JP2965747B2 - Multicomponent separation method and apparatus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 particularly to 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 chromatography technique.

[0002]

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

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

For this reason, a method for fractionating each component from a fluid containing three or more components has been proposed separately.

For example, a method of continuously fractionating three or more components using a fixed-bed type chromatographic separation apparatus (Japanese Patent Laid-Open No. 63-158105), a first component and a second component The undiluted solution containing the third component is prepared by the following order of the affinity of the three components: third component> second component> first component.
And a unit packed tower packed with a first adsorbent, which is a component of the second component, a second component, a third component, and a second component of the first component. A method of separating and separating the three components based on the difference in the adsorption characteristics of the three components by alternately passing the unit packed tower filled with the agent and at least four layers in a simulated moving bed apparatus connected in series and endlessly ( JP-A-64-80409) has been proposed.

[0006]

However, the above-mentioned method of 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 has a feature of having a step of “circulating the fluid in the bed without supplying the fluid to the packed bed and extracting the fluid from the packed bed”. Since it is basically one of the fixed bed type chromatographic separation methods, the circulation flow rate is the same throughout the packed bed. For this reason, 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 packed bed length is required to prevent overtaking. The size of
The amount of the adsorbent becomes much larger than that of the simulated moving bed type apparatus, and this type of apparatus has a problem that the amount of treatment per unit adsorbent, which is an industrially important point, is small. In addition, there is also a problem that since the concentration of the components in the collected fraction is low, the burden of subsequent processing as required is large.

On the other hand, the latter method using different types of adsorbents has the advantage that separation and separation of three components can be performed well, but two types of adsorbents having appropriate adsorption capacities for the three components can be used. Selection is necessary, and the applicable target is restricted in relation to the components contained in the target fluid.

In order to eliminate the disadvantages of these conventional methods,
The present inventor has proposed a completely novel method which can efficiently separate a mixture containing three or more components into three or more fractions enriched with each component (for example, Japanese Patent Application No. 2-40).
No. 2826), but the same operation can be realized without using a mechanical means such as a shut-off valve. It is an object of the present invention to provide a method for separating a component from a ternary fluid, which can perform the following.

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 use a method of chromatographic separation of a simulated moving bed, so that the amount of adsorbent used can be reduced, and therefore the equipment is small and the throughput per unit adsorbent is small. The object of the invention is to provide a novel process which is particularly suitable for implementation on an industrial scale because of its large size.

[0012]

The feature of the method for fractionating and separating three or more components from a multi-component mixture system according to the present invention for realizing the above-mentioned object is that the adsorbent is filled. A large number of unit packed towers are connected endlessly in series with a fluid flow pipe 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. Thus, a component having a weak affinity is enriched in a system in which a component having a low affinity for an adsorbent, a component having a strong affinity, and an intermediate component having an affinity between them are formed as an adsorption zone sequentially divided in the order of the affinity for the adsorbent. The feed fluid is supplied into the system from the top side of the unit packed tower where the adsorption zone is formed, and the adsorption zone is formed which is enriched with components having an intermediate affinity upstream of the feed position of the feed fluid. Has been A first step of extracting the fraction from the end of the packed bed, and circulating the fluid in the system without supplying the raw material fluid, and supplying the desorbent fluid to the system while supplying the desorbent fluid to the system. The fraction of the component remaining in one step is extracted from the end of the unit packed column where the adsorption zone enriched with the component is formed, and the position for supplying the desorbent fluid and the position for extracting the fraction are as follows. And a second step of sequentially shifting to a unit packed tower on the downstream side of the system in accordance with the movement of the enriched adsorption zone as one cycle. The flow rate of the fluid in the system immediately downstream of the source fluid supply position in the first step is made equal to the flow rate of the source fluid 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 raw material fluid supply position equal to the flow rate of the raw material fluid to be supplied to the system, the suction force of the circulation pump may be given in advance by design and fixed. Alternatively, the flow rate may be controlled to be equal by measuring the liquid flow velocity at the corresponding position and comparing it with the supply amount of the raw material fluid. It is also preferable to provide a throttle or an orifice in a pipe located upstream of the system to which the raw material fluid is supplied, in order to improve controllability.

