JPH0383991A - Separation of glucose - Google Patents

Abstract

PURPOSE:To obtain high purity glucose useful for drugs by recycling under a specific condition an aqueous solution containing an oligosaccharide having >= molecular weight of glucose and maltose through a packed layer filled with a cation exchanger and equipped with the front end connected to the rear end and subjecting to chromatographic separation. CONSTITUTION:An aqueous solution containing an oligosaccharide having >= molecular weight of glucose and maltose is fed from a raw material feed pipe 40 to packed layers 1-8 filled with a cation exchanger wherein the front end is connected to the rear end and water as an eluent is fed from a water inlet pipe 30 to the packed layers. The ratio of empty column velocity of fluid in concentration zones of adsorption substance to mobile velocity of adsorbent is made 0.4-0.7 and the similar ratio of non-adsorption substance in recovery zones is made 0.3-0.6 by a pseudo-transfer layer wherein a liquid is recycled from the upper stream through desorption zones 1 and 2 of the adsorption substance from a feed part of eluent to a release part of the adsorption substance, the concentration zones 3 and 4 of the adsorption substance from a removal part of eluent to a raw material feed part, adsorption zones 5 and 6 of the adsorption substance from the feed part of eluent to a removal part of the non-adsorption substance and the recovery zones 7 and 8 of the non-adsorption from the recovery part of eluent to the feed part of eluent and positions of the feed part and the removal part are intermittently transferred to separate glucose.

Description

[Detailed Description of the Invention] <Industrial Application Field> In recent years, highly purified glucose has been required for pharmaceutical use and as a raw material for vitamin C, sorbitol, etc., but the present invention In particular, it is a method for continuously chromatographically separating an aqueous glucose solution containing almost no oligosaccharides from an aqueous solution containing glucose and oligosaccharides using a simulated moving layer.

<Conventional technology> Conventionally, high-purity glucose has been produced from an aqueous solution containing glucose and oligosaccharides using the crystallization method, but since it involves a phase transformation from a liquid phase to a solid phase, it cannot be handled in the WJ example. In some cases, the solubility of glucose is high, requiring careful handling of the mother liquor, and the crystallization method itself requires advanced technology and experience.

On the other hand, glucose and oligosaccharides have been separated using a pseudo moving layer using a chromatographic separation method without using the above-mentioned crystallization method.

However, in the conventional separation method using a pseudo-moving bed, highly pure glucose cannot be separated with a high recovery rate.

<Problems to be Solved by the Invention> An object of the present invention is to provide a separation method capable of separating high-purity glucose from a mixed aqueous solution of glucose and oligosaccharides at a high recovery rate using a pseudo-moving bed. do.

<Means for Solving the Problems> The present inventors have studied a method of continuously chromatographically separating a glucose water WI solution containing almost no oligosaccharides from an aqueous solution containing glucose and oligosaccharides using a pseudo mobile layer. As a result, the ratio β of the circulating flow rate to the fixed bed flow rate was determined in the pseudo-moving bed, which formed a desorption zone for sorbed substances, a concentration zone for sorbed substances, an adsorption zone for sorbed substances, and a recovery zone for non-sorbed substances. 0 in the sorbent concentration zone.
The inventors have discovered that highly pure glucose can be efficiently separated by setting the temperature to 4 to 0.7 degrees and further setting the temperature to 0.3 to 0.6 in the non-sorbing substance recovery zone, and have thus arrived at the present invention.

That is, the present invention is a method for continuously chromatographically separating an aqueous solution containing glucose and an oligosaccharide having a molecular weight greater than maltose as a raw material into an aqueous solution containing glucose and an aqueous solution containing the oligosaccharide using water as an eluent. , a desorption zone for sorbent substances from an eluent supply section to a sorbent extraction section; A concentration zone for sorbent substances from the extraction section to the raw material supply section, an adsorption zone for sorbed substances from the supply section to the non-sorbent material extraction section, and a non-sorption zone from the withdrawal section to the eluent supply section. In a separation method using a pseudo-moving bed, which comprises forming four zones of a substance recovery zone in the above order from upstream, circulating the fluid, and intermittently moving the positions of the supply section and the withdrawal section in the downstream direction. , the ratio β3 of the superficial flow velocity of the circulating fluid in the sorbent concentration zone to the apparent moving velocity of the adsorbent is 0°4 to 0. 7, and the ratio β11t of the superficial flow velocity of the circulating fluid in the recovery zone of non-adsorbed substances to the apparent moving velocity of the adsorbent is 0.3 to 0.7. 6 is a method for separating glucose.

Detailed description of the present invention> The present invention will be explained in detail below.

FIG. 1 is an explanatory diagram showing the flow of a simulated moving bed chromatographic separation apparatus as an example of an embodiment of the present invention.

