JPH05204A - Separation of multicomponent system and device - Google Patents

Abstract

PURPOSE:To separate fractions enriched with the respective components from the fluid of a mixture containing at least three components. CONSTITUTION:The fluid of a raw material containing at least three components different in affinity for an adsorbent is allowed to flow to the circulation system of many unit packed tower groups which are packed with the solid adsorbent and provided in an endless series. An adsorption zone is formed by successively splitting up the same into the component strong in affinity for the adsorbent from the component weak in affinity therefor. The fluid of a raw material is supplied from the top of the unit packed tower enriched with the component weak in affinity. Moreover the flow rate of liquid in the system just under supply of the fluid of the raw material is made equal to the feed rate of this fluid of the raw material by suction force of a circulation pump. Further the first and second stages described below are repeated as one cycle. In the first stage, the component enriched in the unit packed tower of the upstream side from the supply position of the fluid of the raw material is drawn out from the end of this tower. In the second stage, a fraction enriched with the component remaining in the first stage is drawn out from the system while circulating the fluid and also supplying it to the adsorbent. Fractions enriched with the respective components can be efficiently and continuously separated from the fluid of a mixture containing at least three components by using one kind of adsorbent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for separating a mixture fluid containing three or more components into three or more fractions enriched in each component, and more specifically, a gas containing three or more components,
The present invention relates to a method and an apparatus for separating a liquid multi-component system using a chromatographic technique.

[0002]

2. Description of the Related Art A method of separating a plurality of components by a chromatographic method using a solid adsorbent and utilizing a difference in adsorption characteristic for the adsorbent (hereinafter referred to as "chromatographic separation method").
Has been widely used industrially.

The so-called simulated moving bed system, in which a large number of unit packed columns are connected in series by circulation to perform continuous separation, is known as an advantageous apparatus and method with high productivity. Is generally used to fractionate two components from a gas or a liquid, and thus it is difficult to fractionate each of these components from a fluid containing three or more components.

Therefore, another method has been proposed in which each component is fractionated from a fluid containing three or more components.

For example, a method of continuously fractionating each of three or more components using a fixed-bed type chromatographic separation device (Japanese Patent Laid-Open No. 63-158105), and the first and second components. , The stock solution containing the third component, the order of strength of affinity for the three components, the third component> the second component> the first
Unit adsorbent packed with a first adsorbent which is a component of the second adsorbent in which the order of strength of affinity for the three components is second component> third component> first component A method of fractionating and separating these three components by the difference in adsorption characteristics by passing through a simulated moving bed apparatus in which at least four layers are alternately connected with at least four unit-packed towers filled with the agent in series. JP-A-64-80409) has been proposed.

[0006]

However, the above-mentioned method for separating these components into three or more fractions from a fluid containing three or more components has the following problems.

For example, the former method is characterized in that it has a step of "circulating the fluid in the bed without supplying the fluid to the packed bed and withdrawing the fluid from the packed bed". Since it is basically one of the fixed bed chromatographic separation methods, the circulation flow rate is the same throughout the packed bed. Therefore, in the process of circulation, the adsorption zone of the component having a weak affinity for the adsorbent catches up with the adsorption zone of the component having a strong affinity for the adsorbent, and an extra packing layer length is required to prevent overtaking. The size of
The amount of adsorbent is significantly larger than that of the simulated moving bed type device, and there is a problem that the amount of adsorbent to be processed per unit adsorbent, which is an important point industrially in this type of device, is small. There is also a problem that the concentration of the component in the fractionated and recovered fraction is low, and thus the burden of subsequent processing, if necessary, is large.

On the other hand, the latter method of using different kinds of adsorbents has an advantage that the three components can be fractionally separated well, but two kinds of adsorbents having an appropriate adsorption capacity for the three components are used. Selection is required, which limits the applicable target in relation to the components contained in the target fluid.

In order to overcome the drawbacks of these conventional methods,
The present inventor has proposed a novel method, which has never existed before, which can efficiently separate a mixture containing three or more components into three or more fractions enriched in each component (for example, Japanese Patent Application No. 2-40).
No. 2826), it is possible to achieve the same effect as this without using a mechanical means such as a shutoff valve, and therefore, using an existing simulated moving bed in terms of equipment except for the control device. It is an object of the present invention to provide a method for separating a component from a three-component system fluid capable of achieving the above.

Another object of the present invention is to provide a novel method capable of performing fractional separation of three or more components using one kind of adsorbent.