The first step in the method of the present invention is to form a distribution of adsorption zones of each component extracted in the next cycle while supplying the raw material fluid, and to adjust the affinity of the components having already formed the adsorption zone. This is a step of extracting at least one of components classified as intermediate (hereinafter, referred to as “intermediate component”) out of the system, whereby a large amount of intermediate component 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, in accordance with the “simulated moving bed method”, each of the target components other than the intermediate component is subjected to the method. An operation of separately extracting the enriched fraction from the system is performed, 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 for the adsorbent to a component having a strong affinity. This is a step for forming a divided adsorption zone. Here, the "simulated moving bed method" used for extracting each component separately while supplying the desorbent fluid is a conventionally known pseudo moving bed method, except that the supply of the raw material fluid is not performed. For example, the method described in JP-A-62-91205, particularly, page 2, upper right column, second line to lower left column, last line and FIG. Therefore, the first section and the fourth section can be implemented as they are, except that the first section and the fourth section may be considered to be the same section. Specifically, while circulating the fluid in the system by a pump or the like, the desorbent fluid is supplied from the upstream of the adsorption zone in which the predetermined component is distributed, and the fraction enriched in the component from the downstream of the adsorption zone. Can be carried out by sequentially performing the operation of sequentially extracting the components downstream of the circulation flow in accordance with the movement of the adsorption zone for a plurality of components other than the intermediate components.

The present invention is based on a method in which the above-described first step and second step are repeated as one cycle. However, the present invention can be carried out in various modified forms without impairing the effects. Needless to say.

For example, in the first step, an operation of extracting a predetermined component from the upstream of the supply 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 for 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 excluding A,
Assuming that 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 components C and B can be separated by fractionating the above-mentioned fraction over time, or one fraction can be used if the separation of these components C and B is not particularly required.

In the first step, not only the raw material fluid is 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 extraction amount of the intermediate component can be reduced. There is an advantage that adjustment (adjustment of mass balance) can be performed. In particular, there is also an advantage that the moving speed of the predetermined component in the adsorption zone can be selected by increasing the flow velocity downstream thereof by supplying the desorbent fluid. That is, a component having a weak affinity for the adsorbent is changed from a component having a strong affinity (for example, A, B, C
If the desorbent fluid is supplied from the upstream of component C, which has the strongest affinity, to the system that has already formed the adsorption zone sequentially divided into The movement of the components A ', B', C 'and the movement of the weakest component A located downstream of the feed fluid supply position are performed at a flow rate based on the amount of the feed fluid supplied, while being parallel to this. Then, the extraction of the intermediate component B and the movement of the adsorption zone of the component C having the highest affinity can be performed at a large flow rate in which the supply amount of the raw material fluid and the supply amount of the desorbent fluid are added. Effectively, the adsorption band of the component A having a low affinity (moving speed is high) distributed downstream of the raw material fluid supply position can catch up with the adsorption band of the component C having a strong affinity (moving speed is low). Can be prevented.
The supply of the desorbent fluid may be simultaneous or sequential with the supply of the raw material fluid to the system.

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

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

The operation of repeating the first step and the second step of the present invention in the state where the apparatus is continuously operated is described. However, in order to start the apparatus, the first step is performed. Prior to the step, an operation of 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 low affinity for the adsorbent are sequentially separated from components having a low affinity to a strong component. A pre-process of performing only the above may be performed.

