JPH0716401A - Chromatographic separation - Google Patents

Abstract

PURPOSE:To provide a chromatographic separation method where the system is divided into three sections to simplify flow control and the used quantity of an adsorbent is decreased in the case the feed fluid of a multicomponent system including three or more components is caused to flow to separate and recover each component in a pseudo-moving bed type chromatographic separator where a lot of packed columns packed with the adsorbent are connected endlessly and in series. CONSTITUTION:A process 1) where a pseudo-moving bed type chromatographic separator is used, and while the flow of fluid from the 2nd section rich with a component having intermediate affinity B to the 3rd section rich with a component having weak affinity A is stopped by closing a cutoff valve and while feed fluid is fed from the 3rd section downstream of the cutoff valve, the fraction of the component B is caused to flow out from the packed column of the 2nd section, and a process 2) where while the flow of fluid from the 3rd section rich with a component C having strong affinity to the 1st section is stopped by closing a cutoff valve, the fraction of the component C is caused to flow out from the packed column of the 1st section and the fraction of the component A is caused to flow out from the 3rd section, and the operation is repeated while it is moved to the downstream side every specific time are successively and alternatively performed.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a simulated moving bed in which a large number of packed columns packed with an adsorbent having a selective adsorption capacity for three or more components contained in a stock solution are connected in series and endlessly. The present invention relates to a separation method using a chromatographic separation device, for example, a separation method between maltose, glucose and fructose, a separation method between maltotriose, maltose and glucose, and the like.

[0002]

2. Description of the Related Art Conventionally, a chromatographic separation method in which a liquid containing two components is made to flow in a packed column filled with an adsorbent to separate and collect a fraction enriched in these components is a fixed bed type, a simulated moving type. It is known as a layered type or fluidized bed type, and in recent years it has been 3
For the purpose of separating the above components, a simulated moving bed type chromatographic separation method has been attracting attention and some proposals have already been made.

As a method for separating multiple components using such a simulated moving bed chromatographic separation device, a large number of adsorbents having different adsorption capacities with respect to three or more components contained in the raw material fluid are filled. The packed column of No. 1 is connected with one or several circulating pumps in an endless series by piping, and the raw material fluid is flowed through this packed column group to enrich each component from the upstream side to the downstream side. It is typically known that a first section, a second section, a third section, and a fourth section which are different from each other are formed and the following operations a and b are repeated.

A: The shutoff valve between the second and third compartments is closed, and the desorbent is introduced from the inlet of the packed column in the front row of the first compartment,
The raw material is supplied from the inlet of the packed column located in the front row of the third section, and the component B, which has neither strong nor weaker affinity for the adsorbent, is supplied from the outlet of the packed column located in the last row of the second section. First step of flowing out the converted fraction b: Opening the shut-off valve and circulating the fluid in the packed bed, while supplying the desorbent from the inlet of the packed column in the front row of the first section, the third section The fraction enriched with the component A having a weak affinity for the adsorbent from the packed column in the last row of the column is enriched with the component C having a strong affinity for the adsorbent from the outlet of the packed column located in the last row of the first section. The second step in which the desorbent supply position and the outflow position of each fraction are sequentially moved to the downstream side by a rotary valve or a valve attached to each tower.

[0005]

However, the flow control of the above-mentioned conventional multi-component separation pseudo moving bed type chromatographic separation device is complicated, and the flow control device needs to be high performance and expensive. In particular, there has been a demand for a multi-component separation pseudo-moving bed chromatographic separation method that is small in size, versatile in various uses, easy to control, and inexpensive.

From the above viewpoints, the present inventor has conducted various studies and developed the present invention for the purpose of providing a multi-component separation pseudo moving bed type chromatographic separation method which is easy to control and inexpensive. .

[0007]

The present inventors have completed the method of the present invention as set forth in each claim of the above-mentioned claims in order to achieve the above objects.