Another object of the present invention is to reduce the amount of adsorbent to be used by utilizing the method of chromatographic separation of a simulated moving bed. Therefore, the equipment is small and the throughput per unit adsorbent is small. It is intended to provide a novel process which is very suitable for implementation on an industrial scale due to its large size.

[0012]

Means and Actions for Solving the Problems A characteristic of the method for fractionating and separating three or more components from a system of a mixture containing multiple components according to the present invention for achieving the above-mentioned object is that the adsorbent is filled. A plurality of unit packed towers are connected in series by a fluid flow pipe in an endless series to form a circulation flow path, and a raw material fluid containing three or more components having different affinities for an adsorbent is allowed to flow through the system. As a result, components with a weak affinity for the adsorbent, components with a strong affinity, and components with an intermediate affinity between these components are formed as adsorption zones that are sequentially divided in the order of affinity for the adsorbent. The raw material fluid is supplied into the system from the top side of the unit packed column where the adsorption zone is formed, and the adsorption zone is enriched in the component having an intermediate affinity upstream from the feed position of the raw material fluid. Has been The first step of performing the operation of extracting the fraction from the end of the column-packed tower, and the step of circulating the fluid in the system without supplying the raw material fluid and supplying the desorbent fluid into the system. The fraction of the component is withdrawn from the end of the unit packed column in which the adsorption zone enriched with the component remaining in one step is formed, and the position for supplying the desorbent fluid and the position for withdrawing the fraction are set. In a method of repeating a second step of sequentially shifting to a unit packed column on the downstream side of the system in accordance with the movement of the enriched adsorption zone as one cycle, the system on the downstream side of the feed position of the raw material fluid The flow rate of the fluid in the system immediately downstream of the raw material fluid supply position in the first step is made equal to the flow rate of the raw material fluid supplied into the system by the suction action of the circulation pump provided therein.

In order to make the fluid flow rate in the system immediately downstream of the above-mentioned raw material fluid supply position equal to the flow rate of the raw material fluid supplied to the system, the suction force of the circulation pump may be given in advance by design and fixed. Alternatively, the liquid flow velocity at the corresponding position may be measured and compared with the supply amount of the raw material fluid to control these flow rates to be equal. It is also preferable to provide a throttle or an orifice in the pipe at the upstream position of the system to which the raw material fluid is supplied in order to improve the controllability.

The first step in the method of the present invention is to form the distribution of the adsorption zone of each component to be extracted in the next cycle while supplying the raw material fluid, and to determine the affinity of the components having already formed the adsorption zone. This is a step of extracting at least one of the components classified as intermediate (hereinafter, referred to as “intermediate component”) out of the system, whereby a large amount of intermediate components can be extruded by the raw material fluid in a short time.

In the second step, while circulating the fluid in the system without supplying the raw material fluid, in short, according to the "simulated moving bed method", each of the desired components other than the intermediate components is The enriched fractions are individually withdrawn from the system, and each component contained in the raw material fluid newly supplied to the system in the first step is sequentially changed from a component having a weak affinity to the adsorbent to a strong component. This is a process for forming a divided adsorption zone. Here, the "simulated moving bed method" used for extracting each component separately while supplying the desorbent fluid is known as a conventional simulated moving bed method except that the raw material fluid is not supplied. For example, in the method described in JP-A-62-91205, particularly page 2, upper right column, second line to lower left column, last line and FIG. 3, the raw material fluid is not supplied and the raw material fluid is supplied. Therefore, the first section and the fourth section may be considered as being the same section, and thus can be carried out as they are. Specifically, while circulating the fluid in the system by a pump or the like, the desorbent fluid is supplied from the upstream side of the adsorption zone where the predetermined components are distributed, and the fraction enriched with the components from the downstream side of the adsorption zone. Can be carried out separately for each of the plurality of components other than the above-mentioned intermediate components, by extracting each of these components and sequentially moving them to the downstream side of the circulation flow in accordance with the movement of the adsorption zone.

The present invention is based on a method of repeating the above-mentioned first step and second step as one cycle, but can be carried out in various modified modes as long as the effect is not impaired. Needless to say.

For example, in the first step, the operation of extracting a predetermined component from the upstream of the feed position of the raw material fluid can be performed not only for one component but also for two or more components. Specifically, when there are a plurality of intermediate components whose affinity to the adsorbent is classified as intermediate, for example, when the raw material fluid contains four components (A to D), the component D having the strongest affinity and the component having the weakest affinity. Two intermediate components C except A,
When B is extracted from the system, the component B having a relatively low affinity among the intermediate components is extracted first from the system, and the component C having a relatively high affinity is extracted later from the system. The component C and the component B can be separated by fractionating the above fraction with time, or if the separation of these components C and B is not particularly required, they can be combined into one fraction.

