JPH0695090B2 - Pseudo moving bed liquid chromatographic separation device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a simulated moving bed type liquid chromatographic separation device having a simple control mechanism despite the small number of circulation pumps.

[Prior Art] FIG. 6 is a conceptual diagram of two-component separation by a conventional moving bed. Component A (sorbate) that has a strong affinity for the filler (solid sorbent) and component B (non-sorbate) that has a weak affinity for the filler.
When separating and, the component A in the packed bed packed with the packing material
The moving speeds of the component B and the component B are Va and Vb, respectively. Sixth
As shown in the figure, when the filler is moved at the intermediate velocity Vs in the direction opposite to the flow direction of the fluid, the component B moves in the fluid moving direction at a velocity of Vb-Vs, and the component A moves at a velocity of Vs-Va. Since the fillers move in the respective moving directions, it is possible to continuously separate the two components A and B. This is well known as a moving bed type.

However, it is difficult to actually move the filler because it causes wear of the filler and changes in the porosity.

In the simulated moving bed system, one unit packed bed is divided into several to dozens, and the inlet and the outlet of each unit packed bed are moved in the liquid flow direction at a constant cycle so that the packing material is actually added. Since the above-mentioned function can be achieved without moving, the defect of the moving bed type is eliminated and continuous separation of two components (or multiple components that can be regarded as two components) becomes possible.

As shown in FIG. 7, the simulated moving bed usually consists of four zones. Primary purification zone (Zone 1)
Since the component B (non-sorbate) having a weak affinity with the packing material is recovered and the eluent (desorbent fluid) is regenerated, the adsorption zone (zone 2) has a strong affinity with the packing material A (sorbent). Raffinate (fluid rich in non-sorbate)
In order to recover the component B, the secondary purification zone (zone 3) desorbs the component B and purifies the component A, and the desorption zone (zone 4) desorbs the purified component A and extract (collection). It is provided to collect as a fluid with high quality.

Conventionally, as a simulated moving bed, the one shown in FIG. 8 has been known. 11 to 22 are unit packed beds filled with a solid sorbent, and the front ends and the rear ends of these unit packed beds are connected by a flow path to form an endless form. Circulation pump 31 in the packed bed
Causes the fluid to circulate in one direction, the raw material liquid pump 41 introduces the raw material liquid into the circulating fluid, and the eluent pump 42 introduces the eluent liquid. At the same time, a fluid (raffinate) rich in non-sorbate from the packed bed is introduced. ) Is extracted via the flow valve 44, and a fluid (extract) rich in sorbate is extracted by the extract pump 43.

The inlet and outlet of the fluid introduced into the packed bed or withdrawn from the packed bed are alternately arranged along the flow direction of the circulating fluid, and the packed bed is circulated. The positions of the inlet and the outlet of the packed bed can be intermittently moved in the flowing direction of the fluid. VF _{1 to} VF ₁₂ are two-way solenoid valves for switching the supply of raw material liquid, VD _{1 to} VD ₁₂ are two-way solenoid valves for switching the supply of eluent, and VR _{1 to} VR ₁₂ are for switching raffinate withdrawal. The two-way solenoid valves VE _{1 to} VE ₁₂ are two-way solenoid valves for switching the extraction of the extract.

Also, in Japanese Patent Laid-Open No. 55-70336, as shown in FIG. 9, instead of providing one circulation pump in the circulation line in the configuration shown in FIG. There is described a simulated moving bed in which a plurality of metering pumps 51, 52, 53 are installed and these pumps are sequentially switched so that only one pump operates at a time.

[Problems to be Solved by the Invention]

In the conventional simulated moving bed shown in FIG. 8, since the circulation pump 31 is installed between the fixed unit packed beds, the discharge flow rate of the circulation pump 31 must be changed periodically. If this circulating flow rate deviates from the set value, the separation efficiency of the simulated moving bed will drop significantly, so it is necessary to control this flow rate with high accuracy. On the other hand, since the composition of the fluid flowing into the circulation pump also changes sequentially, the physical properties such as the specific gravity and viscosity of the fluid also change accordingly.

Automatically controlling the flow rate by a program control device in accordance with such changes in physical properties and setting values requires an expensive control device and a stable flow rate with an ordinary reciprocating metering pump. There is a drawback that it is difficult to secure.

Further, in the simulated moving bed described in JP-A-55-70336, a circulation pump (quantitative pumps 51, 52, 5
The control mechanism is extremely simple because the flow rate of 3) is not changed.