The feature of the method of the present invention is that, typically, a system of endless packed towers in which a large number of packed towers filled with adsorbents are sequentially connected in series by pipes each having a shutoff valve The three compartments (components having a strong affinity for the adsorbent (hereinafter referred to as “component C”) formed when a raw material fluid containing three or more components having different affinities to To a first section consisting of a plurality of packed tower groups, one or a plurality of packed tower groups enriched with a component having an intermediate affinity for the adsorbent (hereinafter referred to as “component B”), and a component having an intermediate affinity for the adsorbent A second section composed of one or a plurality of packed tower groups in which B and the above-mentioned component C having a strong affinity are mixed, a component having a weak affinity to the adsorbent (hereinafter referred to as "component A"
The third section consisting of the remaining packed tower group including one or a plurality of packed tower groups enriched with
The steps of and are alternately repeated in the order of, or they are repeated in the order of.

With the shutoff valve between the second and third compartments closed to shut off the circulation of the fluid in the entire system, the raw material fluid is supplied from the inlet of the packed column located immediately downstream of the shutoff valve. While performing the operation of flowing out the fraction enriched in the above component B from the outlet of any packed column in the second compartment,
Step of shifting the distribution of the first section to the third section to the downstream side by at least one packed column Continuing from the above step, with the shutoff valve between the transferred third section and the first section closed, An operation of supplying a desorbent fluid from an inlet of a packed column located at the uppermost stream of one section, and flowing out a fraction enriched in the component C from the outlet of the most downstream packed column of the first section; The operation of causing the fraction enriched in the component A to flow out from the outlet of the packed column located at the most downstream side of the third section, and further, the distribution of the first section to the third section is filled one downstream side of the fluid. In synchronism with the transfer of only the tower portion, the desorbent fluid supply position, each fraction extraction position,
And a step of repeating the same operation by lowering the position of the shutoff valve for shutting off by one packed tower and repeating the same operation a predetermined number of times. Following the above steps, with the shutoff valve between the third compartment and the first compartment closed. An operation of supplying the desorbent fluid from the inlet of the packed column located at the uppermost stream of the first section, while flowing out the fraction enriched in the component C from the outlet of the most downstream packed column of the first section. And an operation of flowing out the enriched fraction of the above component A from the outlet of the packed column located at the most downstream side of the third section, and the operation of the above component B from the outlet of the packed column located at the most downstream side of the second section. The operation of causing the enriched fraction to flow out is performed, and further, if necessary, the distribution of the first to third sections is synchronized with the transfer of one packed column to the downstream side of the fluid in synchronization with the desorbent fluid. The supply position of each, the extraction position of each fraction, and the position of the shut-off valve for shutting off each one packed column The step of repeating the same operation by moving back only a predetermined number of times.

In the above, the first section consisting of one or a plurality of packed tower groups enriched with the component C does not strictly require that only the component C is enriched. For example, when the component to be separated and recovered is B, and the component C only needs to be removed, the component B is somewhat mixed in the most downstream packed column of the first section. The packed tower group forming the first section can be set according to the purpose to be carried out, the type of components contained in the raw material fluid, etc. The same applies to the second section and the third section.

In the above process, the operation of supplying the desorbent fluid from the inlet of the most upstream packed column of the first section, the fraction enriched with the component C from the outlet of the most downstream packed column of the first section. At least one of the operation of flowing out the fraction and the operation of flowing out the fraction enriched in the component A from the outlet of the most downstream packed column in the third section may be performed simultaneously or sequentially in combination.

The shutoff valve closed in the above step is not limited to the shutoff valve between these compartments as long as it can block the flow of fluid from the second compartment to the third compartment. Therefore, in this case, while the raw material fluid is supplied from the inlet of one of the packed towers located relatively upstream in the third section located downstream of the closed shutoff valve, the raw material fluid is supplied upstream of the closed shutoff valve. The fraction enriched in the component B can be discharged from the outlet of any one of the packed columns located relatively downstream in the second section. Here, the fact that the packed tower for supplying the raw material fluid is relatively upstream of the third section means that the packed tower does not have to be the uppermost packed tower in the third section, depending on the distribution state of component A and its nature. In general, the most upstream packed tower or the next packed tower downstream thereof is selected, but it is not limited to this depending on the number of installed packed towers and the like. Similarly, the packed column for discharging the component B is located relatively downstream in the second section, generally because the packed column located at the most downstream side in the second section or immediately upstream of the packed tower. A tower is selected, but it is not limited to this depending on the number of installed packed towers and the like.