Further, in the first step, not only the raw material fluid can be supplied to the system, but also the desorbent fluid can be supplied to the system, whereby the supply amount of the raw material fluid and the withdrawal amount of the above-mentioned intermediate component can be controlled. This has the advantage that adjustments (mass balance adjustments) can be made. In particular, there is an advantage that the moving speed of the adsorption zone of a predetermined component can be selected by increasing the flow velocity downstream of the supply of the desorbent fluid. That is, from a component having a weak affinity to the adsorbent to a component having a strong affinity (for example, A, B, C
If the desorbent fluid is supplied from the upstream side of the component C having the strongest affinity to the system in which the adsorption zone that has been sequentially divided into three components) is already formed, The movement of the components A ′, B ′, C ′ and the movement of the weakest component A located downstream of the raw material fluid supply position are performed at a flow rate based on the amount of the supplied raw material fluid, while parallel to this. Then, the withdrawal of the intermediate component B and the movement of the adsorption zone of the component C having the strongest affinity can be carried out at a large flow rate in which the feed amount of the raw material fluid and the feed amount of the desorbent fluid are added. Effectively, the adsorption zone of the component A having a weak affinity (having a high moving speed) distributed downstream of the feed position of the raw material fluid catches up with the adsorption zone of the component C having a strong affinity (having a low moving speed). It can be prevented.
The desorbent fluid may be supplied at the same time as the supply of the raw material fluid to the system or may be sequentially performed.

Furthermore, in the first step, not only the fraction enriched with the intermediate component but also the fraction enriched with other components can be withdrawn in parallel at a predetermined position.

As described above, in the case of extracting a plurality of fluids from the system in the first step, (n-1) of the plurality of piping paths (n) for extracting the fluids, or By providing the flow rate adjusting means in all the pipe paths (n), the total inflow amount of the fluid (in the case of only the raw material fluid or in the case of the two raw material fluids and the desorbent fluid) supplied to the system, It is necessary to equalize the total outflow of fluid withdrawn. When the flow rate adjusting means is not provided in one of the piping paths, the outflow rate of this path is given by the difference between the total inflow quantity and the outflow quantity from the other paths.

The operation of repeating the above-described first step and second step of the present invention describes the state where the apparatus is continuously operated. Prior to the step (1), an operation for supplying a raw material fluid containing three or more components having different affinities to the adsorbent to the system to form an adsorption zone in which components having a weak affinity for the adsorbent are sequentially divided into strong components. You may perform the pre-process which performs only only.

In the present invention, the following third step can be further performed after the above-mentioned second step. That is, while circulating the fluid in the system, supply of the desorbent fluid and the intermediate component to the adsorption zones of the respective components that are separated in the circulation direction and are distributed separately from weak ones to strong ones. The enriched fractions of each component containing is extracted from the separation system separately, and the supply of the desorbent fluid to each component and the extraction position of the fraction are sequentially circulated in accordance with the movement of the adsorption zone. This is a step of shifting to the downstream side of the flow.

In this step, each component in the raw material fluid supplied in the first step moves to the zone enriched with each component in the second step, and the component having a weak affinity to the adsorbent is removed. Performing this step from the time when adsorbing zones that are sequentially separated into strong components are formed to the desired degree, and the significance of performing this step is that each adsorbing zone that has already completed the desired separation is That is, the continuous extraction of the fractions is performed to cyclically move to a predetermined one cycle end position. Usually, an industrial chromatographic separation device is designed with its application, that is, a separation target system limited, but there is a great demand for using one separation device for a plurality of target systems. As an example, five components (A,
B, C, D, and E) are used as the first step when the raw material fluid containing B, C, D, and E) is fractionated into five components using the method and apparatus of the present invention so that each component becomes a single component , C are separated into one fraction, two components of D and E are separated into one fraction, respectively, and as the second stage, the three components of A, B and C are extracted as one fraction in the first stage. An example is a method in which a mixed fluid of the components is supplied to the same device as the raw material fluid and separated into A, B, and C fractions. In such a case, the difficulty levels of the first-stage separation and the second-stage separation are different. ,
In the middle of the second step, the target separation may be completed before the adsorption zone enriched with each component reaches the predetermined end position of one cycle. At this time, the second step can be further continued, but the circulation is performed without extracting the zone enriched in the intermediate component whose affinity for the adsorbent is classified as intermediate, and the zone is broadened. However, it is impossible to prevent thinning that occurs as a result of spreading.