In the present invention, the following third step may be performed after the second step. That is, while circulating the fluid in the system, the desorbent fluid supply and the intermediate component are separated from each other in the circulating direction and are separated from those having a low affinity to those having a high affinity. Separately separate the enriched fractions of each component containing from the separation system, and supply the desorbent fluid to each component and circulate the fraction withdrawal position sequentially according to the movement of the adsorption zone. This is the 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 where each component is enriched in the second step, and the components having a weak affinity for the adsorbent are removed from the components. This step is performed from the point when the adsorption zones sequentially separated into strong components are formed to the desired degree, and the significance of performing this step is that each of the adsorption zones in which the target separation has already been completed is completed. Is continuously circulated to a predetermined one cycle end position while continuously extracting the fraction. Usually, an industrial chromatographic separation apparatus is designed by limiting its use, that is, the system to be separated, but there are many requests to use one separation apparatus for a plurality of target systems. As an example, five components (A,
B, C, D, and E), the first step is to perform A, B as a first step when the component fluid is fractionated into five single components using the method and apparatus of the present invention. , C are separated into one fraction, and the two components D and E are separated as one fraction, respectively. Further, as a second stage, A, B, and C are extracted as one fraction in the first stage. A method in which a mixed fluid of the components is supplied as a raw material fluid to the same apparatus and separated into fractions A, B, and C can be given. In such a case, the difficulty of the first stage separation and the difficulty of the second stage separation will be different, and if the design is performed in accordance with the higher difficulty separation, the lower difficulty separation is performed. ,
In the course of the second step, the target separation may be completed before the adsorption zone enriched with each component reaches a predetermined end position of one cycle. At this time, the second step can be continued, but circulation is performed without extracting a zone enriched with intermediate components whose affinity for the adsorbent is classified as intermediate. However, thinning that occurs as a result of spreading cannot be prevented.

In the third step, an operation of extracting the intermediate component is added to the second step, so that the flow velocity on the upstream side of the extraction point of the intermediate component is changed to a flow velocity at which the intermediate component moves faster, and the intermediate component is extracted. Since the flow velocity downstream of the extraction point can be set to each of the flow velocities for moving the intermediate component slowly, it is possible to prevent the band enriched with the intermediate component from spreading to the front and rear bands, and to achieve the object. An additional advantage is that all fractions can be continuously extracted. That is, by designing the apparatus so that the third step can be performed, the possibility of applying the same apparatus to a plurality of separation target systems can be increased.

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 large volumes of fluids, the sugar refining industry that separates and purifies various sugars or sugar alcohol mixtures using strongly acidic cation exchange resins of the alkali metal type or alkaline earth metal type as adsorbents Its usefulness as a strategic facility is extremely large. Specific examples of such sugar purification include separation of sucrose and other useful substances from molasses, fractionation of isomerized sugar into glucose, fructose, and oligosaccharide, and the separation of each component from lactose, lactulose, and galactose. , Separating each component from a mixture containing glucose, sucrose, fructooligosaccharide, separating each component from a mixture containing glucose, isomaltose, isomaltdextrin, glucose, maltose,
Examples include the case of separating each component from a mixed solution containing maltodextrin, and the case of separating each component from a mixed solution containing a sugar alcohol such as sorbitol and maltitol.

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

That is, a plurality of unit packed towers filled with an adsorbent are connected endlessly in series with a fluid flow pipe to form a unit packed tower group, and three or more components having different affinities for the adsorbent are used. One raw material fluid supply means provided so as to be able to supply the raw material fluid containing from the top of any one of the unit packed towers in this circulation system, and any one of the unit packed towers in the above circulation system A plurality of desorbent fluid supply means provided so as to be able to supply the desorbent fluid from the top of the tower, a circulation pump for circulating the fluid in the circulation system, and any one of the unit packed towers in the circulation system And a plurality of fluid extracting means provided so as to be able to extract the fluid in the unit packed tower from the end of the column, and operating the raw material fluid supplying means and the fluid extracting means in a predetermined relationship. , Raw material fluid The first control means for operating the circulation pump so that the fluid flow rate in the system immediately downstream of the supply position is equal to the supply flow rate of the raw material fluid, and the desorbent fluid supply means and the fluid extraction means are predetermined. A second control means for operating the relation and moving the relation to the downstream side of the circulation system with 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. This is a multi-component separation device provided with a control switching means.