In the above step, before and / or after this step, while supplying the desorbent fluid from the inlet of the packed column located at the uppermost stream of the first section, the most downstream of the first section is supplied. The operation of letting out the fraction enriched in the above component C from the outlet of the packed column, and supplying the desorbent fluid from the inlet of the packed column located at the uppermost stream of the first section, to the most downstream of the third section. The operation of flowing out the fraction enriched in the component A from the outlet of the packed column located at the same time, sequentially, or simultaneously performing these operations, and at least these operations Either may be performed sequentially.

In addition, in the repeated steps, or in the step and the subsequent steps, the shut-off valves in the system are all opened before the operation of each repetition. An operation of supplying the desorbent fluid from the inlet of the packed column located at the uppermost stream of the first section, while flowing out the fraction enriched in the component C from the outlet of the packed column located at the most downstream side of the first section. It is also preferable to perform.

[0015]

According to the method of the present invention, the number of sections is 1 as compared with the conventional method in which the system of the packed tower group is divided into 4 sections.
Since the number is 3 which is small, there is an effect that the flow rate control for flowing out the fraction of the component having a weak affinity for the adsorbent becomes unnecessary.

Further, a step of supplying the fluid from the packed column located in the last row of the third section to the packed column located in the front row of the first section without closing the shutoff valves of the third section and the first section With the addition, there is an effect that the amount of the desorbent used can be reduced.

Furthermore, it is said that the separation performance can be improved by adding a step of flowing out only a component having a strong affinity to the adsorbent and / or a step of flowing out only a component having a weak affinity to the adsorbent. effective.

[0018]

EXAMPLES The present invention will be described in detail below based on examples, but it goes without saying that the present invention is not limited to these examples.

Example 1 (maltotriose and malteau)
Separation of glucose and glucose) FIG. 1 is an explanatory view showing the flow of the apparatus used in this example.

A packed tower T having an inner diameter of 3.7 cm and a length of 50 cm
(T1 ... T8) Each of the eight ends is connected endlessly to the top of the next packed column via a shutoff valve K (K1 ... K8) with a pipe H, upstream of each shutoff valve K. The liquid A outflow valve A (A1 ... A8) and the liquid B outflow valve B (B4, B
5, B6), the C liquid outflow valve C (C1 ... C8) and the circulation valve M (M1 ... M8) are connected, and the stock solution supply valve F is connected to the pipe H on the downstream side of each shutoff valve K. (F1 ... F
8) and the eluent supply valve D (D1 ... D8) are connected,
Furthermore, an experimental apparatus was used in which the other end of the circulation valve M was connected to the inlet of the eluent pump P11, and a check valve was installed on the upstream side of the connecting portion. Each packed column was filled with the strongly acidic cation exchange resin Amberlite CG-6000 Na type.

The shutoff valve is a normally open valve, each supply valve, each outflow valve, and the circulation valve are normally closed valves.

As one step, the shutoff valve K5 is operated to shut off the flow between the packed towers 5 and 6, the stock solution supply valve F6 is opened to introduce the stock solution from the top of the packed tower T6, and the eluent supply valve D
1 was opened to introduce water as an eluent from the top of the packed tower T1, and the B solution outflow valve B5 was opened to withdraw a solution containing a large amount of maltose (B solution) from the bottom of the packed tower T5.

After a lapse of a predetermined time, the shutoff valve K1 is closed and the eluent supply valves D2 and A2 are closed in two steps.
The liquid outflow valves A1 and C were opened.