In the third step, by adding the operation of extracting the intermediate component to the second step, the flow velocity upstream of the extraction point of the intermediate component becomes a flow velocity for moving the intermediate component faster, and Since the flow velocity on the downstream side of the extraction point can be set to the flow velocity that moves the intermediate component slowly, the objective is to prevent the zone enriched with the intermediate component from spreading to the front and rear zones. The added advantage is that all the fractions can be extracted continuously. That is, by designing the apparatus so that the third step can be performed, it is possible to increase the possibility of applying the same apparatus to a plurality of separation target systems.

The method of the present invention can be applied as a method for fractionating and separating three or more components contained in a gas or as a method for fractionating and separating three or more components contained in a liquid. As an industrial object for treating a large amount of fluid, a sugar refining industry that uses an alkali metal type or alkaline earth metal type strongly acidic cation exchange resin as an adsorbent to separate and purify various sugars or sugar alcohol mixtures. The usefulness as an industrial facility is extremely large. Specific examples of such sugar purification include separation of sucrose and other useful substances from molasses, fractionation of isomerized sugars into glucose, fructose and oligosaccharides, and mixed components containing lactose, lactulose and galactose. Separating each component from the mixed solution containing glucose, sucrose, fructooligosaccharide, separating each component from the mixed solution containing glucose, isomaltose, isomaltodextrin, glucose, maltose,
Examples include cases where each component is separated from a mixed solution containing maltodextrin, and each component is separated from a mixed solution containing a sugar alcohol such as sorbitol or maltitol.

The present invention also provides an apparatus having the following features for carrying out the above method.

That is, a unit packed tower group in which a large number of unit packed towers packed with an adsorbent are connected in series by a fluid flow pipe to form a circulation system, and three or more components having different affinities for the adsorbent. One raw material fluid supply means provided so that the raw material fluid containing the above can be supplied from the top of any one unit packed tower in the circulation system, and any one of the unit packed towers in the circulation system is selected. Then, a plurality of desorbent fluid supply means provided so that the desorbent fluid can be supplied from the top of the tower, a circulation pump for circulating the fluid in the circulation system, and any unit packed tower in the circulation system A plurality of fluid withdrawing means provided so that the fluid in the unit packed tower can be withdrawn from the end of the column, and the raw material fluid supplying means and the fluid withdrawing means are operated in a predetermined relationship. , Raw material fluid First control means for operating the circulation pump so that the flow rate of the fluid in the system immediately downstream of the supply position and the supply rate of the raw material fluid are equalized, the desorbent fluid supply means and the fluid withdrawal means are predetermined. Second control means for operating the relationship and moving this relationship to the downstream side of the circulation system over time, and switching between the operation of the circulation system by the first control means and the operation of the circulation system by the second control means. It is a multi-component separating apparatus having control switching means.

[0028]

[Effects of the Invention] According to the above constitution, there is an effect that a mixture containing three or more components can be efficiently separated into three or more fractions enriched in each component.

Further, fractional separation of three or more components can be carried out by using one kind of adsorbent, and further, three or more components from a mixture containing three or more components can be utilized by utilizing the technique of chromatographic separation of a simulated moving bed. There is also an effect that the above fractions can be continuously separated.

Further, according to the present invention, the amount of the adsorbent used is small, the equipment is small, and the treatment amount per unit adsorbent is large, and it is extremely suitable for implementation on an industrial scale. There is an effect that there is.

[0031]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but it is needless to say that the present invention is not limited to the following examples without departing from the gist thereof.

FIG. 1 shows an outline of the structure of an apparatus provided for carrying out the method of the present invention.
In the figure, 1 to 8 are unit packed towers each filled with the same adsorbent, and the unit packed towers 1 to 8 are connected to each other by a pipe so that the liquid can flow, and the last unit packed tower The end of the column 8 is the liquid channel 1 at the top of the unit packing column 1 in the first stage.
They are connected via 0. Reference numeral 9 is a circulation pump which is provided downstream of a supply position of the undiluted solution which will be described later and in the middle of the liquid flow path between the unit packed tower 5.