[0028]

According to the above arrangement, a mixture containing three or more components can be efficiently separated into three or more fractions enriched with each component.

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

Furthermore, according to the present invention, the amount of adsorbent to be used is small, the size of the equipment is small, and the processing amount per unit adsorbent is large, and it is particularly suitable for implementation on an industrial scale. There is an effect that there is.

[0031]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but it is needless to say that the present invention is not limited to the following examples unless 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, reference numerals 1 to 8 denote unit packed towers each filled with the same adsorbent, and the unit packed towers 1 to 8 are connected by pipes so as to allow liquid flow, and the last unit packed tower 8 is located at the top of the unit packing tower 1 at the forefront.
0. Reference numeral 9 denotes a circulation pump provided in the middle of the liquid flow path between the unit packing tower 5 and the downstream of the supply position of the undiluted solution described later.

A liquid supply pipe is connected to a liquid flow path between the unit packed towers 4 and 5, and a raw liquid supply pipe 11e is connected to the liquid supply pipe via an open / close switching type raw liquid supply valve 5e. A common eluent supply pipe 11d is connected via an open / close switching eluent supply valve 5d for an eluent as a desorbent fluid. A liquid extraction pipe for extracting liquid from the end of the unit packing tower 4 on the upstream side of the stock solution supply position to the outside of the system is connected, and as described below, this enriches each of the three components. The separated fractions are separated into three parts on the way so that they can be extracted and fractionated by different routes, and each component has a low affinity for the adsorbent (hereinafter, referred to as “component A”) and a strong component (hereinafter, referred to as “component C”). , For the fraction of intermediate components (hereinafter referred to as "component B"), common extraction pipes 11a, 11 for each component via opening / closing extraction valves 4a, 4b, 4c.
b, 11c.

The common eluent supply pipe 11d is provided between the unit packed towers 1-4, 5-8, and 8-1, respectively, with the eluent supply valves 2d, 3d, 4d, 6d, 7d, 7d, respectively. 8
These supply valves are connected via d and 1d, and their opening and closing can be appropriately switched by a control device (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 each of the unit packed towers 1-4, 5-8, and 8-1. The pipes for extracting these liquids are the extraction valves 1a, 1b for extracting the components A and C in the unit between the unit packed towers 1 and 2.
1c, are connected to common extraction pipes 11a, 11c, and components A to
The common extraction pipes 11a, 11a, 3b, 3c are withdrawn through the extraction valves 2a, 2b, 2c and 3a, 3b, 3c.
11b, 11c, and the unit packed towers 5-8 and 8-
1 are connected to common extraction pipes 11a and 11c via extraction valves 5a to 8a and 5c to 8c for extracting the components A and C, respectively. The opening and closing of the valves 4a, 4b, and 4c are appropriately switched by a control device (not shown) together with the valves 4a, 4b, and 4c.

The undiluted solution supply pipe 11e has an undiluted solution supply pump 12e, the eluent supply pipe 11d has an eluent supply pump 12d, and the drainage pipes 11a and 11c have variable flow rate liquid extraction pumps 12a and 12c, respectively. It is interposed.

The circulating pump 9 and the stock solution supply pump 12e are provided such that when they are operated simultaneously, the flow rates of both are equal. As a method of equalizing the flow rates, a method of providing a flow meter at both pump discharge ports and variably controlling a variable displacement pump (either one may be used) based on the measured values can be exemplified. However, the present invention is not particularly limited to this.

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

FIG. 4A is a diagram showing a state in which the raw material fluid f is introduced to the top of the unit packed column 5 through the raw material fluid supply valve 5e, and the eluent D is simultaneously filled in the unit packed column in which the component C is enriched. The eluent is supplied from the top of the column 1 via an eluent supply valve 1d, and on the other hand, at the upstream of the supply position of the undiluted solution, withdrawal from the end of the unit packed column 4 enriched with the component B via the withdrawal valve 4b FIG. 7 is a diagram schematically illustrating a state in which an amount equal to the sum of the supply amounts of the undiluted solution and the eluent has begun to be extracted. At this time, as indicated by the broken line in the figure, one of the components A and C is simultaneously detected.
The fraction enriched in one or both components can also be withdrawn via the withdrawal valves 6a, 2c, in which case the withdrawal of component B is (stock feed) + (eluant feed)
− (Amount of extraction of component A) − (amount of extraction of component C).

