JPH03100459A - Pseudo moving bed type chromato separation - Google Patents

Abstract

PURPOSE:To allow inexpensive sepn. of products without lowering sepn. performance and without diluting the products by transferring shut off position of shut off valves, the supply position of liquid and the recovery position of fluid by each column to the downstream at every specified time. CONSTITUTION:An endless packed column group is formed by connecting, in an endless state, >=3 pieces of the packed columns each packed with an adsorbent having the selective adsorptive power to a specific component A among >=2 components contained in the raw material fluid as compared to the other component B in series by pipings having the shut off valves. The packed column group is divided to a 1st block to a 3rd block along the flow of the fluid flowing in the inside. The shut off position of shut off valves, the supply position of liquid and the recovery position of fluid are transferred to the downstream side by each one column at every specified time while at least the two stages of the stage for recovering the extract liquid essentially composed of the component A by closing the shut off valve between the 2nd and 3rd blocks, the stage for recovering the extract liquid essentially composed of the component A by closing the shut off valve between the 1st and the 2nd blocks and the stage for recovering the raffinate liquid essentially composed of the component B from the rear end of the 1st block are carried out in arbitrary order.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for chromatographically separating a specific component out of two or more components in a raw material containing various chemical components by a simulated moving bed method using an adsorbent. .

[Conventional technology]

Conventionally, adsorbents such as ion exchange resins and zeolites are used to separate two or more components contained in raw materials such as isomer mixtures, and the separation takes advantage of the difference in adsorption performance of these components to the adsorbent. Chromatographic techniques are widely used. As this type of chromatographic separation method, fixed bed method and moving bed method have been known for a long time.
In recent years, due to problems such as separation efficiency and movement of adsorbent, a pseudo moving bed system (for example, Japanese Patent Publication No. 42-15681 for a continuous system, and Japanese Patent Publication No. 41559 1989 for a batch system) has been proposed in recent years. In addition, as a modification of the pseudo moving bed, C0B, Ching
have proposed a system in which a shutoff valve is connected between each column (bed) (for example, Chem, Eng.

Sci, Vol. 40. No.6. pp8? ? -885
, 1985).

FIG. 1 is an explanatory diagram of a separation method using such a simulated moving bed device with a shutoff valve, in which adsorbent packed columns 1 to 12 are connected in series and endlessly through pipes each having a shutoff valve a to Q. is,
It forms an endless group of packed towers. This packed tower group consists of towers 1 to 5 along the flow of fluid flowing inside (clockwise in the figure).
A first section consisting of a tower 6, a second section consisting of a tower 6, and a tower 7~
It is divided into 12 third sections. It is assumed that the adsorbent packed in the packed tower has a selective adsorption power for a specific component A out of two or more components contained in the raw material over the other component B. Conventionally, in such an apparatus, after closing the shutoff valve e between the first and second compartments and the shutoff valve f between the second and third compartments and supplying the raw material from the column 1 at the front end of the first compartment, After collecting the raffinate liquid mainly consisting of the B component that is difficult to adsorb from the column 5 at the rear end of the first section, and supplying the eluent (I) from the column 6 at the front end of the second section, From the outlet of 6, extract liquid mainly composed of component A, which is easily adsorbed, is collected, and while supplying the eluent (2) again from the front end of the third compartment, the cutoff position of the cutoff valve is adjusted at regular intervals. Both the A and B components are separated by moving the fluid supply position and the fluid recovery position to the downstream side one tower at a time.

If eluents (I) and (2) have the same composition, the combined amount of eluents (I) and (2) will be injected from the inlet position of eluent (I) as shown in Figure 2. However, it is also possible to operate with the shutoff valve between the second section and the third section open.

Compared to the normal simulated moving bed method that does not have a shutoff valve, these methods do not require flow rate control of the pump on the effluent (recovered liquid) side, and do not require an inter-column pump, or even if there is one, flow rate control is easy. This simplifies the device. These effects will be explained using the method shown in FIG.

In the system shown in FIG. 2, when extract liquid is recovered in the second compartment, if component B, which is difficult to be adsorbed, is contained, the purity of component A in the extract liquid will be reduced. Therefore, it refers to a step (operation for a certain period of time before the shutoff position of the shutoff valve, the fluid supply position and the fluid recovery position are moved further downstream).

The operation of repeating the transition and returning to the initial position is called one cycle. ) is transferred (switched), it is necessary to increase the number of columns so that no B component remains in the second section. Similarly, if a component A that is easily adsorbed remains at the end of the step in the second section, the remaining component A flows into the raffinate liquid as an impurity after the step movement. in this case,
It is necessary to completely flow out (expel) component A from the raffinate solution by increasing the amount of eluent. On the other hand, after the step transition, the B component, which is difficult to adsorb, flows into the raffinate liquid at the rear end of the first section, but gradually the A component, which is easily adsorbed, also begins to flow into the raffinate liquid. The step transition time is determined at this timing. Also, the number of packed columns and operating conditions are determined in this way.