A liquid supply pipe is connected to the liquid flow path between the unit packed towers 4 and 5, and a raw material liquid supply pipe 11e is connected to the liquid supply pipe via an open / close switchable stock liquid supply valve 5e. In addition to being connected, a common eluent supply pipe 11d is connected through an open / close switching type eluent supply valve 5d for the eluent that is a desorbent fluid. Further, a liquid extraction pipe for extracting the liquid out of the system from the end of the unit packed tower 4 on the upstream side of the stock solution supply position is connected, and this is enriched in each of the three components as described below. The separated fractions are divided into three in the middle so that they can be extracted and fractionated by different routes, and each has a weak affinity for the adsorbent (hereinafter referred to as "component A") and a strong component (hereinafter referred to as "component C"). , Common extraction pipes 11a, 11 for each component through the open / close switching type extraction valves 4a, 4b, 4c for the fraction of the intermediate component (hereinafter referred to as "component B").
It is connected to b and 11c.

Further, the common eluent supply pipe 11d is provided between the unit packed towers 1 to 4, 5 to 8 and 8 to 1, and the common eluent supply valves 2d, 3d, 4d, 6d and 7d, respectively. 8
The supply valves are connected via d and 1d, and the opening and closing of each of these supply valves can be appropriately switched by a controller (not shown) together with the eluent supply valve 5d and the stock solution supply valve 5e.

Similarly to the eluent supply valve, a pipe for extracting a liquid is connected between the unit packed towers 1 to 4, 5 to 8 and 8 to 1. The pipes for withdrawing these liquids are, in the one between the unit packed towers 1 and 2, a withdrawal valve 1a for withdrawing the components A and C,
1c is connected to common extraction pipes 11a and 11c, and in the case between the unit packed towers 2 to 4, the components A to
Common extraction pipe 11a, via extraction valves 2a, 2b, 2c and 3a, 3b, 3c for extracting C
11b and 11c, and unit packing towers 5-8 and 8-
1 is connected to common withdrawal pipes 11a and 11c through withdrawal valves 5a to 8a and 5c to 8c for withdrawing components A and C, and these withdrawal valves are the above withdrawal valves. Along with the valves 4a, 4b and 4c, the opening and closing of the valves can be appropriately switched by a control device (not shown).

Further, the stock solution supply pipe 11e is provided with a stock solution supply pump 12e, the eluent solution supply pipe 11d is provided with an eluent supply pump 12d, and the solution withdrawing pipes 11a and 11c are provided with variable flow rate liquid withdrawal pumps 12a and 12c, respectively. It is installed.

The circulation pump 9 and the stock solution supply pump 12e are provided so that the flow rates of the two become equal when they are simultaneously operated. An example of a method for equalizing the flow rates is a method in which a flow meter is provided at both pump discharge ports and a variable displacement pump (either one is good) is variably controlled based on the measured value. However, it is not particularly limited thereto.

Next, in the apparatus configured as described above, the separation of the enriched fraction of each component from the liquid containing the three components is performed, for example, according to the flow chart described in FIG.

In FIG. 4A, the raw material fluid f is introduced into the top of the unit packing tower 5 via the raw material fluid supply valve 5e, and at the same time, the eluent D is packed into the unit C in which the component C is enriched. It is supplied from the top of the tower 1 via the eluent supply valve 1d, while on the other hand, upstream of the feed position of the stock solution, from the end of the unit packed tower 4 enriched with the component B via the extraction valve 4b, It is the figure which simulatedly showed the state which has begun to withdraw the amount equal to the sum total of the supply amount of the undiluted solution and the eluent. At this time, as shown by the broken line in the figure, one of the components A and C is simultaneously measured.
A fraction enriched in one or both components can be withdrawn via the withdrawal valves 6a and 2c. In this case, the withdrawal amount of component B is (stock solution supply amount) + (eluent supply amount)
-(Amount of extracted component A)-(amount of extracted component C)

In FIG. 4 1-2, the eluent D is supplied to the supply valve 1 thereof.
The amount of the component B withdrawn is made equal to the amount of the eluent D supplied, so that the unit packed towers 5, 6,
FIG. 9 is a diagram schematically showing a state in which the liquid flow without 7 and 8 is substantially zero and the component B is further extracted. In this figure, A ', B', and C'indicate the components A, B, and C existing in the stock solution supplied in FIG.

The above-mentioned FIG. 4A-1 shows the first step of flowing in the undiluted solution and the eluent, and FIG.
Is a step of lengthening the inflow time of the eluent to extract a larger amount of component B, which may or may not be present depending on the system to be separated.

