JPH067612A - Pseudo moving bed device provided with check valve - Google Patents

Abstract

PURPOSE:To effectively separate a specified component at high speed without causing a backflow phenomenon of circulating liquid due to pressure loss of a filler even if raw material liquid or desorbed liquid is introduced into an introducing port at high speed by installing a check valve between a liquid outlet and the introducing port of respective unit packed beds connected in series. CONSTITUTION:Unit packed beds 2a-2h are connected in series and their front and rear ends are connected by a liquid passage 1 to made them in an endless form and liquid is unidirectionally circulated. In the unit packed beds, a desorbed liquid introducing port 3, a withdrawal port 4 for a liquid contg. a material easy to adsorb (extract), a raw material mixture contg. liquid introducing port 5 and a withdrawal port 6 for a liquid contg. a material hard to adsorb (raffinate) are arranged and they are intermittently and successively moved in the flow direction of fluid in the beds, and solvent and components are recovered from the extract and raffinate. At this time, a check valve 7 is installed between the liquid outlet and the introducing port of the respective unit packed beds 2a-2h. Therefore, the backflow of the circulated liquid is prevented to cause no large pressure loss in the unit packed beds.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a simulated moving bed apparatus with a check valve, and more specifically, it is possible to introduce a raw material multi-component mixture and / or a desorbed liquid at high speed, and to efficiently supply necessary components. The present invention relates to a pseudo moving bed device with a check valve that can be separated.

[0002]

2. Description of the Related Art Conventionally, a method using a simulated moving bed apparatus has been proposed as a method for separating necessary components from a mixture of plural components (Japanese Patent Publication No. 4).
2-15681).

The proposed simulated moving bed apparatus, as described in the above publication, connects four treatment zones filled with a solid sorbent in a line, and these four treatment zones are the outlets of the fourth zone. The fluid is circulated through the four treatment zones by connecting the inlet and the inlet of the first zone, and an introduction point and a sorption for supplying the raw material multi-component mixture to be separated to the treatment zones. Raffinate withdrawal point for drawing out a portion (raffinate) not treated, desorbent introduction point for supplying desorbent to the treatment zone, and desorbent for withdrawing desorbent and sorbed components from the treatment zone / The content is to advance the sorbent withdrawal points simultaneously and periodically.

The solid sorbent filled in this treatment zone is a fine powder, and its size is usually 0.15 mm or more (Japanese Patent Publication No. 42-15681, No. 11).
(See right column, lines 6 to 10). Since the solid sorbent having such a particle size has a large particle size, the feed mixture and the desorbent can be introduced at a high speed. However, in order to perform the separation efficiently and at high speed using such a simulated moving bed apparatus, the particle size of the solid sorbent must be made finer. Then, if it is attempted to fill the treatment zone with a solid sorbent having a smaller particle size and introduce the feed mixture and the desorbent into the treatment zone at a high speed as in the conventional case,
Pressure loss occurs in the treatment zone and backflow of the circulating fluid occurs in the treatment zone. This backflow of circulating fluid significantly reduces the separation efficiency. Therefore, even if the particle size of the solid sorbent is made fine to improve the separation efficiency, for example, the introduction speed of the feed fluid into the treatment zone must be decreased, and the separation efficiency cannot be said to be industrial due to the decrease of the introduction speed. It will be lowered.

Further, in the case where the particle size of the packing material in the conventional simulated moving bed apparatus is originally small, if the introduction speed of the supply fluid is increased in order to further improve the separation efficiency, the circulating fluid as described above is obtained. Backflow phenomenon occurs, and the separation efficiency decreases.

In fact, in recent years, attempts have been made actively to separate, for example, optical isomers by using such a simulated moving bed apparatus. In that case, 1 to
The packed bed is filled with a very fine optical resolving agent having a particle size range of several tens of microns, and it is a desorbing agent (desorbing agent) at high speed.
The feed mixture (raw material liquid) is introduced between the unit packed bed and the next unit packed bed. However, the pressure loss due to the packing material becomes extremely large, and the pressure at the outlet of the unit packed bed becomes the desorbed liquid or the raw material. In many cases, the pressure became lower than the liquid pressure, and the desorbed liquid or the raw material liquid flows backward in the direction opposite to the originally intended flowing direction of the circulating liquid.