In the following, until the 8th step, the shut-off valve for shutting off, the eluent supply valve for opening, the A liquid outflow valve, and the C liquid outflow valve were sequentially moved in the liquid flow direction. In the first embodiment, the circulation valve M is closed in all steps.

21 cycles were repeated with the above steps 1 to 8 as one cycle.

The stock solution composition and operating conditions are shown in Table 1 below, and the composition of each recovered fraction is shown in Table 2 below.

[0027]

[Table 1]

[0028]

[Table 2]

Example 2 The apparatus of FIG. 1 was used also in this example.

The shut-off valve is normally open, and each supply valve, each outflow valve, and the circulation valve are normally closed.

As one step, the shutoff valve K5 is operated to shut off the flow between the packed towers 5 and 6, the stock solution supply valve F6 is opened to introduce the stock solution from the top of the packed tower T6, and the solution B outflow valve B5.
The liquid containing a large amount of maltose (liquid B) was extracted from the bottom of the packed tower T5.

After the elapse of a predetermined time, the shutoff valve K1 was closed and the circulation valve M1, the eluent supply valve D2, and the C liquid outflow valve C3 were opened as 1 of 2 steps. After the lapse of a certain period of time, as 2 of 2 steps, in addition to 1 of 2 steps, the circulation valve M1 was closed and the A liquid outflow valve A1 was opened.

Similarly, up to 8 steps, a shutoff valve that shuts off, a circulation valve that opens and closes, and an eluent supply valve that opens, A
The liquid outflow valve and the C liquid outflow valve were sequentially moved along the liquid flow direction.

The above steps 1 to 8 were set as one cycle, and 21 cycles were repeated.

The stock solution composition and operating conditions are shown in Table 3 below, and the composition of each recovered fraction is shown in Table 4 below.

[0036]

[Table 3]

[0037]

[Table 4]

The composition of the effluent after 21 cycles is as shown in Table 4 when one cycle of opening and closing of the valve, that is, from 1 step to 8 steps is defined as Table 4, and the amount of the eluent used is larger than that in Example 1. The concentration of the fraction A was increased.

Example 3 The apparatus of FIG. 1 was used also in this example.

The shut-off valve is normally open, each supply valve, each outflow valve, and the circulation valve are normally closed. Unless otherwise specified, they are in the normal state.

As one step, the shutoff valve K5 is operated to shut off the flow between the packed towers 5 and 6, the stock solution supply valve F6 is opened to introduce the stock solution from the top of the packed tower T6, and the solution B outflow valve B5.
The liquid containing a large amount of maltose (liquid B) was extracted from the bottom of the packed tower T5.

After the elapse of a predetermined time, the shutoff valve K1 is closed and the circulation valve M1, the eluent supply valve D2, and the C liquid outflow valve C3 are opened as one of the two steps (from the third section). Supply effluent to the first compartment).

After the elapse of a certain time, as 2 of 2 steps, in addition to 1 of 2 steps, the shutoff valve K1 and the circulation valve M1 were closed (only C was extracted).

After the elapse of a certain time, in addition to step 2 of step 2 as step 3, the liquid A outflow valve A1 was opened (A and C).
Extraction).

After the elapse of a certain time, the liquid C outflow valve C3, which was opened in 3 of 2 process, was closed in 4 of 2 process, and the other valves were left as they were (only A was extracted).

In the following, up to 8 steps, the shutoff valve, the circulation valve, the eluent supply valve, the A liquid outflow valve, and the C liquid outflow valve which were opened and closed were sequentially moved in the liquid flow direction.

The above steps 1 to 8 were set as one cycle, and 20 cycles were repeated.

The stock solution composition and operating conditions are shown in Table 5 below, and the composition of each recovered fraction is shown in Table 6 below.

[0049]

[Table 5]

[0050]

[Table 6]

The composition of the effluent after 20 cycles is as shown in Table 6 when one cycle of opening and closing the valve, that is, 1st to 8th steps is defined as one cycle. The purity of the target component is improved.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing a schematic configuration of a device used in an embodiment.