FIGS. 2-1 to 2-7 are steps for explaining the second step. According to the simulated moving bed method, the fluid is circulated in the system without supplying the stock solution f. The eluent D is supplied, the component C is extracted, and the component A is extracted. The eluent supply position, the component C extraction position, and the component A extraction position are sequentially downstream according to the movement of each component. It is the figure which showed the operation which transfers to.

In FIGS. 2-6 to 2-7, if the extraction of the component B is also performed as shown by the broken line, this step should be called the third step, and these steps should be called 3-1 respectively. , 3-2 is more appropriate.

Although the apparatus and the method for chromatographic separation of the present invention in the above-described embodiments have been described with respect to the case of passing a liquid, the apparatus and the method of the present invention can also be used for the chromatographic separation of a gas body.

Although the apparatus shown in FIG. 1 uses eight unit packed towers, the number of the unit packed towers is the target mixture,
The number of unit packed towers is generally 3 to 36, preferably 3 to 2 depending on the purpose of fractional separation.
4, more preferably 3 to 16.

Although the present invention provides an apparatus and method capable of continuously separating three or more fractions from a mixture containing three or more components, it is generally necessary to separate the components to be separated from each other. The minute is preferably 3 to 16, more preferably 3 to 6, and most preferably 3.

Example 1 This example illustrates the separation of oligosaccharides, glucose and fructose.

Chromatographic separation of the raw materials (isomerized sugar solution) shown in Table 1 using the apparatus shown in FIG.
Type strong acid cation exchange resin (Amberlite CG60
00; trade name) and water as the eluent.

Eight inner diameters 108.3 m connected in series
m, packed bed height 1000 mm packed tower with a total of 7 adsorbents
The packed bed filled with 3.7 liters was kept at 60 ° C., and the separation operation was repeated according to the time schedule shown in Table 2.
In this example, the order of the affinity with the adsorbent is as follows: fructose>
Glucose> oligosaccharide, and the extraction valve (1a-8
From a), a liquid rich in oligosaccharide components, a withdrawal valve (4
Liquid rich in glucose component from b), withdrawal valve (1c
A liquid rich in fructose component is taken out from ~ 8c). In the first step, the flow rate was measured by providing a flow meter on the discharge side path of the circulation pump provided between the eluent supply position and the unit packed tower 1.

The flow rate in each step is shown below. Flow rate in the first step Stock solution supply flow rate 36.3 l / hr Eluent supply flow rate 18.9 l / hr Oligosaccharide fraction extraction flow rate 11.0 l / hr Glucose fraction extraction flow rate 36.8 l / hr Fructose fraction withdrawal flow rate 7.4 l / hr Flow rate in passage on discharge side of circulation pump 44.2 l / hr Flow rate in second step Eluent supply flow rate 18.4 l / hr Oligosaccharide Fraction withdrawal flow rate 11.0 l / hr Fructose fraction withdrawal flow rate 7.4 l / hr Flow rate in packed bed between eluent supply part and fructose fraction withdrawal part 44.2 l / hr

[0051]

[Table 1]

After performing the operation shown in Table 2 for 9 cycles at the above flow rate, the concentration distribution in the packed bed was measured. Second result
Shown in the figure. Table 3 shows the component composition of each fraction obtained in the 9th cycle.

[0053]

[Table 2]

[0054]

[Table 3]

Example 2 This example illustrates the separation of oligosaccharides, maltose and glucose.

Using the same apparatus as in Example 1, the raw materials shown in Table 4 (oligosaccharide, maltose, glucose mixed solution)
Was carried out by using a Na-type strongly acidic cation exchange resin (Amberlite CG6000: trade name) as an adsorbent and water as an eluent.

Eight inner diameters 108.3 m connected in series
m, packed bed height 1000 mm packed tower with a total of 7 adsorbents
The packed bed filled with 3.7 liters was kept at 70 ° C., and the separation operation was repeated according to the time schedule shown in Table 5. In this example, the order of the affinity with the adsorbent is
Glucose>maltose> oligosaccharide, in that order, a fluid rich in oligosaccharide components from the extraction valve (1a to 8a), a fluid rich in maltose component from the extraction valve (2b to 4b), from the extraction valve (1c to 8c). A fluid rich in glucose is extracted.