The present invention has been made based on the above circumstances. That is, the object of the present invention is to introduce the raw material liquid or the desorbed liquid at a high speed into the inlet provided between the unit packed bed filled with the filler having a very fine particle size and the next unit packed bed. Even so, it is an object of the present invention to provide an efficient simulated moving bed apparatus capable of efficiently separating a predetermined component at high speed.

[0008]

According to the present invention for solving the above-mentioned problems, a plurality of unit-packed beds containing a filler therein are connected in series, and a front end and a rear end of the unit-packed beds are connected to each other. Introducing a liquid containing a raw material mixture and a desorbed liquid into a packed bed in which a liquid is circulated in one direction by being connected by a fluid passage and circulating in one direction, and at the same time, with a liquid containing a component separated from the packed bed. It consists of withdrawing a liquid containing other components, and the packed bed has a desorption liquid inlet, a liquid (extract) outlet containing a substance that is easily adsorbed, a raw material mixture-containing liquid inlet, which is difficult to be adsorbed. Simulating by arranging the outlets for the liquid containing the substance (raffinate) in this order along the flow direction of the liquid, and moving these positions intermittently in the flow direction of the fluid in the bed. Uses moving floor system A check valve, wherein a solvent and a component are recovered from the extract and / or raffinate obtained, and a check valve is provided between an outlet and an inlet of the liquid in each unit packed bed. It is a simulated moving bed equipment.

The present invention will be described in more detail below. A. Pseudo moving bed In the pseudo moving bed system, for example, as shown in FIG.
A plurality of (for example, 12
A simulated moving bed is used which is divided into unit packed beds 2a to 2h (groups or 8 units) and each unit packed bed 2a to 2h is arranged in series. The liquid circulates in one direction in the liquid passage. Note that the number of unit packed beds in the simulated moving bed is not limited to the above number, and can be arbitrarily selected from the viewpoint of implementation scale and adsorption engineering.

As shown in FIG. 1, this simulated moving bed has
A desorbed liquid introduction port 3, an extract withdrawal port 4 for withdrawing a liquid (extract) containing a component that is easily adsorbed to the filler, a raw material multi-component mixture-containing liquid introduction port 5, and a filler along the flow direction of the liquid. A raffinate withdrawing port 6 for withdrawing a liquid (raffinate) containing a component that is difficult to be adsorbed in is provided in this order, and these positions can be intermittently moved sequentially in the fluid flow direction in the packed bed. It has become.

In the present invention, the unit packed bed 2 is also used.
In the liquid passage 1 that connects the a to 2h and the adjacent unit packed beds 2a to 2h, between each of the introduction holes of the desorbed liquid introduction port 3 and the raw material mixture-containing liquid introduction port 5 and the upstream unit packed bed. Check valves 7 are provided respectively.

In the simulated moving bed apparatus shown in FIG. 1, the desorbed liquid introduction port 3 is connected to the liquid passage 1 connecting the eighth unit packed bed 2h and the first unit packed bed 2a, and the first unit packed bed 2a is connected. The extract withdrawing port 4 is connected to the liquid passage 1 that connects the second unit packed bed 2b with the second unit packed bed 2b, and the raw material mixture-containing liquid is introduced into the liquid passage 1 that connects the third unit packed bed 2c and the fourth unit packed bed 2d. Mouth 5 is connected, and 7th unit packed bed 2
A raffinate outlet 6 is connected to a liquid passage 1 that connects g with the eighth unit packed bed 2h. A rotary valve or the like is used to intermittently sequentially move these inlets and outlets along the liquid flow direction. A recycle pump 8 is used to circulate the liquid in the liquid passage of the simulated moving bed apparatus.

