strongly acidic cation exchange resin as a filler. CONSTITUTION:A sorbose-containing solution is subjected to chromatographic development at a column temperature of preferably 43-70 deg.C using a salt-type strongly acidic cation exchange resin as a filler and fractionated into a pre- sorbose dilute fraction, a sorbose fraction and a post-sorbose dilute fraction. A sorbose solution having increased sorbose purity is obtained by collecting the sorbose fraction. The above resin is preferably produced by sulfonating a styrene-divinylbenzene copolymer and converting the obtained strongly acidic cation exchange resin into a salt. The developing agent is usually water.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a method for fractionating and purifying sorbose from a solution containing sorbose.

[Prior Art] Sorbose, which is a raw material for ascorbic acid synthesis, is synthesized by fermentation using glucose as a starting material and sorbitol. In this step, sorbose is purified and separated from the fermentation liquid by crystallization. Therefore, a large amount of sorbose, which is the desired product, remains in the crystallization mother liquor together with other saccharides, nurturing acids, and salts which are by-products. However, since there has not yet been a method for effectively separating and recovering sorbose in an industrially efficient manner, the crystallization mother liquor had to be disposed of as waste liquid, causing a large loss of sorbose.

[Problems to be Solved by the Invention] The purpose of the present invention is to make it possible to industrially utilize active ingredients that were conventionally discarded by efficiently separating and recovering sorbose from a solution containing sorbose. .

[Means for Solving the Problems] As a result of intensive studies to solve these problems, the present inventors have developed a solution containing sorbose using a cation exchange resin prepared in a salt form as a separating agent and water as a developing agent. The present invention was completed by discovering that sorbose can be very effectively separated from other coexisting components by chromatographic separation. That is, the present invention basically performs chromatographic separation of a solution containing sorbose using a salt-shaped steel cation exchange resin as a separating agent and water as a developing agent, thereby separating the solid content contained in the solution. The present invention provides a method for fractionating sorbose characterized by relatively increasing the sorbose content, and more precisely, it involves chromatographically developing a solution containing sorbose using a salt-type strongly acidic cation exchange resin as a filler. sorbose fractionation into a pre-sorbose diluted fraction, a sorbose fraction, and a post-sorbose diluted fraction, and a sorbose solution with relatively improved sorbose purity is obtained by collecting the sorbose fraction. It is the law.

The present invention will be explained in detail below.

As the cation exchange resin in the present invention, a strongly acidic cation exchange resin which is a sulfonated product of styrene-divinylbenzene copolymer is usually used. Examples of this type of cation exchange resin include Levacint 5100 and Levacint 5109.
, 5P112, TSW40 (manufactured by Bayer),
Diaion 5KIB (manufactured by Mitsubishi Chemical Corporation), DOWEX HCR-3 (manufactured by Dow Chemical Company), Amberlite 1R
120, 1R122 (manufactured by Rohm and Haas)
Any of those commercially available under various trademarks, such as, can be suitably used. Among them, those with a narrow particle size distribution such as Revachi MD31368 and DOWEX MONOSPHERE 99, which are commercially available for chromatographic separation, are more suitable because they provide a good degree of chromatographic separation. In order to use these cation exchange resins for this purpose, it is necessary to prepare them in a salt form.

The salt types include alkali metal salts such as Na and Ni; or alkaline earth metal salts such as Ca and Ba; furthermore, Pb,
One or more types of Ag salt types are used as appropriate.

The solution containing sorbose, which is the raw material for recovering sorbose used in the present invention, only needs to contain sorbose in the solid content dissolved in the solution. Examples include saccharides and organic acids, but other substances derived from glucose, which is the raw material for sorbose, can be used.

As an example of a specific chromatography separation operation according to the present invention, a column is first filled with a cation exchange resin, and then filled with water to near the surface of the resin layer, and then a predetermined amount of the liquid to be treated containing sorbose is supplied to the top of the resin layer. 1. After that, water, which is a developing agent, is supplied from the top of the column, and at this time, while drawing the liquid from the bottom of the column, adjust the amount of water drawn so that the liquid level at the top of the column remains slightly above the surface of the resin layer. is preferred. The liquid that flows out from the bottom of the column is first a liquid containing almost no sorbose and mainly other dissolved solids (pre-sorbose diluted fraction), and then a liquid rich in sorbose (sorbose fraction). After that, the liquid (-
The sorbose dilute fraction) flows out. If the sorbose fraction is recovered from this effluent fraction, the sorbose content in the dissolved solids is relatively larger than the sorbose content in the solids dissolved in the raw material sorbose solution. It is possible to increase the sorbose content and recover sorbose. After the diluted sorbose fraction has finished flowing out of the column, if the liquid to be treated and water are repeatedly supplied, the cation exchange resin in the column can be used again without being regenerated. The above-mentioned method is generally referred to as a batch method in the chromatographic separation method, but
The method of the present invention can be carried out not only by a batch method but also by a known chromatographic separation method.