In FIG. 1, the pseudo mobile bed is divided into eight unit separation columns, and each unit separation column is filled with a salt-type cation exchanger that adsorbs a larger amount of glucose than oligosaccharides. As the cation exchanger, various commercially available cation exchange resins or zeolites can be used. Usually, a strongly acidic cation exchange resin in which a sulfonic acid group is bonded to a crosslinked copolymer of styrene and divinylbenzene is used.

Cation exchange resins are usually used to increase the difference between the adsorption power for glucose and the adsorption power for oligosaccharides.
Used in sodium, potassium, or calcium form.

In addition, as a glucose raw material, the total sugar concentration is usually 40~
An aqueous solution with a glucose content of 75% by weight and a glucose content of 70-97% by weight based on total sugars is used.

A valve 11 is provided in the fluid passage connecting each unit separation column 1 to 8.
Glucose fraction liquid extraction pipe 10 via valves 21 to 18, oligosaccharide fraction liquid extraction pipe 20 via valves 21 to 28, glucose raw material introduction pipe 40 via valves 41 to 48, and glucose raw material introduction pipe 40 via valves 31 to 38. The water inflow pipes 30 are communicated with each other. Note that 51 to 58 each indicate a circulation pump.

Next, to explain the operation of the pseudo moving bed, at the time when the glucose raw material liquid is being supplied through the valve 44, the water is flowing through the valve 3.
The glucose fraction is withdrawn through valve 12 and the oligosaccharide fraction is withdrawn through valve 26. In addition, during this operation, a recovery zone (hereinafter referred to as zone 1) of non-sorbed substances in separation towers 8 and 7 is used.
, an adsorption zone for sorbent substances in separation columns 6 and 5 (hereinafter referred to as zone 2), a concentration zone for sorbent substances in separation columns 4 and 3 (hereinafter referred to as zone 3), and an adsorption zone for sorbent substances in separation columns 2 and 1 (hereinafter referred to as zone 3). A desorption zone (hereinafter referred to as zone 4) for the adsorbent is formed. A concentration distribution of each sugar is formed in each zone, and this concentration distribution moves downstream while maintaining its shape. Following this movement, the supply of the glucose raw material liquid to the separation column, the supply of water, the withdrawal of the glucose partitioned liquid, and the withdrawal of the oligosaccharide partitioned liquid are sequentially switched to the downstream side by switching the valves.

Switching may be performed for the four types of pipes at the same time, or may be performed at different times for each pipe.The time for which each method continues to flow in or out depends on the size of the unit packed bed and the strong acid Although it varies depending on the type of ion exchange resin, the flow rate of the liquid flowing down the layer, etc., it is usually several minutes to more than ten minutes.

By this switching, the four zones described above sequentially move their positions in the packed bed in the flow direction and circulate.

The degree of separation of glucose and oligosaccharides in a pseudo-mobile bed using a cation exchanger as a separation agent is influenced by various factors, but a particularly large factor is the superficial flow rate of the circulating fluid in the bed (
The apparent moving speed of the adsorbent (hereinafter referred to as the fixed bed flow rate), that is, the circulating flow rate of the liquid, differs for each zone. The ratio of the circulation flow rate in zone 3 to the fixed bed flow rate (circulation flow rate/fixed bed flow rate) β3 and the zone 1 It was found that the ratio of the circulation flow rate to the fixed bed flow rate (circulation flow rate/fixed bed flow rate) is the value of β1, and these values are each 0. 4-0.7 and 0. 3-0.
It was also found that setting the value of 6 is most suitable for separating glucose and oligosaccharides. In order to obtain more favorable results, the ratio γ between the amount of water supplied and the amount of raw material liquid supplied should be 2 to 2.
It is desirable that it be within the range of 4. If the value of β3 or β1 is not within the above range, the glucose or oligosaccharide will be distributed throughout the packed bed, and the oligosaccharide will be present in the oligosaccharide fraction that is withdrawn or the oligosaccharide will be present in the glucose fraction. becomes mixed in in large quantities. However, if the above conditions are met, glucose will be in zone 3.
In addition, most of the oligosaccharides are distributed in zone 2, and therefore a highly purified glucose aqueous solution can be obtained with a high recovery rate.

Note that in this specification, the fixed bed flow rate is the apparent volume of the cation exchanger in the packed bed divided by the time required for zone 1 to go around the packed bed.

The present invention will be described in detail below, but the present invention is not limited to the following examples.

Example 1 Oligosaccharide containing 96.0% glucose and maltose 3.
7%, fructose 0. Total sugar concentration 60% consisting of 3%
The glucose raw material solution was separated using a simulated moving bed chromatographic separation device according to the flow shown in FIG.

In Figure 1, unit separation columns 1 to 8 are cylinders with an inner diameter of 108 mm and a height of 1.5 m, and inside the cylinder is a sodium-type strongly acidic cation exchange resin Amberly) CG6000 (manufactured by Rohm and Haas). A total of 110L is filled. The inside of each unit separation column was maintained at 60°C. In this pseudo-moving bed, the amounts of glucose raw material solution and water supplied were set at 6. 05L/hr, 19.8L/hr, the extraction amount of the glucose fractionated liquid and the oligosaccharide fractionated liquid is 11, OL/hr, 14.85L/hr, respectively, the circulation flow rate of zone 3 is 45.8L/hr, the fixed bed flow rate 8
In this example, the engine was operated at 5.4L/hr.
The values of β1, β3 and γ are as follows.