-Type of Filler- Further, each unit packed bed contains a filler capable of adsorbing components to be separated. Examples of the filler include an optically active polymer compound and an optical resolution filler that uses a low molecular weight compound having an optical resolution when separating an optical isomer mixture. Examples of the optically active polymer compound include a polysaccharide derivative (ester of cellulose or amylose or carbamate), a polyacrylate derivative, or a filler in which a polyamide derivative is supported on silica gel, or the polymer itself without using silica gel. Examples of the filler include granules. Further, examples of the low molecular weight compound having optical resolution include crown ether or its derivative and cyclodextrin or its derivative. These low molecular weight compounds are usually used by supporting them on a carrier such as silica gel.

A commercially available product may be used as the optical resolution filler, for example, CH manufactured by Daicel Chemical Industries, Ltd.
IRALCEL OB (registered trademark), CHIRALCEL OD (registered trademark),
CROWNPAK CR (+) (registered trademark), CHIRALCEL CA-1 (registered trademark), CHIRALCEL OA (registered trademark), CHIRALCEL OK (registered trademark), CHIRALCEL OJ (registered trademark), CHIRALCEL OC (registered trademark), CHIRALCEL OF ( Registered trademark), CHIRALCEL OG
(Registered trademark), CHIRALPAK WH (registered trademark), CHIRALPAK
WM (registered trademark), CHIRALPAK WE (registered trademark), CHIRALPA
Preferable examples include K OT (+) (registered trademark), CHIRALPAK OP (+) (registered trademark), CHIRALPAK AS (registered trademark), and CHIRALPAK AD (registered trademark).

Alkaline earth metal salts such as calcium, barium and stringent are suitable as fillers for partitioning an isomerized sugar aqueous solution containing oligosaccharides into a fructose-rich fructose aqueous solution and a glucose-rich dextrose aqueous solution. Type of strong acid ion exchange resin or exchangeable cation is ammonium,
Sodium, potassium, calcium, strontium,
Examples thereof include crystalline aluminosilicates such as zeolite Y substituted with barium sugar.

Suitable fillers for separating fatty acids and triglycerides include basic ion exchange resins having a copolymer of styrene and divinylbenzene as a skeleton. Commercially available products include, for example, Rohm and A weakly basic ion exchange resin such as Amberlite IRA93 manufactured by Haas, Duolite A377 manufactured by Sumitomo Chemical Co., Ltd., Amberlite IRA manufactured by Rohm and Haas
400, Duolite A16 manufactured by Sumitomo Chemical Co., Ltd.
There may be mentioned strong basic ion exchange resins such as 1.
Various known fillers that are said to be suitable for separating various other substances can be used.

-Particle Size of Filler- The average particle size of the filler varies depending on the type of components to be separated, the volumetric flow rate of the solvent flowing in the simulated moving bed, and the like. , Usually 1 to 100 μm,
It is preferably 5 to 75 μm. However, if the pressure loss in the simulated moving bed is to be suppressed to a small value, it is 15 to 75 μ.
It is desirable to adjust the average particle size of the filler to m. When the average particle size of the filler is within the above range, pressure loss in the simulated moving bed can be reduced, and for example, 10 kgf / c
It can be suppressed to m ² or less. On the other hand, the larger the average particle size of the filler, the lower the theoretical plate number for adsorption.
Therefore, if only considering that a practical theoretical adsorption plate number is achieved, the average particle size of the filler is usually 1 to
It is 50 μm.

-Desorbing liquid-As the desorbing liquid supplied to the desorbing liquid introducing port, for example, alcohols such as methanol, ethanol and isopropanol, organic solvents such as hydrocarbons such as hexane, for example, an aqueous solution of copper sulfate, An aqueous solution containing a salt such as a perchlorate aqueous solution can be mentioned. Which desorption solution is preferable is appropriately determined depending on the kind of the component or compound to be separated.

-Components or substances to be separated-The raw material multi-component mixture introduced into the raw material multi-component mixture-containing liquid introduction port is not particularly limited, and is used in the fields of medicine, agricultural chemicals, foods, feeds, perfumes, etc. Various compounds such as pharmaceutical thalidomide, organophosphorus pesticide EPN, chemical seasoning glutamic acid monosodium salt, perfume menthol and the like can be mentioned, further, optically active alcohols, optically active Examples thereof include various esters.