However, since the composition of the fluid flowing into the circulation pump (quantitative pumps 51, 52, 53) also changes sequentially, the physical properties such as the specific gravity and viscosity of the fluid also change accordingly. In particular, when the viscosity of the raw material is large due to separation of sugar or the like, the change is large, and it is difficult to secure a stable flow rate with an ordinary reciprocating metering pump.

The present invention has been made in view of the above points, and the unit packed beds are shifted one by one and switched to form four zones (zones) so that the circulation pump always stays at a fixed position and is introduced into the circulation pump. It is an object of the present invention to provide a simulated moving bed type liquid chromatographic separation device capable of performing stable operation with an ordinary reciprocating type quantitative pump by being configured so that the change in the physical properties of the liquid to be treated becomes small. Is.

[Means and Actions for Solving the Problems]

In order to achieve the above object, the simulated moving bed type liquid chromatographic separation device of the present invention will be described with reference to FIG.
Filled with solid sorbent and arranged in series 4
Consisting of more than one unit packed bed 11 to 22, the front end and the rear end of these unit packed beds are connected in a flow path to circulate a fluid in one direction in an endless packed bed, The raw material liquid and the eluent are introduced into this circulating fluid, and at the same time, the fluid rich in non-sorbate and the fluid rich in sorbate are extracted from the unit packed bed (introduced into or extracted from the packed bed). The above-mentioned four kinds of fluids are sometimes referred to as side flows in the following description), and the inlets and outlets of the above-mentioned fluids that are introduced into or withdrawn from the packed bed (hereinafter, these are referred to as side flow ports). Are alternately arranged along the flow direction of the circulating fluid, and the positions of the inlet and the outlet of the packed bed are intermittent in the flow direction of the fluid circulating through the packed bed. Simulated moving bed liquid chromatographic separation configured to move dynamically In the apparatus, one circulation pump 46 was provided, and a solenoid valve for switching the flow path was arranged so that this circulation pump 46 was always between the primary purification zone (zone 1) and the desorption zone (zone 4). It is characterized by that.

Further, the back pressure of the circulation pump 46 can be controlled by an eluent pump and a back pressure valve, or by an eluent head tank as shown in FIG. Back pressure valve 48 or eluent head tank 49
Connect.

In the simulated moving bed, four side outlets are activated at the same time, and the function of the packed bed is four zones (zones) due to these side outlets, that is, the non-sorbed material from the raw material liquid inlet is rich. Adsorption zone (zone 2) that occupies the fluid (raffinate) outlet, and primary purification zone (zone 1) that occupies the non-sorbate-rich fluid outlet and desorbent fluid (eluent) inlet ), Desorption zone (zone 4) occupying from the desorbent fluid inlet to the outlet of the sorbate rich fluid (extract), from the outlet of the sorbent rich fluid to the raw material liquid inlet The secondary purification zone (zone 3) occupies four zones (zones).

〔Example〕

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. However, the shape of the components described in this embodiment, the relative arrangement, and the like, unless otherwise specified, are not intended to limit the scope of the present invention to only those, and are merely illustrative examples. Only.

FIG. 1 shows, as an example, a simulated moving bed type liquid chromatographic separation apparatus provided with 12 unit packed beds 11 to 22. Circulation conduits 601 to 612 connect the unit packed beds. The raw material liquid is introduced into each unit packed bed through the raw material liquid pump 41, the raw material liquid conduit 807 and the raw material liquid introduction branch pipes 401 to 412 communicating with the raw material liquid pipe 807.

Two-way solenoid valves VF _{1 to} VF ₁₂ are provided in the raw material liquid introducing branch pipes 401 to 412. Desorbent fluid (eluent) is the eluent pump
It is introduced into each unit packed bed through 47, an eluent conduit 808, a circulation pump 46, a circulation conduit 810, and eluent introduction branch pipes 501 to 512. The branch pipes 501 to 512 are also provided with two-way solenoid valves VD _{1 to} VD ₁₂ .

The sorbate-rich fluid (extract) is extracted from each unit packed bed via the extract extraction branch pipes 201 to 212, the extract conduit 805, and the extract pump 43. Two-way solenoid valves VE _{1 to} VE ₁₂ are connected to these branch pipes 201 to 212.
Is provided. On the other hand, the fluid (raffinate) rich in non-sorbate is extracted from each unit packed bed via the raffinate extraction branch pipes 301 to 312, the raffinate conduit 806, and the raffinate pump 45. Two-way solenoid valves VR _{1 to} VR ₁₂ are also provided in these branch pipes 301 to 312.