Therefore, in order to improve the separation performance using the simulated moving bed system with a shutoff valve as shown in Figure 2, it is necessary to increase the number of columns or increase the amount of eluent, which may increase equipment costs or utility costs, and reduce recovery. It has drawbacks such as dilution of the product.

[Problems to be Solved by the Invention] The purpose of the present invention is to eliminate the above-mentioned drawbacks of the prior art, and to produce a product at low cost without deteriorating separation performance, with simple equipment or with a small utility burden. An object of the present invention is to provide a simulated moving bed chromatographic separation method that allows separation without dilution.

[Means to solve the problem]

The purpose is to provide three or more packed towers each filled with an adsorbent having a selective adsorption power for a specific component A among two or more components contained in the raw material fluid compared to other components B, each having a cutoff valve. They were connected in series and endlessly with piping to form an endless group of packed towers, and this group of packed towers was divided into a first section, a second section, and a third section along the flow of the fluid flowing inside. Up,
(I) After closing the shutoff valve between the second compartment and the third compartment and supplying the raw material from the column at the front end of the first compartment and/or supplying the eluent from the column at the front end of the second compartment, after the second compartment A step of recovering extract liquid mainly consisting of component A from the end tower, (I
I) After closing the shutoff valve between the first compartment and the second compartment, supplying the raw material from the column at the front end of the first compartment, and supplying the eluent from the column at the front end of the second compartment, the column at the rear end of the first compartment a step of recovering a raffinate liquid mainly consisting of component B from the column, and recovering an extruded liquid mainly consisting of component A from the column at the rear end of the second section, and (m) blocking between the first section and the second section. After the valve is closed and the raw material is supplied from the column at the front end of the first section and/or the eluent is supplied from the column at the front end of the second section, the raffinate liquid mainly containing component B is supplied from the column at the rear end of the first section. It is characterized by moving the shutoff position of the shutoff valve, the liquid supply position, and the fluid recovery position to the downstream side one tower at a time at regular intervals while performing at least two recovery steps in an arbitrary order. This can be achieved by a simulated moving bed chromatographic separation method. Note that the step (II) itself corresponds to the method shown in FIG.

In this way, in the conventional method, the fluid supply or recovery position and the shutoff position of the shutoff valve are fixed during one step, whereas the present invention includes the above-mentioned plurality of steps during one step. It is a feature. Note that the amounts of raw materials and eluent used in each step may be set to be the same, or may be set to be individually different.

[For production]

In order to improve the separation performance without increasing the number of columns in the present invention, in particular, based on the step (II), (I) and/or (m)
It is preferable to perform the operation by adding the step of. This will be specifically explained using a four-column simulated moving bed apparatus (the first section is the first and second columns, the second section is the third column, and the third section is the fourth column) having a shutoff valve.

In order to separate component A, which is easily adsorbed by the adsorbent, and component B, which is difficult to adsorb to the adsorbent, using this device, the process cycle of (It) is repeated. , the extract liquids are represented by F, W, R, and E, respectively, and the A component is shown by a solid line, and the B component is shown by a broken line. The vertical axis of the square representing the tower represents the concentration, and the horizontal axis represents the position (upstream → downstream). The closed position of the shutoff valve is indicated by X. 4 as shown in ]
A tower concentration pattern results. When moving from this state to the next step, component A is added to the raffinate solution as described above.
In addition, component B flows into the extract liquid, reducing the purity of each component. Therefore, the steps (I) and/or (m) are added to the step (II) before and after the step transition.

An example of this state is shown in FIGS. 4(a), (b), and (C). That is, when the state as shown in FIG. 3 occurs during step transition, the (ffl) shown in FIG. 4(a) The process moves on to step 2, stopping the recovery of the extract liquid with a low concentration, and causing the component A in the third column to flow into the fourth column. At this time, component B from the fourth column can also be allowed to flow into the first column. Next, when the step is shifted to the state shown in Figure 4(b),
As shown in FIG. 4(c), impurity components are prevented from flowing into the extract liquid and raffinate liquid. After that, when the state shown in Fig. 3 is reached, the operation of repeating the step (m) of Fig. 4 (a) may be continued, but immediately after the step transition, the eluent containing no component A is recovered from the raffinate solution. This prevents a decrease in the concentration of the raffinate solution and
In order to speed up the movement of the components, the process may proceed to step (I) above. The situation in this case is shown in Figure 4 (d) and (e).
Shown below. That is, by moving to the step (I), the state shown in FIG. 4(b) changes to the state shown in FIG. 4(d).

At this time, collection of the raffinate solution is stopped and only the extract solution is collected. When the state shown in FIG. 4(e) is reached, the state shown in FIG. 4(C) is returned by moving to step (II).

Therefore, it can be easily understood that adding steps (I) and (m) to step (II) improves the purity of each.

The above is a repetition of steps (II) and (m), or (I)
, (II) and (m).
) Similar performance improvement effects are observed by repeating the process.