FIG. 4B is a diagram showing the state where the eluent D is supplied to the supply valve 1 thereof.
d, and the extraction amount of the component B is made equal to the supply amount of the eluent D, whereby the unit packed columns 5, 6,
FIG. 7 is a diagram schematically illustrating a state where the flow of the liquid without the components 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, respectively, which were present in the stock solution supplied in FIG. 4A.

FIG. 4A is a first step in which an undiluted solution is introduced and an eluent is introduced, and FIG.
Is a step of extracting the component B in a larger amount by elongating the inflow time of the eluent, and may or may not be present depending on the system to be separated.

FIGS. 2-1 to 2-7 illustrate the second step, in which the fluid is circulated in the system without supplying the undiluted solution f, according to the method of the simulated moving bed. The supply of the eluent D, the withdrawal of the component C, and the withdrawal of the component A are performed, and the supply position of the eluent, the withdrawal position of the component C, and the withdrawal position of the component A are sequentially downstream in accordance with the movement of each component. FIG. 7 is a diagram schematically illustrating an operation of shifting to (1).

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

In the apparatus and the chromatographic separation method of the present invention in the above-described embodiment, the case where a liquid is passed has been described. However, the apparatus and the method of the present invention can also be used for chromatographic separation of gaseous substances.

The apparatus shown in FIG. 1 uses eight unit packed towers.
It can be changed depending on the purpose of fractionation and the like, and the number of unit packed columns is generally 3 to 36, preferably 3 to 2
4, more preferably 3 to 16.

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

Example 1 This example shows the separation of oligosaccharide, glucose and fructose.

Using the apparatus shown in FIG. 1, the chromatographic separation of the raw materials (isomerized sugar solution) shown in Table 1 was performed using Ca as an adsorbent.
Type strongly acidic cation exchange resin (Amberlite CG60
00; trade name) and water as the eluent.

Eight inner diameters of 108.3 m connected in series
m, adsorbent in a packed tower with a packed bed height of 1000 mm
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 embodiment, the order of the affinity strength with the adsorbent is fructose>
In the order of glucose> oligosaccharide, the extraction valves (1a-8
From a), a liquid rich in the oligosaccharide component, a withdrawal valve (4
b) From the liquid rich in glucose component, withdraw valve (1c
8c), a liquid rich in fructose components is taken out. In the first step, a flow meter was provided on the discharge-side path of the circulation pump provided between the eluent supply position and the unit packed column 1 to measure the flow rate.

The flow rate in each step is shown below. (Step 1) Flow rate in the first step 35.0 l / hr of undiluted solution supply flow rate of eluent 18.4 l / hr extraction flow rate of oligosaccharide fraction 11.0 l / hr extraction of glucose fraction Flow rate 35.0 l / hr Fructose fraction extraction flow rate 7.4 l / hr (Step 2) Eluent supply flow rate and glucose fraction extraction flow rate 18.4 L / hr Flow rate in second step Eluent 18.4 l / hr Extraction flow rate of oligosaccharide fraction 11.0 l / hr Extraction flow rate of fructose fraction 7.4 l / hr In packed bed between eluate supply section and fructose fraction extraction section Flow rate 42.4 l / hr

[0051]

[Table 1]

After performing the operations shown in Table 2 for 9 cycles at the above flow rates, 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 ninth cycle.

[0053]

[Table 2]

[0054]

[Table 3]

Example 2 This example shows the separation of oligosaccharide, maltose and glucose.