FIG. 2 is an explanatory diagram showing an operation flow and a distribution of each component of the first embodiment.

FIG. 3 (a) is an explanatory diagram showing the operation flow and the distribution of each component of Example 2.

FIG. 3 (b) is an explanatory view showing the operation flow and the distribution of each component of the second embodiment.

FIG. 5 (a) is an explanatory diagram showing an operation flow of Example 3 and distributions of respective components.

FIG. 4 (b) is an explanatory view showing the operation flow and the distribution of each component of Example 3.

FIG. 7 (c) is an explanatory diagram showing the operation flow and the distribution of each component of Example 3.

FIG. 4 (d) is an explanatory diagram showing the operation flow and the distribution of each component of Example 3.

[Explanation of symbols]

T1 to T8: packed tower, A1 to A8: A liquid outflow valve, A9:
Back pressure valve B4 to B6: B liquid outflow valve, C1 to C8: C liquid outflow valve, D
1 to D8: eluent supply valve, D9: check valve, F1 to F8:
Stock solution supply valve K1 to K8: Shutoff valve, M1 to M8: Circulation valve, P11: Eluent solution supply pump P12: Stock solution supply pump, P13: C solution extraction pump, H: Packing tower connection pipe, I: B solution extraction pipe, J:
Circulation piping.

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[Procedure amendment]

[Submission date] October 4, 1993

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[Brief description of drawings]

FIG. 1 is an explanatory diagram showing a schematic configuration of a device used in an embodiment.

FIG. 2 is an explanatory diagram showing an operation flow and a distribution of each component of the first embodiment.

FIG. 3 is an explanatory diagram showing an operation flow and a distribution of each component of the second embodiment.

[4] FIG. 4 is an explanatory view showing the distribution of the operation flows and the ingredients of Example 2.

[5] FIG. 5 is an explanatory view showing the distribution of the operation flows and the ingredients of Example 3.

[6] FIG. 6 is an explanatory diagram showing the distribution of the operation flows and the ingredients of Example 3.

[Figure 7] Figure 7 is an explanatory view showing the distribution of the operation flows and the ingredients of Example 3.

[Figure 8] Figure 8 is an explanatory view showing the distribution of the operation flows and the ingredients of Example 3.

[Explanation of Codes] T1 to T8: Packing tower, A1 to A8: A liquid outflow valve, A9:
Back pressure valve B4 to B6: B liquid outflow valve, C1 to C8: C liquid outflow valve, D
1 to D8: eluent supply valve, D9: check valve, F1 to F8:
Stock solution supply valve K1 to K8: Shutoff valve, M1 to M8: Circulation valve, P11: Eluent solution supply pump P12: Stock solution supply pump, P13: C solution extraction pump, H: Packing tower connection pipe, I: B solution extraction pipe, J:
Circulation piping.

Front page continuation (72) Inventor Kikuzo Kaneko 5-5-16 Hongo, Bunkyo-ku, Tokyo Organo Corporation

Claims (5)