〔Example〕

The present invention will be explained below by way of examples.

Example 1 A four-column shutoff valve in which each column has an inner diameter of 1.5 cm and a length of 50 cm is a pseudo moving bed device (the first section is the first to second column, the second section is the third column, and the third section is the fourth column). HPI as an adsorbent in each column of
Filled with MG (Diaion), a 15 wt% ethanol solution containing 5 wt% of caffeine (CAF) and 15 wt% of epigallocatechin gallate (EgCg) was used as a raw material, and a separation operation was performed using 15% ethanol as an eluent. I did it. This operation lasts for one step (
The steps were repeated by performing steps I), (II) and (II[) in this order.

The operating conditions are shown in Table 1.

After reaching a steady state after passing through the barley IO psi, CA from the extract solution to EgCglQO% from the raffinate solution.
A purity and recovery of 100% F was obtained.

Comparative Example 1 The same operation as in Example 1 was performed with one step interval (II
) carried out in the state of the process. However, the step movement time is shown in the table.
The state retention time of steps (I), (ff), and (III) was set to a total of 103 minutes. After 10 cycles, EgCg purity was 90% and recovery rate was 9 from the extract liquid.
6%, CAF purity 85% from raffinate solution, recovery rate 6
8% was obtained.

Comparative Example 2 The same operation as Comparative Example 1 was performed using a 6-column type shutoff valve equipped pseudo moving bed device (
The first section was carried out using the 1st and 2nd columns, the second section was carried out using the 3rd and 4th columns, and the third section was carried out using the 5th and 6th columns). After 10 cycles, a purity and recovery rate of 100% EgCg was obtained from the extract solution and 100% CAF from the raffinate solution.

As is clear from Comparative Example 1, the purity is low when only the base step (II) is operated, but according to the method of the present invention in Example 1, although the raw material throughput is reduced to about 90%, the amount of eluent used is It can be seen that the purity is further reduced to 80%, and the separation performance is improved. Also, from Example 1 and Comparative Example 2, the purity of the 6-column type using only the base step (II) and the purity of the 4-column type using the method of the present invention are shown. The purity of the formula is the same.

This seven uses 66% of the filling amount and 90% of the raw material processing amount.
This shows the superiority of the present invention because the load on the filler is improved and equipment costs can be reduced.

〔Effect of the invention〕

The method of the present invention uses a conventional simulated moving bed device with a shutoff valve and operates at least two of steps (I), (II), and (m) in combination, without reducing separation performance and at low cost. ,
And with simple equipment or a small utility burden,
Moreover, the desired component can be separated from the raw material with high purity and high recovery rate without diluting the product.

[Brief explanation of drawings]

Fig. 1 is an explanatory diagram of the conventional method using a pseudo moving bed device with a shutoff valve, Fig. 2 is a modification of Fig. 1, and Fig. 3 is an explanatory diagram of the conventional method using a pseudo moving bed device with a four-column shutoff valve. Figures 4 (a), (b), and (c) represent the concentration patterns in each column when the separation operation was performed by repeating the process cycle of (It).
4 represents the concentration pattern in each column when the method of the present invention is carried out by adding the step (III) of the present invention to the step (II), and FIGS. 4(d) and (e)
The concentration pattern in each column is shown when the method of the present invention is carried out by adding the step (I) of the present invention to the steps [) and (m). 1 to 12... Packed tower ayQ... Shutoff valve F.
...Raw material W...Eluent R...Raffinate solution E...Extract liquid Solid line...Component A Broken line...Component B Figure 2 Figure 3

Claims (1)

[Claims] 1. Three or more packed towers filled with an adsorbent that has a selective adsorption power for a specific component A out of two or more components contained in the raw material fluid than other components B are installed in piping with a shutoff valve. Connecting in series and endlessly to form an endless group of packed columns, dividing this group of packed columns into a first section, a second section, and a third section along the flow of the fluid flowing inside, (I)
After closing the shutoff valve between the second compartment and the third compartment, supplying the raw material from the column at the front end of the first compartment, and/or supplying the eluent from the column at the front end of the second compartment, the column at the rear end of the second compartment (II) Close the shutoff valve between the first compartment and the second compartment to supply the raw material from the column at the front end of the first compartment, and After supplying the eluent from the column, a raffinate liquid mainly consisting of component B is recovered from the column at the rear end of the first section, and an extract liquid mainly consisting of component A is recovered from the column at the rear end of the second section. and (III) after closing the shutoff valve between the first compartment and the second compartment and supplying the raw material from the column at the front end of the first compartment and/or supplying the eluent from the column at the front end of the second compartment, While performing at least two steps in any order of the step of recovering the latinate liquid mainly containing component B from the column at the rear end of one section,
A pseudo moving bed chromatography separation method characterized by shifting the shutoff position of a shutoff valve, the liquid supply position, and the fluid recovery position to the downstream side one tower at a time at regular intervals.