The flow rate in each step is shown below. Flow rate in the first step Stock solution supply flow rate 36.8 l / hr Eluent supply flow rate 23.9 l / hr Oligosaccharide fraction withdrawal flow rate 13.8 l / hr Maltose fraction withdrawal flow rate 36.8 l / hr Glucose fraction extraction flow rate 10.1 l / hr Circulation pump discharge side flow rate 46.9 l / hr Second step flow rate Eluent supply flow rate 23.9 l / hr oligosaccharide Fraction withdrawal flow rate 13.8 l / hr Glucose fraction withdrawal flow rate 10.1 l / hr Flow rate in packed bed between desorbent supply section and glucose fraction withdrawal section 46.9 l / hr Third step Flow rate of the eluent 23.9 l / hr Extraction flow rate of oligosaccharide fraction 11.7 l / hr Maltose fraction extraction flow rate 5.8 l / hr Glucose fraction extraction flow rate 6.4 l / Provided with hr eluent Flow rate in packed bed between the feeding section and the glucose fraction extraction section 46.9 l / hr

[0059]

[Table 4]

After performing the operation shown in Table 5 for 10 cycles at the above flow rate, the concentration distribution in the packed bed was measured. Results are shown in FIG. Table 6 shows the component composition of each fraction obtained in the 10th cycle.

[0061]

[Table 5]

[0062]

[Table 6]

Example 3 In this example, sugar beet molasses was treated with raffinose fraction, sucrose fraction,
An example in which the monosaccharide fraction and the betaine fraction are separated into four fractions is shown.

Only the column length of the apparatus of Example 1 was changed,
Other than that, the same equipment was used for the chromatographic separation of the raw materials (beet molasses) shown in Table 7, using Na-type strongly acidic cation exchange resin (Amberlite CG6000: trade name) as the adsorbent, and water as the eluent. Done using.

Eight inner diameters 108.3 m connected in series
m, the total height of the adsorbent is 11 in a packed tower with a packed bed height of 1500 mm
The packed bed filled with 0.6 liter was kept at 80 ° C., and the separation operation was repeated according to the time schedule shown in Table 8. In this example, the order of the affinity with the adsorbent is
Betaine>monosaccharide>sucrose> raffinose, in that order, a liquid rich in raffinose components from the extraction valves (1a to 8a), a liquid rich in sucrose components first from the extraction valve (4b), and then rich in monosaccharides. The liquid is drained, (1
From c, and 3c to 8c), a liquid rich in betaine component is taken out.

The flow rate in each step is shown below. Flow rate in the first step Stock solution supply flow rate 19.8 l / hr Eluent supply flow rate 45.7 l / hr Raffinose fraction extraction flow rate 2.1 l / hr Sucrose fraction and monosaccharide fraction extraction Flow rate 63.4 l / hr Flow rate in the passage on the discharge side of the circulation pump 63.4 l / hr Flow rate in the second step Eluent supply flow rate 16.6 l / hr Raffinose fraction extraction flow rate 4.2 l / Hr Extraction flow rate of betaine fraction 12.4 l / hr Flow rate in packed bed between desorbent supply part and betaine fraction extraction part 52.0 l / hr

[0067]

[Table 7]

The operation shown in Table 8 was repeated at the above flow rate until a steady state was reached. 10 after the steady state
Table 9 shows the component composition of each fraction obtained in the cycle.

[0069]

[Table 8]

[0070]

[Table 9]

In all of the above three examples, the separation target of the remaining three components was separated into three or four fractions, respectively, and good separation results which could not be obtained by the conventional method and apparatus were obtained. ing.

[Brief description of drawings]

FIG. 1 is a diagram showing a schematic configuration of an apparatus which is an embodiment of the present invention.

FIG. 2 is a diagram showing the concentration distribution inside the packed bed of Example 1 performed using the apparatus shown in FIG.

FIG. 3 is a diagram showing the concentration distribution inside the packed bed of Example 2.

FIG. 4 is a flowchart (charts 1-1 to 2-3) showing the operation of the apparatus of FIG. 1 in relation to opening / closing of each valve and supply / drain of liquid.

FIG. 5 is a continuation of FIG. 4 (charts 2-4 to 2-7).