In addition to the above, as a raw material multi-component mixture which can be separated by using the simulated moving bed apparatus of the present invention, a mixture of normal hexane and cyclohexane, a normal mixture of hydrocarbons, alcohols, aldehydes, ketones and the like is used. Examples thereof include a mixture of a compound and compounds having boiling points close to each other such as isomers thereof, an aqueous solution containing grapes and fructose, a mixture of maltose and a polysaccharide of maltotriose or higher, and the like.

-Process in the simulated moving bed system-In the adsorption separation of the multi-component mixture by the simulated moving bed system in the present invention, the following adsorption process, concentration process, desorption process and desorbed liquid recovery process are continuously performed as basic processes. It is realized by being cyclically performed.

(1) Adsorption step A mixture of a plurality of raw materials comes into contact with a packing material, and the packing material adsorbs an easily adsorbed composition (strongly adsorbed composition), while another adsorbed component (weakly adsorbed composition) becomes a raffinate component. It is collected together with the desorbed liquid.

(2) Concentration step The filler adsorbing the strongly adsorbed component contacts with a part of the extract described later, the weakly adsorbed component remaining on the filler is expelled, and the strongly adsorbed component is concentrated. .

(3) Desorption step The packing material containing the concentrated strong adsorbing component is brought into contact with the desorbing liquid, the strong adsorbing component is expelled from the packing material, and the desorbing liquid accompanies the simulated moving bed as an extract component. Emitted from.

(4) Desorbed liquid recovery step The packing material that substantially adsorbed only the desorbed material comes into contact with a part of the raffinate portion, and a part of the desorbed solution contained in the packing material is recovered as the desorbed solution. Recovered in minutes. The details will be described below with reference to the drawings.

Reference numerals 2a to 2h in FIG. 2 denote unit packed beds containing a packing material, which are connected to each other by a liquid passage. Denoted as 9 is a desorption liquid supply pump,
The desorbed liquid discharged from the desorbed liquid supply pump 9 is sent to the first rotary pump 10, and the first rotary valve 10 supplies the desorbed liquid to the liquid passage 1 from the designated discharge position. Reference numeral 11 is a second rotary valve, which is connected to a liquid passage for allowing liquid to flow into each unit packed bed, and reference numeral 12 is an extract extraction pump, which is designated through the second rotary valve 11. Extract is extracted from the unit packed bed of. Denoted at 13 is a third rotary valve, which is connected to a liquid passage for allowing liquid to flow into each unit packed bed,
4 is a raffinate extraction pump,
The raffinate is extracted from the designated unit packed bed through the third rotary valve 13. Reference numeral 15 is a fourth rotary valve, which is connected to a liquid passage for allowing liquid to flow into each unit packed bed, and reference numeral 16 is a raw material multi-component mixture supply pump, which is connected through a fourth rotary valve 15 The raw material multi-component mixture is supplied to a specified unit packed bed.

The liquid passage for passing the liquid from the unit packed bed to another adjacent unit packed bed is provided with a liquid passage outlet of the unit packed bed and a supply line from the first rotary valve 10 or a fourth rotary valve 15. Check valves 7a to 7h are interposed between the supply line and the supply line.

In the simulated moving bed apparatus shown in FIG.
For example, from the first rotary valve 10 to the first unit packed bed 2
The desorbed liquid is supplied to the liquid flow path 1 between the a and the eighth unit packed bed 2h by the supply line, and the extra liquid is discharged from the liquid flow path 1 between the first unit packed bed 2a and the second unit packed bed 2b. Is extracted by the second rotary valve 11 and the extract extraction pump 12, and the third unit packed bed 2
The raw material multi-component mixed liquid is supplied by the raw material multi-component mixture supply pump 16 and the fourth rotary valve 15 via the supply line to the liquid flow path 1 between the c and the fourth unit packed bed 2d, and the seventh unit packed bed Raffinate is extracted from the liquid flow path 1 between 2 g and the eighth unit packed bed 2 h by the third rotary valve 13 and the raffinate extraction pump 14.