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

Eight inner diameters of 108.3 m connected in series
m, adsorbent in a packed tower with a packed bed height of 1000 mm
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 strength of the affinity with the adsorbent is
In the order of glucose>maltose> oligosaccharide, a fluid rich in an oligosaccharide component is from the extraction valves (1a to 8a), a fluid rich in a maltose component from the extraction valves (2b to 4b), and from an extraction valve (1c to 8c). A fluid rich in glucose components is removed.

The flow rates in each step are shown below. Flow rate in the first step Supply flow rate of stock solution 36.8 l / hr Supply flow rate of eluent 23.9 1 / hr Extraction flow rate of oligosaccharide fraction 13.8 l / hr Extraction flow rate of maltose fraction 36.8 l / hr Glucose fraction withdrawal flow rate 10.1 l / hr Flow rate in packed bed between eluent supply section and glucose fraction withdrawal section 46.9 l / hr Flow rate in second step Eluent supply flow rate 23.9 l / hr Extraction flow rate of oligosaccharide fraction 13.8 l / hr Extraction flow rate of glucose fraction 10.1 l / hr Flow rate in packed bed between eluate supply unit and glucose fraction extraction unit 46. 9 l / hr Flow rate in the third step Supply flow of eluent 23.9 l / hr Extraction flow rate of oligosaccharide fraction 11.7 l / hr Extraction flow rate of maltose fraction 5.8 l / hr Glucose fraction Extraction flow rate The filling layer between .4 l / hr eluent supply and glucose fraction extraction unit flow rate 46.9 l / hr

[0059]

[Table 4]

After performing the operations shown in Table 5 at the above flow rate for 10 cycles, the concentration distribution in the packed bed was measured. The 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, beet molasses was prepared by mixing raffinose fraction, sucrose fraction,
The example which separated the monosaccharide fraction and the betaine fraction into four fractions is shown.

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

Eight inner diameters of 108.3 m connected in series
m, a total of 11 adsorbents 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 strength of the affinity with the adsorbent is
Betaine>monosaccharide>sucrose> raffinose in this order, with a liquid rich in raffinose component from the extraction valves (1a to 8a), a liquid rich in sucrose component first from the extraction valve (4b), and then rich in monosaccharide character. The liquid is extracted and (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 : supply flow rate of stock solution 19.8 l / hr supply flow rate of eluent 45.7 l / hr extraction rate of raffinose fraction 2.1 1 / hr extraction of sucrose fraction and monosaccharide fraction Flow rate 63.4 l / hr Flow rate in the packed bed between the eluent supply section and betaine fraction extraction section 63.4 l / hr Flow rate in the second step Eluent supply flow rate 16.6 l / hr Raffinose fraction 4.2 l / hr Flow rate of betaine fraction 12.4 l / hr Flow rate in packed bed between eluent supply and betaine fraction withdrawal 52.0 l / hr

[0067]

[Table 7]

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

[0069]

[Table 8]

[0070]

[Table 9]

In each of the above three embodiments, the object to be separated of more than three components is separated into three or four fractions, respectively, and a good separation result which cannot be obtained by the conventional method and apparatus can be obtained. ing.

[Brief description of the drawings]

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

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

FIG. 3 is a diagram showing a concentration distribution inside a packed layer of Example 2;

FIG. 4 is a flowchart (chart 1-1 to 2-3) showing the operation of the apparatus of FIG. 1 in relation to the opening and closing of each valve and the supply and withdrawal 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-8a: Extraction valve for components with low affinity 2b-4b: Extraction valve for intermediate components 1c-8c: Extraction valve for components with high affinity 1d-8d: Eluent supply valve 5e: Stock solution supply Valve 9: Circulation pump 10: Liquid flow path 11a: Extraction pipe for components with high affinity 11b: Extraction pipe for intermediate components 11c: Extraction pipe for components with low affinity 11d: Eluent supply pipe 11e: Stock solution supply pipe

──────────────────────────────────────────────────続 き Continuing the front page (72) Fumihiko Matsuda 1-4-9 Kawagishi, Toda City, Saitama Prefecture Inside Organo Research Institute (58) Field surveyed (Int.Cl. ⁶ , DB name) B01D 15 / 00 G01N 30/42