[Explanation of symbols]

1-8: Unit packed tower 1a to 8a: Extraction valve for components with weak affinity 2b-4b: Intermediate component withdrawal valve 1c-8c: Extraction valve for components with strong affinity 1d to 8d: Eluent supply valve 5e: Stock solution supply valve 9: Circulation pump 10: Liquid flow path 11a: Piping for extracting components with strong affinity 11b: Pipe for extracting intermediate component 11c: Pipe for extracting components with weak affinity 11d: Eluent supply pipe 11e: undiluted solution supply pipe

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Fumihiko Matsuda             Olga, 1-4-9 Kawagishi, Toda City, Saitama Prefecture             No. Research Institute

Claims (8)

[Claims] 1. A raw material containing three or more components having different affinities for an adsorbent, wherein a large number of unit-packed towers filled with the adsorbent are connected in series by a fluid flow pipe to form a circulation flow path. By letting a fluid flow through the system, a component having a weak affinity to the adsorbent, a component having a strong affinity, and an intermediate component having an affinity between them are formed as adsorption zones in order of the affinity to the adsorbent. On the other hand, while supplying the raw material fluid into the system from the top side of the unit packed column in which the adsorption zone enriched with the component having a weak affinity is formed,
The first step of performing the operation of extracting the fraction from the end of the unit packed column in which the adsorption zone enriched with the component having an intermediate affinity is formed upstream of the feed position of the raw material fluid; A unit-packed tower column in which an adsorption zone enriched with the components remaining in the first step is formed while the fluid is circulated in the system without being supplied and the desorbent fluid is supplied into the system. The fraction of the component is extracted from the end, and the position for supplying the desorbent fluid and the position for extracting the fraction are sequentially transferred to the unit packed column on the downstream side of the system according to the movement of the enriched adsorption zone. A second step of performing the operation,
In one cycle, the flow rate of the fluid in the system immediately downstream of the raw material fluid supply position in the first step is changed by the suction action of the circulation pump provided in the system on the downstream side of the supply position of the raw material fluid. A method for separating a multi-component system, characterized in that the flow rate of the raw material fluid is made equal to the flow rate supplied to the system. 2. The step of extracting the fraction of the adsorption zone enriched with a component having a strong affinity from the system in the first step of claim 1, wherein the fraction of the adsorption zone enriched with a component having an intermediate affinity is used. A method for separating a multi-component system, which is characterized in that it is carried out simultaneously or sequentially with the operation of taking out. 3. The method for separating a multi-component system according to claim 1, wherein a desorbent fluid is supplied into the system. 4. The unit according to claim 3, wherein the desorbent fluid is supplied from the top of the unit packed column in which the adsorption zone enriched with the component having the strongest affinity for the adsorbent is formed. Characteristic multi-component separation method. 5. The method for separating a multi-component system according to any one of claims 2 to 4, wherein there are a plurality of positions for extracting the fluid from the system. 6. The method according to claim 5, wherein the withdrawal amount of each of the fluids withdrawn from the system is set to a predetermined amount by the flow rate adjusting means provided in the pipe path for withdrawing the fluids from the system, and the total amount of the fluids supplied to the system is increased. A method for separating a multi-component system, characterized in that the inflow rate and the total outflow rate of the fluid withdrawn from the system are made equal. 7. The method according to claim 1, wherein, following the second step, the fluid is circulated in the system and the desorbent fluid is supplied into the system while changing from a weak affinity to a strong affinity. The fractions of each component in which the adsorbed zone that has been separated and enriched is formed are extracted, and the position for supplying the desorbent fluid and the position for extracting each fraction are adjusted according to the movement of the adsorption zone. The method for separating a multi-component system, which comprises performing a third step of sequentially transferring to a unit packed tower on the downstream side of. 8. A unit packed tower group in which a large number of unit packed towers filled with an adsorbent are connected endlessly in series by a fluid flow pipe to form a circulation system, and three or more components having different affinities for the adsorbent. A raw material fluid supply means provided so that a raw material fluid containing the above can be supplied from the top of any unit packed tower in the circulation system, and any unit packed tower in the circulation system is selected and the tower is selected. By selecting a plurality of desorbent fluid supply means provided so as to be able to supply the desorbent fluid from the top, a circulation pump for circulating the fluid in the circulation system, and one of the unit packed towers in the circulation system, A plurality of fluid withdrawing means provided so that the fluid in the unit packed tower can be withdrawn from the end of the tower, the raw material fluid supply means and the fluid withdrawing means are operated in a predetermined relationship, and the raw material fluid is supplied. System immediately downstream of location First, the circulation pump is operated so as to equalize the flow rate of the fluid inside and the supply rate of the raw material fluid.
Control means, the desorbent fluid supply means and the fluid withdrawal means are operated in a predetermined relationship, and the relationship is temporally shifted to the downstream side of the circulation system, and the first control means. A multi-component separation device comprising: a control switching means for switching the operation of the circulation system by the control means and the operation of the circulation system by the second control means.