The conduit connecting the extract draw-out branch pipe 201 to 212 and raffinate draw-out branch pipe 301 to 312 respectively, the three-way solenoid valve VT ₁ ~VT ₁₂ are respectively provided, these three-way electromagnetic valve VT ₁ to VR ₁₂ One of them is connected to a circulation conduit 810 to which the eluent pump 47 is connected via conduits 901 to 912.

The raffinate pump 45, the extract pump 43, the raw material liquid pump 41, and the circulation pump 46 are all controlled so that the flow rate becomes a set value (constant). In addition, the circulation pump 46
Eluent pump 47 so that the back pressure of
And the back pressure valve 48 is controlled.

Next, an example of the opening / closing cycle of the solenoid valve according to the present invention will be described in the case where the unit packed bed is 12 beds. The separation pattern has three primary purification zones (zone 1), adsorption zones (zone 2), secondary purification zones (zone 3), and desorption zones (zone 4).

Since there are twelve unit packed beds, twelve steps will be performed. As an example, step 1 is shown in FIG.
Step 2 is shown in FIG. 3 and step 3 is shown in FIG. The open / closed state of each solenoid valve in this case is as shown in Table 1.

In step 1 of FIG. 2, the raw material liquid is supplied to the unit packed bed 17 and circulates through the unit packed beds 18 and 19. During this time, the sorbate-rich substance is adsorbed by the packing material and the non-sorbate-rich fluid is withdrawn from the unit packed bed 19 as a raffinate.
That is, the unit packed beds 17 to 19 are adsorption zones (zone 2).

On the other hand, the circulating fluid containing the eluent is supplied to the unit packed bed 11 and circulates through the unit packed beds 12 and 13. During this time, the adsorbate adsorbed by the packing material is desorbed, and the fluid rich in sorbate is extracted from the unit packed bed 13 as an extract. That is, the unit packed beds 11 to 13 are desorption zones (zone 4).

The circulating fluid is circulated to the unit packed beds 20 to 22. During this time, the non-sorbate is adsorbed by the packing material, becomes a fluid containing neither sorbate nor non-sorbate, and is extracted from the unit-packed bed 22. That is, the unit packed beds 20 to 22 are the primary purification zone (zone 1).

The circulating fluid is circulated to the unit packed beds 14 to 16, while the non-sorbate in which the packing material is adsorbed is desorbed, while the sorbate is adsorbed in the packing material and purified. That is, the unit packed beds 14 to 16 become the secondary purification zone (zone 3).

In step 2 of FIG. 3, the state in step 1 is shifted to the left by one unit packed bed, and the unit packed beds 12 to 14 are desorbed zone (zone 4), unit packed bed 15 to
17 is the secondary purification zone (zone 3), the unit packed beds 18-20 are the adsorption zone (zone 2), and the unit packed beds 21, 22, 11 are the primary purification zone (zone 1).

In step 3 of FIG. 4, the state in step 2 is further shifted to the left by one unit packed bed, the unit packed beds 13 to 15 are desorption zones (zone 4), and the unit packed beds 16 to 18 are two. Next purification zone (zone 3), unit packed bed 19
21 to 21 are adsorption zones (zone 2), and the unit packed beds 22, 11, and 12 are primary purification zones (zone 1).

Although not shown, the unit packed beds are shifted to the left one by one, and the operation is repeated up to step 12 to repeat these operations.

In either step, the suction conduit of the circulation pump 46 is connected to the outlet of the final stage unit packed bed of the primary purification zone (zone 1) and the discharge conduit of the circulation pump 46 is the first stage unit of the desorption zone (zone 4). It will be connected to the inlet of the packed bed. Therefore, the change in the physical properties of the liquid introduced into the circulation pump 46 is reduced, and stable operation can be performed. In particular, the viscosity between the primary purification zone (zone 1) and the desorption zone (zone 4) is the lowest, which is preferable.

In the present invention, the number of solenoid valves is increased compared to the device of JP-A-55-70336, but the number of pumps is reduced, the solenoid valve is cheaper than a metering pump, and the control system is simple. Therefore, the total device cost is reduced.

FIG. 5 shows another embodiment of the device of the present invention. In this example, instead of connecting the eluent pump and back pressure valve to the circulation conduit 810, the eluent head tank 49 is connected to the circulation conduit 810. The eluent is supplied to the tank 49 so as to always have a constant depth. Other configurations and operations are similar to those in the case of FIGS. 1 to 4.

〔The invention's effect〕

Since the present invention is configured as described above, it has the following effects.

(1) Since the flow rate of the circulation pump is not changed during operation, the control mechanism is extremely simple and can be manufactured at low cost.