Claims (8)

(57) [Claims] 1. A raw material containing three or more components having different affinities for an adsorbent, wherein a plurality of unit packed towers filled with an adsorbent are connected endlessly in series by a fluid flow pipe to form a circulation channel. By flowing a fluid into the system, a system having a component having a low affinity for an adsorbent, a component having a high affinity, and an intermediate component having an affinity for the adsorbent formed as an adsorption zone sequentially divided in the order of the affinity for the adsorbent. On the other hand, the raw material fluid is supplied into the system from the top side of the unit packed column in which the adsorption zone in which the component having low affinity is enriched is formed,
A first step of performing an operation of extracting the fraction from the end of a unit packed column in which an adsorption zone enriched with an intermediate component is formed upstream of the supply position of the raw material fluid, and A unit packed column in which an adsorption zone enriched with the components remaining in the first step is formed while supplying a desorbent fluid into the system while circulating the fluid in the system without supplying the fluid. A fraction of the component is extracted from the powder, and a position for supplying the desorbent fluid and a position for extracting the fraction are sequentially shifted to the unit packed tower on the downstream side of the system in accordance with the movement of the enriched adsorption zone. A second step of performing an operation;
Is repeated as one cycle, the suction flow of the circulating pump provided in the system downstream of the supply position of the raw material fluid, the fluid flow in the system immediately downstream of the raw material fluid supply position in the first step, A method for separating a multi-component system, wherein a flow rate of a raw material fluid supplied into the system is equalized. 2. The method according to claim 1, wherein the step of extracting a fraction of the adsorption zone enriched with a component having a strong affinity from the system is performed by a step of extracting the fraction of the adsorption zone enriched with a component having an intermediate affinity. A method for separating a multi-component system, wherein the method is carried out simultaneously or sequentially with the operation of extracting the components. 3. The method according to claim 1, wherein a desorbent fluid is supplied into the system. 4. The method according to claim 3, wherein the position for supplying the desorbent fluid is from the top of the unit packed column in which the adsorption zone enriched with the component having the highest affinity for the adsorbent is formed. Characteristic multi-component separation method. 5. The method for separating a multi-component system according to claim 1, wherein a plurality of positions for extracting a fluid from the system are provided in the first step according to claim 2. 6. The system according to claim 5, wherein the flow rate adjusting means provided in the piping path for extracting the fluid from the system sets the amount of each fluid extracted from the system to a predetermined amount and sets the total amount of the fluid to be supplied to the system. A method for separating a multi-component system, comprising equalizing an inflow amount and a total outflow amount of a fluid extracted from the system. 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 the affinity is changed from a weak affinity to a strong affinity. The respective fractions of each component in which the separated and enriched adsorption zone is formed are extracted, and the position for supplying the desorbent fluid and the position for extracting each fraction are adjusted in accordance with the movement of the adsorption zone. A multi-component separation method, wherein a third step of sequentially transferring to a unit packed tower on the downstream side of the step (c) is performed. 8. A unit packed tower group in which a large number of unit packed towers filled with an adsorbent are connected in an endless 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 as to be able to supply a raw material fluid containing from the top of any of the unit packed towers in the circulation system, and selecting any one of the unit packed towers in the circulation system 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 selecting one of the unit packed towers in the circulation system A plurality of fluid extracting means provided so as to be able to extract the fluid in the unit packed tower from the end of the column, the raw material fluid supplying means and the fluid extracting means are operated in a predetermined relationship, and the raw material fluid is supplied. System immediately downstream of the location Operating the circulating pump so that the fluid flow rate in the inside and the supply flow rate of the raw material fluid are equalized.
A second control means for operating the desorbent fluid supply means and the fluid extracting means in a predetermined relation and shifting this relation to the downstream side of the circulation system over time; An apparatus for separating a multi-component system, comprising: a control switching means for switching operation of the circulation system by the control means and operation of the circulation system by the second control means.