Then, the desorbing step by the first unit packed bed 2a, the concentration step by the second unit packed bed 2b and the third unit packed bed 2c, the fourth unit packed bed 2d to the seventh unit packed bed 2g.
The adsorption process and the desorbed liquid recovery process are performed by the eighth unit packed bed 2h. In such a simulated moving bed, the desorbed liquid supply position, the feed multiple-component mixture-containing liquid supply position and each withdrawal position are moved by a unit packed bed in the solvent flow direction by operating the rotary valve at regular time intervals. Let

Therefore, in the second stage, the desorption process is performed by the second unit packed bed 2b, the third unit packed bed 2c and the fourth unit packed bed 2c.
Concentration step by unit packed bed 2d, 5th unit packed bed 2e-
The adsorption step is performed by the 82nd h, and the desorbed liquid recovery step is performed by the first unit packed bed 2a. By sequentially performing such an operation, each process is performed in the unit packed bed 1
As a result, the separation treatment of a mixture of a plurality of components is continuously and efficiently achieved.

In this case, since a check valve is provided between the supply line for supplying the raw material multi-component mixture-containing liquid or the desorbed liquid and the fluid outlet of each unit packed bed, each unit packed bed is loaded with a check valve. Even if a pressure loss occurs in the fluid due to the filled filler,
The liquid supplied from each supply line to the liquid flow path does not flow back to the upstream unit packed bed.

Therefore, when the simulated moving bed apparatus with a check valve according to the present invention is used, even if the unit packing material is packed with a packing material having a very fine particle size, the liquid flow does not reversely flow and the apparatus operates smoothly. As a result, it is possible to improve the separation efficiency by using the fine packing and realize the long-term continuous operation by not causing the backflow of the circulating liquid.

[0033]

EFFECTS OF THE INVENTION According to the present invention, when the desorbed liquid and the raw material multi-component mixture-containing liquid are supplied from the supply line to the circulation line, the back flow of the circulating liquid does not occur in the unit packed bed on the upstream side. It is possible to realize a smooth separation operation without operating trouble due to backflow generation, and since backflow of the circulating liquid is prevented, it is possible to load a packing material with a fine particle size that causes a large pressure loss in the unit packed bed. As a result, it is possible to achieve a dramatic improvement in separation efficiency by loading a packing material having a fine particle size into a unit packed bed.

[0034]

EXAMPLES Examples of the present invention will be described below. The present invention is not limited to the contents of the examples shown below. (Example 1) As a unit packed bed, the inner diameter is 2 cm and the length is 2
8 columns of 5 cm are connected to each other, and a packing material for optical isomer resolution (CHIR, manufactured by Daicel Chemical Industries, Ltd.) is connected in each column.
A simulated moving bed apparatus as shown in FIG. 2 packed with ALCEL OD, particle size 20 μm) was used. In this simulated moving bed apparatus, two unit packing beds are used as a set to perform an adsorption step,
The rotary valve was switched so that the concentration step, the desorption step and the desorbed liquid recovery step could be performed. As a liquid containing a mixture of optical isomers, 1-phenylethyl alcohol was supplied at 1 ml / min (total isomer concentration: 21 mg / ml). As a desorbed liquid, a mixed liquid of hexane / isopropanol (volume ratio: 9/1) was supplied at 32.1 ml / min. The solvent circulating through the solvent circulation passage was the same as the desorbed liquid.

From the extract outlet of this simulated moving bed apparatus, a strongly adsorptive optical isomer having a concentration of 0.3 was obtained.
6 mg / ml, optical purity 94% e. e. The extract contained in 1. was obtained at a rate of 28.2 ml / min.

On the other hand, from the raffinate withdrawal port of this simulated moving bed apparatus, another weakly adsorbing optical isomer was found to have a concentration of 2.2 mg / ml and an optical purity of 99.9% e. e. Was obtained at a rate of 4.9 ml / min.