[Claims] 1. A system of endless packed towers in which a large number of packed towers filled with an adsorbent are sequentially connected in series by pipes each having a shutoff valve, and three or more components having different affinities for the adsorbent are provided. Three compartments formed when a raw material fluid containing a is passed through the system (first compartment consisting of one or a plurality of packed tower groups enriched with components having a strong affinity for the adsorbent, intermediate affinity for the adsorbent) Adsorbent, which is composed of one or a plurality of packed tower groups enriched with the above components, and one or a plurality of packed tower groups in which a component having an intermediate affinity for this adsorbent and a component having a strong affinity are mixed. The third step consisting of the remaining packed tower group including one or a plurality of packed tower groups enriched with a component having a weak affinity for Alternatively,
The chromatographic separation method is characterized by repeating in the order of, and the packing located immediately downstream of the shut-off valve with the shut-off valve between the second and third compartments closed to shut off the fluid circulation in the entire system. Performing an operation of flowing out a fraction enriched in the intermediate component of the affinity from the outlet of any packed column in the second compartment while supplying the raw material fluid from the inlet of the column,
Step of shifting the distribution of the first section to the third section to the downstream side by at least one packed column Continuing from the above step, with the shutoff valve between the transferred third section and the first section closed, An operation of supplying a desorbent fluid from an inlet of a packed column located at the uppermost stream of one section, and flowing out a fraction enriched with the component having high affinity from the outlet of the most downstream packed column of the first section. And the operation of flowing out the fraction enriched with the component having a weak affinity from the outlet of the packed column located at the most downstream side of the third section, and the distribution of the first section to the third section is further downstream of the fluid. In synchronism with the transfer of only one packed column to the side, the same operation is performed by lowering the supply position of the desorbent fluid, the extraction position of each fraction, and the position of the shutoff valve for shutting off by one packed column. Steps repeated a predetermined number of times Following the above steps, the third section and the first section While the shutoff valve between the compartments is closed, the desorbent fluid is supplied from the inlet of the packed column located in the uppermost stream of the first section, and the affinity of the affinity is increased from the outlet of the most packed column in the first section. An operation of flowing out a fraction enriched in a strong component, an operation of flowing out a fraction enriched in a component having a weak affinity described above from an outlet of a packed column located at the most downstream side of the third compartment, and a second compartment The operation of flowing out the enriched fraction of the component having the intermediate affinity is performed from the outlet of the packed column located at the most downstream side of the column, and if necessary, the distribution of the first section to the third section is downstream of the fluid. In synchronism with the transfer of only one packed column to the side, the same operation is performed by lowering the supply position of the desorbent fluid, the extraction position of each fraction, and the position of the shutoff valve for shutting off by one packed column. A process of repeating a predetermined number of times. 2. The process according to claim 1, wherein the desorbent fluid is supplied from the inlet of the most upstream packed column in the first section, and the affinity for the adsorbent is adjusted from the outlet of the most downstream packed column in the first section. At least one of an operation of flowing out a fraction enriched in a strong component and an operation of flowing out a fraction enriched in a component having a weak affinity for an adsorbent from the outlet of the packed column at the most downstream side of the third section. A chromatographic separation method characterized by being performed simultaneously or sequentially. 3. The process according to claim 1 or 2, in which the shutoff valve in the system is closed so as to prevent the flow of fluid from the second compartment to the third compartment, instead of the step of While being supplied with the raw material fluid from the inlet of one of the packed towers located on the upstream side in the third compartment located downstream of this shutoff valve, it is located on the downstream side in the second compartment located upstream of the shutoff valve The first compartment to the third compartment is operated by flowing out the fraction enriched in the intermediate component from the outlet of any of the packed towers.
A chromatographic separation method comprising the step of shifting the distribution of compartments to the downstream side by at least one packed column. 4. A filling located upstream of the first compartment with the shutoff valve between the third compartment and the first compartment closed before and / or after the step of any one of claims 1 to 3. An operation of causing the enriched fraction of the component having a strong affinity to flow out from the outlet of the packed column at the most downstream side of the first compartment while supplying the desorbent fluid from the inlet of the tower; While supplying the desorbent fluid from the inlet of the packed tower located at the same time, the operation of causing the enriched fraction of the component having a weak affinity to flow out from the outlet of the packed tower located at the most downstream side of the third section is simultaneously performed. A chromatographic separation method, characterized in that it is performed sequentially, or at least one of these operations is performed in addition to performing these operations simultaneously. 5. The method according to any one of claims 1 to 4,
Prior to the operation of each of the repeated steps, or the step and the subsequent steps, with the shut-off valves in the system open, the uppermost stream of the first compartment While supplying the desorbent fluid from the inlet of the packed tower located at 1, the fraction enriched with the component having a strong affinity for the adsorbent is discharged from the outlet of the packed tower located at the most downstream side of the first section. A chromatographic separation method characterized by the above.