(2) Since the circulation pump is always located between the primary purification zone (zone 1) and the desorption zone (zone 4), the change in the physical properties of the liquid introduced into the circulation pump is small, and therefore the ordinary reciprocating quantitative measurement is performed. The pump can ensure a stable flow rate. Particularly, it has the lowest viscosity and is suitable.

[Brief description of drawings]

FIG. 1 is a conceptual explanatory view showing one embodiment of the simulated moving bed type liquid chromatographic separation device of the present invention, FIG. 2 is a conceptual explanatory view showing the state of step 1 in the device shown in FIG. 1, and FIG. FIG. 4 is a conceptual explanatory diagram showing the state of step 2, FIG. 4 is a conceptual explanatory diagram showing the state of step 3, FIG. 5 is a conceptual explanatory diagram showing another embodiment of the apparatus of the present invention, and FIG. A conceptual diagram of two-component separation by bed, FIG. 7 is an explanatory diagram showing a general configuration of a simulated moving bed type continuous liquid chromatographic separation device, and FIGS. 8 and 9 are conceptual explanatory diagrams showing a conventional simulated moving bed. Is. 11 to 12 ... Unit packed bed, 31 ... Circulation pump, 41 ... Raw material liquid pump, 42 ... Eluent pump, 43 ... Extraction pump, 44
… Flow valve, 45… Raffinate pump, 46… Circulation pump,
47 ... eluent pumps, 48 ... back pressure valve, 49 ... eluent head tank, 51, 52, 53 ... metering pump, VF ₁ ~VF ₁₂ ... raw-liquid two-way solenoid valve for, VD ₁ to VD ₁₂ ... eluent 2-way solenoid valve for VR ₁ , VR ₁ ~
VR ₁₂ ... 2-way solenoid valve for raffinate, VE _{1 to} VE ₁₂ ... 2-way solenoid valve for extract, VT _{1 to} VT ₁₂ ... 3-way solenoid valve, 2
01-212 ... Extract extraction branch pipe, 301-312 ... Raffinate extraction branch pipe, 401-412 ... Raw material liquid introduction branch pipe, 50
1-512 ... Eluent introduction branch pipe, 601-612 ... Circulation conduit, 805
… Extract conduit, 806… Raffinate conduit, 807…
Raw material liquid conduit, 808 ... Eluent conduit, 810 ... Circulation conduit, 901-9
12 ... conduit

Front page continued (72) Inventor Tatsuya Imura 1-1 Kawasaki-cho, Akashi-shi, Hyogo Kawasaki Heavy Industries Ltd. Akashi factory (72) Inventor Seiichi Nakanishi 3-1-1 Higashikawasaki-cho, Chuo-ku, Kobe-shi, Hyogo Kawasaki Heavy industry Co., Ltd. Kobe factory (72) Inventor Hiroyasu Edo 3-1, 1-1 Higashikawasaki-cho, Chuo-ku, Kobe-shi, Hyogo Kawasaki Heavy Industry Co., Ltd., Kobe factory (56) Reference JP-A-2-49159 (JP, A) JP-A-55-70336 (JP, A) JP-A-62-190463 (JP, A) JP-A-64-83152 (JP, A) Practical application JP-A-62-199674 (JP, U) JP-A-1-165953 (JP, A) JP-A-2-64453 (JP, A)

Claims (2)

[Claims] 1. A solid sorbent-packed bed composed of four or more unit-packed beds (11-22) arranged in series, wherein the front and rear ends of these unit-packed beds are A fluid is unidirectionally circulated in an endless packed bed connected by a flow path, and a raw material liquid and an eluent are introduced into this circulating fluid, and at the same time, a non-sorbed material from the unit packed bed. The fluid-rich fluid and the sorbate-rich fluid are extracted, and the fluid inlets and outlets introduced into the packed bed or withdrawn from the packed bed are alternated along the flow direction of the circulating fluid. 1. A simulated moving bed liquid chromatographic separation device which is arranged and is configured to intermittently move the positions of the inlet and the outlet of the packed bed in the flow direction of the fluid circulating in the packed bed. Circulating pump (46) is provided for this table, and this circulating pump (46)
The simulated moving bed liquid chromatographic separation device is characterized in that a solenoid valve for switching the flow path is arranged so that is always between the primary purification zone and the desorption zone. 2. An eluent pump (47) at the inlet side of the circulation pump (46) so that the back pressure of the circulation pump (46) can be controlled by an eluent pump and a back pressure valve or by an eluent head tank. The simulated moving bed type liquid chromatographic separation apparatus according to claim 1, further comprising a back pressure valve (48) or an eluent head tank (49) connected thereto.