(Comparative Example 1) The simulated moving bed apparatus shown in FIG. 2 was operated in the same manner as in Example 1 except that the check valve was not provided in the simulated moving bed apparatus shown in FIG. did.

As a result, from the extract withdrawal port of this simulated moving bed apparatus, the strongly adsorptive optical isomer had a concentration of 0.395 mg / ml and an optical purity of 46% e. e. The extract contained in 1. was obtained at a rate of 28.2 ml / min.

On the other hand, from the raffinate withdrawal port in this simulated moving bed apparatus, another weakly adsorptive optical isomer having a concentration of 2.014 mg / ml and an optical purity of 52% e. e. Was obtained at a rate of 4.9 ml / min.

[Brief description of drawings]

FIG. 1 is an explanatory view showing the concept of a simulated moving bed apparatus with a check valve according to the present invention.

FIG. 2 is an explanatory view showing an example of a simulated moving bed apparatus with a check valve according to the present invention.

[Explanation of symbols]

 1 Liquid Flow Path 2a-2h Unit Packing Bed 3 Desorbed Liquid Inlet 4 Extract Extract Outlet 5 Raw Material Mixture Containing Liquid Supply Inlet 6 Raffinate Outlet 7 Check Valve 8 Recycle Pump

[Procedure amendment]

[Submission date] May 25, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

The present invention has been made based on the above circumstances. That is, the object of the present invention is to introduce the raw material liquid or the desorbed liquid at a high speed into the inlet provided between the unit packed bed filled with the filler having a very fine particle size and the next unit packed bed. Even if it does, even if it does not cause the backflow phenomenon of a circulating fluid, it aims at providing the efficient simulated moving bed apparatus which can isolate | separate a predetermined component efficiently at high speed.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Reference numerals 2a to 2h in FIG. 2 denote unit packed beds containing a packing material, which are connected to each other by a liquid passage. Denoted as 9 is a desorption liquid supply pump,
The releasing liquid releasing liquid discharged from the supply pump 9 is fed to the first rotary valve 10, supplies the releasing liquid the first rotary valve 10 from the specified discharge position in the liquid passage 1. Reference numeral 11 is a second rotary valve, which is connected to a liquid passage for allowing liquid to flow into each unit packed bed, and reference numeral 12 is an extract withdrawing pump, which is designated through the second rotary valve 11. Extract is extracted from the unit packed bed of. Denoted at 13 is a third rotary valve, which is connected to a liquid passage for allowing liquid to flow into each unit packed bed,
4 is a raffinate extraction pump,
The raffinate is extracted from the designated unit packed bed through the third rotary valve 13. Denoted at 15 is a fourth rotary valve, which is connected to a liquid passage for allowing the liquid to flow into each unit packed bed, and denoted at 16 is a raw material multi-component mixture supply pump, and through a fourth rotary valve 15. The raw material multi-component mixture is supplied to a specified unit packed bed.

Claims (1)

[Claims] 1. A unidirectional liquid in which a plurality of unit-packed beds containing a filler therein are connected in series, and a front end and a rear end of the unit-packed beds are connected by a fluid passage to form an endless shape. It consists of introducing the raw material multi-component mixture-containing liquid and the desorbed liquid into the packed bed circulating in the above, and at the same time withdrawing the liquid containing one component and the liquid containing the other component separated from the packed bed. In the packed bed, the desorbed liquid inlet, the liquid (extract) outlet that contains the component that is more easily adsorbed, the raw material multi-component mixture-containing liquid inlet, the liquid that contains the component substance that is less adsorbed (Raffinate) is arranged in this order along the flow direction of the liquid, and a pseudo moving bed system is used in which these positions are intermittently moved in the flow direction of the fluid in the bed. The ext obtained by A simulated moving bed with a check valve, characterized in that a solvent and a component are recovered from lacto and / or raffinate, and a check valve is provided between an outlet and an inlet of the liquid in each unit packed bed. apparatus.