The appropriate column temperature range for carrying out the above chromatographic separation method is usually 30°C to 80°C, preferably 40°C.
℃~70℃. When the temperature exceeds 80°C, the rate of sorbose contamination in the post-sorbose diluted fraction increases, and below 30°C, the rate of sorbose contamination in the pre-sorbose diluted fraction increases, and in both cases, the sorbose recovery rate in the sorbose fraction decreases. This causes the inconvenience of doing so.

Hereinafter, embodiments of the present invention will be explained in detail using Examples.

In the following, % represents the composition fraction based on the total dissolved solids in the solution, and all percentages are based on weight. Liquid chromatography was used to analyze the compositional components in the solution, and the compositional fraction was determined from the area ratio of the chromatography.

[Example 1] A column with a diameter of 20.0 mm and a height of 1200 mm was coated with Bayer's strongly acidic cation exchange resin Revatit TSW4ONa.
The mold was filled to a height of 1200 mm, and a tube for supplying the stock solution to be treated was provided so as to be almost in contact with the surface of the resin layer. From this stock solution supply pipe, the stock solution to be treated having the composition shown in Table 1 is supplied at a rate of 314 m1/hour.
7 ml was supplied, and then water was supplied from the same supply pipe at a rate of 314 ml/hour. While the liquid was being supplied to the top of the column, the liquid was extracted from the bottom of the column at the same rate as the supply rate. The column temperature was set at 50' by circulating hot water through the jacket attached to the column.
I decided to keep it at C.

As the sorbose solution to be treated, a sorbose crystallization mother liquor derived from a sorbose fermentation liquid having a composition of 60.3% total solid content and 457% sorbose purity in solid content was used.

The effluent from the above column is divided into two parts, the first half of which contains dissolved solids in the effluent, as the "pre-sorbose diluted fraction", the middle part as the "sorbose fraction", and the second half as the "post-sorbose diluted fraction". did. Its composition is shown in Table 1. The total solid content concentration (%) in the table below represents the total solid content dry form 1 (g) dissolved in 100 ml of both solutions, and the sorbose purity in the solid content. represents the weight percentage of sorbose in the dry weight of solids dissolved in each percentage solution. Further, the sorbose recovery rate represents the weight percentage of sorbose in each of the two solutions relative to the weight of sorbose in the original solution subjected to separation.

Table 1 [Example 2] The results shown in Table 2 were obtained by changing the strongly acidic cation exchange resin of Example 1 to Revachit MD3136SCa type manufactured by Bayer AG, and setting the column temperature to 60° C. and keeping the other conditions the same.

Table 3 Table 2 (Example 3) The strongly acidic cation exchange resin of Example 1 was changed to Revachit MD31368 manufactured by Bayer, and the column temperature was set at 70°C.
The results shown in Table 3 were obtained under the same conditions.

[Example 4] The strongly acidic cation exchange resin used in Example 1 was changed to Revatit MDS1368Na type manufactured by Bayer, and the column temperature was increased to 40°C.
The results shown in Table 4 were obtained under the same conditions as above.

Table 4 Table 5 [Example 5.6] [Comparative Example 1.2] The strongly acidic cation exchange resin of Example 1 was changed to Revachit MDS1368Na type manufactured by Bayer, and the column temperature was set to the values shown in Table 5. The results shown in Table 5 were obtained under the same conditions.

Claims (2)

[Claims] (1) A solution containing sorbose is chromatographically developed using a salt-type strongly acidic cation exchange resin as a packing material to fractionate it into a pre-sorbose diluted fraction, a sorbose fraction, and a post-sorbose diluted fraction. A sorbose fractionation method characterized by obtaining a sorbose solution with relatively improved sorbose purity by collection. (2) The method for fractionating sorbose according to claim 1, wherein the chromatographic development is carried out at a temperature range of 30°C to 80°C.