β3=0. 536, β1=0. 433γ =
3.27 Table 1 shows the sugar compositions in the glucose fraction and oligosaccharide fraction extracted under steady state conditions.

The recovery rate of glucose in the glucose fraction was 99.
It was 2%.

Table 1 Comparative Example 1 Glucose was separated from a glucose raw material solution having the same composition and sugar concentration as in Example 1 under the following conditions in the same manner as in Example 1.

Glucose raw material liquid supply amount 6.05L/hr Water supply amount 19. 8 L/hr Glucose separation liquid withdrawal amount 11. OL/hr Oligosaccharide separation liquid withdrawal amount 14.85L/hr Circulation flow rate in zone 3 3
9. 4 L/hr fixed bed flow rate 100.
8 L/hrβ3=0.391, β1=0.30
4γ = 3.27 Table 2 shows the sugar compositions in the glucose fraction and oligosaccharide fraction extracted under steady state conditions.

The recovery rate of glucose in the glucose fraction was 80.
It was 1%.

Table 2 Comparative Example 2 Glucose was separated from a glucose raw material solution having the same composition and sugar concentration as in Example 1 under the following conditions in the same manner as in Example 1.

Glucose raw material liquid supply amount 6.05L/hr Water supply amount 19. 8 L/hr Glucose separation liquid withdrawal amount 6. 6 L/hr Oligosaccharide separation extraction amount 19.25L/hr Zone 3 circulation flow rate
38. OL/hr fixed bed flow rate 85
．． 4 L/hrβ3=0.445, β1=0.
290γ = 3.27 Table 3 shows the sugar compositions in the glucose fraction and oligosaccharide fraction extracted in a steady state.

The recovery rate of glucose in the glucose fraction was 79.
It was 3%.

Table 3 Comparative Example 3 Glucose was separated from a glucose raw material solution having the same composition and sugar concentration as in Example 1 under the following conditions in the same manner as in Example 1.

Glucose raw material liquid supply amount 8. 8 L/hr water supply amount 16. 5 L/hr Glucose separation liquid withdrawal amount 11. OL/hr Oligosaccharide separation liquid withdrawal amount 14. 3 L/hr Circulation flow rate in zone 3 45. 8 L/hr fixed bed flow rate
85. 4 L/hrβ3=0.536, β1
=0.472γ =1. 88 Table 4 shows the sugar compositions in the glucose fraction and oligosaccharide fraction extracted under steady state conditions.

The recovery rate of glucose in the glucose fraction was 87.
It was 7%.

Table 4 <Effects of the Invention> According to the present invention, the following effects can be obtained, and the invention is excellent in industrial effects.

(1) Highly purified glucose can be obtained through a simple process.

(2) Glucose can be separated and recovered from the raw material at a high recovery rate without any loss in quality of the raw material.

(3) Separation and recovery can be performed without using reagents, resulting in low running costs.

(4) It can be carried out continuously and industrially.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the flow of a simulated moving bed filled with a cation exchanger used for the separation of glucose according to the present invention. Procedural amendment (voluntary) November 6, 2017

Claims (1)

[Scope of Claims] 1. A method in which an aqueous solution containing an oligosaccharide having a molecular weight greater than glucose and maltose is used as a raw material and is subjected to continuous chromatographic separation using water as an eluent into an aqueous solution containing glucose and an aqueous solution containing the oligosaccharide. The desorption of the sorbed substance from the eluent supply section to the sorbed substance extraction section is performed in a packed bed filled with a cation exchanger and whose front end and rear end are connected by a fluid passage. a concentration zone for sorbent substances from the extraction section to the raw material supply section, an adsorption zone for sorption substances from the supply section to the non-sorbent material extraction section, and a zone from the extraction section to the eluent supply section. By a pseudo-moving bed, which consists of forming four zones of the recovery zone for non-sorbed substances in the above order from upstream, circulating the fluid, and intermittently moving the positions of the supply section and the extraction section in the downstream direction. In the separation method, the ratio β3 of the superficial flow rate of the circulating fluid in the sorbent concentration zone to the apparent moving velocity of the adsorbent is set to 0.4 to 0.7, and the ratio β3 of the circulating fluid in the non-sorbing substance recovery zone is set to 0.4 to 0.7. The ratio β1 of the superficial flow velocity to the apparent moving velocity of the adsorbent is 0.
．． 3 to 0.6. A method for separating glucose. 2. The ratio γ of the eluent supply amount to the raw material supply amount is 2 to 4.
The method for separating glucose according to claim 1, characterized in that: