KR101533508B1 - Three-port in Three-zone simulated moving bed (TT-SMB) operation for improving the separation performance - Google Patents

Abstract

The present invention relates to a method for separating a mixture using a similar mobile bed adsorptive separation (SMB) process wherein the composition of the three chromatographic zones and the three ports (desorbent inlet port, separation inlet mixture inlet port and product outlet port) (SMB) apparatus, the switching section is divided into a first half portion and a second half portion. By varying the position of the port, only the product (extract or raffinate The present invention also provides a separation method for producing a separation membrane.
Accordingly, the conventional four-zone SMB process and the conventional four-zone SMB process, while using a smaller amount of the adsorbent in the conventional four-zone SMB process, Quot; three-zone SMB process " can provide a method for separating a mixture that can yield products of higher purity.

Description

[0001] The present invention relates to a three-port three-port simulated moving bed (TT-SMB)

The present invention relates to a method for operating a three-zone three-port similar mobile bed adsorption separation process for improving the separation of a mixture.

The separation method using adsorption is a separation method that secures stability of material and high separation efficiency. In the liquid phase adsorption separation furnace, the chromatographic separation method is widely used. In the conventional batch chromatographic separation method, since the mobile phase used for separating the mixture, that is, the desorbent is used in a very large amount, The consumption amount is increased. In addition, there is a problem that the productivity is deteriorated due to the disadvantage of the batch reaction.

In order to solve these problems, an actual moving bed adsorption separation (TMB) process capable of producing a large amount of high purity product as a continuous process adopting the concept of counter current flow has been developed.

In this actual moving bed adsorption separation (TMB) process, the stationary phase and the mobile phase move countercurrently to cause countercurrent contact, so that when the mixture solution to be separated is injected into the middle portion of the TMB column, Due to the difference, the component with strong adsorption (extract) is discharged to the bottom of the column according to the flow of the stationary phase, and the component with weak adsorption (raffinate) is discharged from the column above the mobile phase. Therefore, in the actual mobile bed adsorption separation (TMB) process using this continuous process, separation can be performed at both ends of the column if there is a difference in adsorption force between the two components in the mixture, .

However, the actual moving bed adsorption separation (TMB) process has a disadvantage in that the amount of the filler must be increased compared to the conventional batch process, and the operation of the steady state is difficult due to friction or leakage of the filler. In addition, back mixing of adsorbent particles by countercurrent flow is a big problem, and when a small amount of desorbent is used to prevent this, separation efficiency and productivity are lowered.

In order to overcome the disadvantages of the actual mobile bed adsorption separation (TMB) fixation, a simulated moving bed (SMB) process has been developed which is a process that does not actually move, but has the same effect as moving the stationary phase. This was proposed in U.S. Patent No. 2,985,589 in 1961. In the simulated moving bed adsorption separation (SMB) process, the movement of the stationary phase is simulated through the port movement between the columns. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow diagram of a conventional similar mobile bed adsorptive separation (SMB) process. In a conventional basic similar-mobile bed sorbent separation (SMB) process, a total of four zones are comprised of one or more columns, with a desorbent inlet port, an extract- a feed inlet port and a raffinate outlet port are located. A similar moving bed adsorption separation (SMB) process consisting of four zones and four ports as described above is referred to as " four zone similar mobile bed adsorption separation (four-zone SMB) process ".

In the similar moving bed adsorption separation (SMB) process, all the inlet ports and the outlet ports are moved in the moving direction of the moving phase fluid by a predetermined time each time to simulate the flow of the fixed phase. This port movement produces the same effect as if each column moved in the opposite direction of the moving direction of the mobile phase desorbent. The movement of the port is referred to as a switch, and the time interval between the switches is referred to as a switch time (tsw) or a switching period.

The target mixture to be separated (the mixture to be separated) is introduced into the mixture inlet port between the second and third sections, and the extract having a strong adsorption ability to the stationary phase is extracted from the third section To the second zone again from the second zone to the first zone and to the product at the extract outlet port between the first zone and the second zone while being desorbed by the mobile phase fluid as the desorbent in the first zone. A raffinate component with poor adsorption to the stationary phase is obtained as a product at the raffinate outlet port between the third and fourth zones as the port moves.

Thus, the simulated moving bed adsorptive separation (SMB) process overcomes the practical problem of the flow of the fixed bed in the actual moving bed adsorption separation (TMB) process described above by simulating the countercurrent contact with the mobile phase by creating a virtual fixed bed flow Could.

Figure 2 is an example of a conventional similar mobile bed adsorptive separation (SMB) process. When a cyclic steady state is reached in a " four-zone SMB process, Lt; / RTI > Specifically, Figures 2 (a) and 2 (b) show the concentration gradient at the extract outlet port and the raffinate outlet port, respectively.

In the concentration gradient of each product discharge port in Fig. 2, the extract and raffinate become impurities to each other. (Fig. 2 (a)). In the raffinate outlet port where the pure raffinate should be obtained, impurities are present in the latter half of the switching section in the extract outlet port where the pure extract should be obtained (Fig. 2 (b)). Therefore, as shown in FIG. 2, how to treat a section containing relatively large amounts of impurities in the product discharge port of the conventional similar moving bed adsorption separation (SMB) It can play an important role in improving performance.

Conventional similar moving bed adsorptive separation (SMB) devices generally consist of four zones, while the "three zone-like moving bed adsorptive separation" with three chromatographic zones and four ports to reduce the use of adsorbents -zone SMB) process " has been proposed. The above-described " three zone-like mobile bed adsorption separation (three-zone SMB) process " means that the mixture in the chromatographic zone corresponding to the third zone of FIG. 1 in the conventional similar mobile bed adsorption separation (SMB) ) And the chromatographic section corresponding to the second zone of Fig. 1 in the conventional similar mobile bed adsorptive separation (SMB) process, Quot; SMB without zone I ", in which the mixture in step (1) is entirely obtained as an extract product.

Fig. 3 shows the construction and operation of the general three-zone SMB process. The above-mentioned general three-zone SMB process can be classified into a "process for removing the fourth zone (SMB without zone IV)" and a process for " SMB without zone I process "have been reported.

3 (a) is a schematic process diagram of the " SMB without zone IV process " in the above " SMB without zone IV process " There is no fluid circulating from the outlet of zone 3 to the inlet of zone 1 because there is no fourth zone in the conventional " four-zone SMB (Fig. 1) process " All fluids will be obtained as raffinate products. 3 (b) is a process schematic diagram of the " SMB without zone I process " in the above " SMB without zone I process " The first zone of the conventional " four zone-like SMB process " is omitted and all of the fluid discharged from the discharge port of the fourth zone is obtained as an extract product.

The "three zone-like mobile bed adsorption separation (three-zone SMB) process" is different from the conventional "four zone-like mobile bed adsorption separation (four-zone SMB process)" in that the desorbent is not re- . That is, the fluid flow in the conventional "four zone-like moving bed adsorption separation (four-zone SMB) process" is a closed loop while the "three zone-like moving bed adsorption separation (three-zone SMB) And has an open loop. Because of this feature, the " three zone-like moving bed adsorption separation (three-zone SMB) process " generally requires a smaller amount of adsorbent This was about 3/4, but the use of desorbent was increased.

The " SMB without zone I process " as used herein refers to a process in which a product is obtained at a high flow rate at the extract outlet port in a conventional " four zone-like SMB process " . In this case, as shown in FIG. 2 (a), in the product concentration gradient at the outlet port of the extract, the concentration of the product is higher in the temporal portion containing the main impurity than in the temporal region not containing the main impurity, The proportion of impurities in the total product increases and the average purity of the product decreases.

It should be noted that the "SMB without zone IV process" described above can be applied to a raffinate discharge port at a higher flow rate than in a conventional "four zone-like moving bed adsorption separation (four-zone SMB) Thereby obtaining a product. In this case, as shown in FIG. 2 (b), in the product concentration gradient at the raffinate outlet port, the concentration of the raffinate product is higher in the temporal portion containing the main impurity than in the temporal portion not containing the main impurity, As the flow rate increases, the proportion of impurities in the total product increases, resulting in a decrease in the average purity of the product.

As described above, since the "three zone-like moving bed adsorption separation (three-zone SMB) process" has an open loop, in the "SMB without zone IV process" The SMB without zone I process "is higher than that in the conventional" four zone-like moving bed adsorption separation (four-zone SMB process) ", and similarly, the flow rate of the raffinate product obtained from the" Quot; four zone-like mobile bed adsorption separation (four-zone SMB) process ".

In the first half of the switching period, the extract product produced from the extract outlet port contains raffinate and acts as an impurity. In the latter half of the switching section, the raffinate product produced from the raffinate outlet port contains the extract and acts as an impurity do. However, as shown in Fig. 2, the section where impurities are included in each product is a section where the concentration of the product and the impurity is high.

Thus, the use of the above-described " three zone-like mobile bed adsorption separation (three-zone SMB process) " results in the conventional " four- zone similar mobile bed sorbent separation " process due to the increased flow rate of the impurity- There is a drawback that the purity is lowered.

In the present invention, in the separation process of a mixture using a similar mobile bed adsorptive separation (SMB) apparatus, which comprises the construction of three chromatographic zones and three ports (desorbent inlet port, separation subject inlet port and product outlet port) By dividing the switching section into the first half and the second half, by changing the positions of the ports. (Extract or raffinate) only during a time interval during which the impurities are contained in a small amount.

Accordingly, the conventional four-zone SMB process and the conventional four-zone SMB process, while using a smaller amount of the adsorbent in the conventional four-zone SMB process, Quot; three-zone SMB process " can provide a method for separating a mixture that can yield products of higher purity.

In the present invention, a similar moving bed adsorptive separation (SMB) apparatus comprising three chromatographic zones defined by the first to third chromatographic zones, and including a switching interval defined by a Δt _A section and a Δt _B section,

In the interval Δt _A ,

A chromatograhy zone I in fluid communication with the desorbent inlet port; A second chromatography chromatographic region fluidly connected to the first chromatographic region; And a third chromatography zone fluidly connected to the second chromatography zone, the separation subject mixture inlet port and the raffinate outlet port being fluidly connected,

In the? T _B section,

A chromatography chromatographic section fluidly connected to the Ⅲ chromatographic section and fluidly connected to the extract outlet port; A chromatographic region II fluidly connected to the desolvating agent inlet port in fluid communication with the first chromatographic section; Chromatographic separation zone in fluid communication with the second chromatographic zone and comprising a third chromatography zone in fluid communication with the separation subject mixture inlet port.

At this time, the similar moving bed adsorption separation apparatus may satisfy the following general formulas (1) and (2).

[Formula 1]

[Formula 2]

는 스위칭 구간에 대한 전반부의 시간(Δt_A)의 비율을 나타낸다.
In the equations (1) and (2),? _{T A} represents the time of the first half of the switching period _,? T _B represents the time of the second half of the switching period, t _sw represents the switching time,

Represents the ratio of the time of the first half of the switching period (Δt _A).

In the present invention, in a similar mobile bed adsorption separation (SMB) apparatus having three chromatographic zones and three port configurations, an extract outlet port containing a large amount of impurities in the product is not used in the first half of the switching section, It does not use a raffinate discharge port containing a lot of impurities,

By increasing the flow rate of the product in the conventional " four-zone SMB process, "

In addition to the improvement in productivity through reduction of the adsorbent, the conventional four-zone SMB process and the three-zone SMB process have been proposed It is possible to maximize the purity of the more excreted product.

값이 0.5 일 때의 생산물 농도구배 그래프이다.FIG. 1 is a schematic diagram showing a conventional 4 zone-like moving bed adsorption separation (SMB) operation method.
FIG. 2 is a graph showing the concentration gradient at each product discharge port in the operation method of the conventional four-zone-like moving bed adsorption separation (SMB) process shown in FIG. 1, wherein the concentration gradient (a) and (B) at the raffinate outlet port.
FIG. 3 is a schematic view showing a conventional method of operating a "three zone-like moving bed adsorption separation (three-zone SMB) process", wherein FIG. 3 (a) And Fig. 3 (b) shows the " first zone excluded SMB without zone I process ".
4 is a schematic diagram showing a method of operating a " three-zone three-port similar mobile bed adsorption separation (TT-SMB) process " according to the present invention.
5 is a graph of product concentration gradient when the " fourth zone without SVI without zone IV " process is used.
6 is a graph of the product concentration gradient when the " first zone excluded SMB without zone I process " is used.
Figure 7 is a flow chart of a " three-zone three-port similar mobile bed adsorptive separation (TT-SMB) process "

Is a product concentration gradient at a value of 0.5.

The present invention is a similar moving bed adsorptive separation (SMB) apparatus comprising three chromatographic zones defined by the chromatographic zones I to III, comprising a switching section defined by a section Δt _{A and a} section Δt _B ,

In the interval Δt _A ,

A chromatograhy zone I in fluid communication with the desorbent inlet port; A second chromatography chromatographic region fluidly connected to the first chromatographic region; And a third chromatography zone fluidly connected to the second chromatography zone, the separation subject mixture inlet port and the raffinate outlet port being fluidly connected,

In the? T _B section,

A chromatography chromatographic section fluidly connected to the Ⅲ chromatographic section and fluidly connected to the extract outlet port; A chromatographic region II fluidly connected to the desolvating agent inlet port in fluid communication with the first chromatographic section; To a similar moving bed adsorption separation apparatus in fluid communication with the second chromatography zone and comprising a third chromatography zone in fluid communication with the separation subject mixture inlet port.

At this time, the separation apparatus satisfies the general formulas 1 to 2.

[Formula 1]

 [Formula 2]

는 스위칭 구간에 대한 전반부의 시간(Δt_A)의 비율을 나타낸다.
In the equations (1) and (2),? _{T A} represents the time of the first half of the switching period _,? T _B represents the time of the second half of the switching period, t _sw represents the switching time,

Represents the ratio of the time of the first half of the switching period (Δt _A).

Hereinafter, a similar moving bed adsorptive separation (SMB) apparatus according to the present invention will be described in more detail.

An exemplary similar moving bed adsorptive separation (SMB) device in accordance with the present invention comprises three chromatographic zones and three ports. Therefore, the separation apparatus according to the present invention can be referred to as a " three-zone three-port similar moving bed adsorption separation (TT-SMB) apparatus ".

In an exemplary " three-port three-port similar mobile bed adsorptive separation (TT-SMB) apparatus " according to the present invention, the three chromatographic zones are defined as Zone I chromatography zone, Zone II chromatographic zone and Zone III chromatographic zone, respectively. And the chromatographic zone may be configured as an open loop. The chromatographic zone may comprise at least one chromatographic column, and in particular may comprise from 1 to 5, more particularly from 1 to 3 chromatographic columns.

The port is fluidly connected to the chromatographic section. Specifically, in the present invention, three ports are fluidly connected, wherein the ports can be a desorbent inlet port, a separation subject mixture inlet port, and a product outlet port (an extract outlet port or a raffinate outlet port). The connection position of the port to the crossover region will be described later.

Further, an exemplary " three-zone three-port similar moving bed adsorptive separation (TT-SMB) apparatus " according to the present invention may further include a valve for controlling the movement of each port for each set switching interval. With such a valve, it is possible to simulate the flow of the fixed phase countercurrent to the movement of the fluid in the separating device of the present invention. The type of the valve is not particularly limited as long as it is a valve commonly used in this field. Specifically, a rotary valve, a multi-directional valve, a multifunctional valve or an on-off valve can be used.

An exemplary " three-port three-port similar moving bed adsorptive separation " (TT-SMB) apparatus according to the present invention may be configured by dividing the switching section into a first half portion and a second half portion. In the present invention, a switch means a movement of a port, which has the same effect as when each chromatographic column is moved in a direction opposite to the moving direction of the mobile phase desorbent, and the switching period may be defined as a time interval between the respective switches. The switching period may be referred to as a switch time (tsw). There the first half and the second half of such a switching interval may be defined as Δt _A period and Δt _B intervals, respectively, Δt _A period refers to a period of time up to t _A 2 at t _A 1 hour and, Δt _B interval t _B 1 It can mean the interval from time to t _B 2 hours. In this case, t _A 1 is equal to the starting point of the switching period, t _B 2 is equal to the last point of the switching period, and t _A 2 has the same point as t _B 1.

An exemplary "three zone three ports similar to a moving bed adsorption separation (TT-SMB) apparatus" according to the invention, has three chromatographic zones, and three ports, detaching the first half, i.e., Δt _A period of the switching interval the A first chromatographic region in fluid communication with the inlet port; A second chromatography chromatographic region fluidly connected to the first chromatographic region; And a third chromatography zone in fluid communication with the second chromatography zone, the separation subject mixture inlet port and the raffinate outlet port comprising a fluidly connected third chromatography zone,

In the latter half of the switching period, that is,? T _B Chromatographic region fluidly connected to the Ⅲ chromatographic region and fluidly connected to the extract outlet port; A chromatographic region II fluidly connected to the desolvating agent inlet port in fluid communication with the first chromatographic section; A second chromatographic zone in fluid communication with the second chromatographic zone and a third chromatographic zone in fluidic connection with the subject mixture inlet port.

In the case of a conventional similar moving bed adsorption separation apparatus, for example, a " four-zone similar mobile bed adsorption separation apparatus " having four chromatographic zones and four port configurations, impurities A large amount of impurities (extract) are discharged in the latter half portion of the switching section in the raffinate discharge port (see FIG. 2). Therefore, in the present invention, a product of high purity can be obtained by not using the extract discharge port in the first half of the switching section and not using the raffinate discharge port in the second half of the switching section. Also, by constituting the open loop using three chromatographic zones, it is possible to obtain a product intensively in a temporal section in which impurities are not contained at a high flow rate, thereby further increasing the purity of the product.

At this time, there is no particular limitation on a method for implementing the device that does not use the extract discharge port in the first half of the switching section and does not use the raffinate discharge port in the latter half of the switching section. For example, two discharge ports (extract discharge port and raffinate discharge port) may be provided, but only one discharge port may be used for each of the first half and the second half by limiting the flow of the fluid using the valve. That is, by locking the extract outlet port in the first half and locking the raffinate outlet port in the second half, the separator can use only one outlet port over the switching interval.

In addition, for example, after one product discharge port is installed, the discharge port is connected to the raffinate product storage tank in the first half, and the discharge port is connected to the extract product storage tank in the latter half have. In this case, the discharge port can be used as a raffinate product discharge port during the first half, and can be used as an extract product discharge port in the second half.

In the similar fluidized bed adsorption separation apparatus according to the present invention, the first half of the switching period (? A section) and the second half section (? TB section) may satisfy the following formulas (1) and (2).

[Formula 1]

[Formula 2]

는 스위칭 구간에 대한 전반부의 시간(Δt_A)의 비율을 나타낸다.In the equations (1) and (2),? _{T A} represents the time of the first half of the switching period _,? T _B represents the time of the second half of the switching period, t _sw represents the switching time,

Represents the ratio of the time of the first half of the switching period (Δt _A).

Where Δt _A interval section means, and the interval of time Δt _B in _A t 1 to time t 2 _A can mean a range of up to t _B 2 _B 1 t hours at the time. In this case, t _A 1 is equal to the starting point of the switching period, t _B 2 is equal to the last point of the switching period, and t _A 2 has the same point as t _B 1.

)은 배출되는 생산물의 순도가 높은 범위에서 적절히 조절될 수 있다. 상기

의 범위는 하기 혼합물의 분리방법에서 구체적으로 설명하도록 한다. In the above general formula, the time of the switching section t _sw is not particularly limited and can be appropriately adjusted according to the characteristics of the mixture. In the above equation, the ratio of the time of the first half? _{T A} to the switching interval

) Can be appropriately controlled within a range of high purity of the product to be discharged. remind

Is specifically described in the separation method of the following mixture.

In the similar moving bed adsorbing and separating apparatus according to the present invention, one switching section is repeatedly performed. One switching period is divided into a first half (Δt _A section) and a second half section (Δt _B The apparatus configuration of the first half and the second half is repeatedly performed.

The present invention also relates to a method for separating a mixture using a similar moving bed adsorption separation apparatus.

The separation method of the mixture according to the present invention comprises the above-described separation apparatus, that is, three chromatographic zones defined by the chromatographic zones I to III, and includes a switching section defined by the? _{T A} section and the? _{T B} section Similar mobile bed adsorptive separation (SMB) devices can be used.

In the separation method according to the present invention, the fluid is moved in the order of Δt _A , that is, in the first half of the switching section, in the order of the I, II, and III chromatographic zones, and the desorbent is introduced into the I chromatography zone; Introducing the mixture to be separated into the Ⅲ chromatographic section; And separating the mixture by the step of discharging the raffinate product in the III chromatography zone,

In step Δt _B , that is, in the second half of the switching section, fluid is transferred in the order of II, III and I chromatographic zones, and the desorbent is introduced into the II chromatographic zone; The step of introducing the mixture to be separated into the Ⅲ chromatographic section; And separation of the mixture by the step of discharging the extract product in the first chromatographic region.

Since the separation apparatus used in the separation method according to the present invention uses three zones (chromatographic zone) and three port configurations, the separation method is called "three zone three port similar moving bed adsorptive separation (TT-SMB ) Process. &Quot;

In the method for separating a mixture according to the present invention, the switching section is divided into a first half portion and a second half portion, and a discharge port is not used in a time interval in which a concentration gradient of the exhaust port of each product (extract or raffinate) By increasing the flow rate in the time domain in which the impurity is less contained due to the use of the chromatographic zone than in the conventional " four-zone SMB process, " The purity of the product can be increased.

The kind of the mixture to be separated which can be used in the separation method of the mixture according to the present invention is not particularly limited and a mixture having a linear or nonlinear adsorption characteristic can be used. Specific examples thereof include a substance which is difficult to separate such as an aromatic hydrocarbon, an ethylbenzene, a chiral compound, or a racemic mixture (a substance having low selectivity).

4 is a schematic diagram showing an exemplary operating method of a " three-port in three-zone SMB (TT-SMB) process " according to the present invention.

As shown in FIG. 4, the operation method according to the TT-SMB has the composition of the mixture inlet port, the desorbent inlet port, the extract outlet port, and the raffinate outlet port. In the first half of the switching section, Since the raffinate discharge port is locked, three ports are actually used throughout the switching period.

The method for separating a mixture according to the present invention is a four-zone similar four-zone SMB process having a closed loop having four zones and two adjacent ports connected to each other through a chromatographic zone In the first half of the switching section, the fluid discharged from the Ⅲ chromatographic section is all the raffinate product, and in the latter half of the switching section, the fluid discharged from the Ⅰ chromatographic section is an open loop Lt; / RTI >

The desorbent inlet port is located at the inlet node of the Ⅰ chromatographic section in the first half of the switching section and at the inlet node of the Ⅱ chromatographic section in the latter half of the switching section. Therefore, desorbent is introduced into the first chromatographic section in the first half of the switching section and to the Ⅱ chromatographic section in the latter half. Further, since one product discharge port (raffinate discharge port or product discharge port) is not used in one of the first half and the second half of the switching period, a situation in which a product is not obtained or is obtained is repeated for each switching period. When one switching period passes, the mixture inlet port and the product outlet port are respectively moved by a single chromatographic column in the flow direction of the fluid.

In the " three-zone three-port similar mobile bed adsorption separation (TT-SMB) process " according to the present invention, the three chromatographic zones play different roles. In the first half of the switching section, the substance (A, extract) having high adsorption power among the substances injected through the mixture inlet port between the Ⅱ chromatographic section and the Ⅲ chromatographic section is adsorbed on the adsorbent and the substance , Raffinate moves along the mobile phase, desorbent, and is obtained as a raffinate product along with all the remaining fluid through the raffinate outlet port of the Ⅲ chromatographic zone. In the first half of the switching section, the Ⅱ chromatographic region and the Ⅲ chromatographic region become the separation regions.

In the latter half of the switching period, desorbent enters the II chromatographic region. The mixture to be separated flows through the mixture inlet port between the II chromatographic zone and the III chromatography zone equally in the first half and the second half of the switching zone. In the latter half of the switching section, the fluid in the Ⅲ chromatographic section moves to the Ⅰ section and all the remaining fluid through the extract port in the Ⅰ chromatographic section is obtained as an extract product. In the latter half of the switching section, the Ⅲ chromatographic region and the Ⅰ chromatographic region become the separation regions.

In the first half of the switching section, the first chromatographic region is located, and in the latter half of the switching region, the second chromatography region is the regeneration region. That is, the desorption agent is introduced into the first chromatographic region in the first half of the switching period and the second chromatographic region in the latter half of the switching period, thereby washing the chromatographic column.

As described above, in the method for separating a mixture according to the present invention, since the extract outlet port is not used in the first half of the switching section, all the fluid flow can be discharged from the raffinate discharge port. In the latter half of the switching section, Since no ports are used, all of the fluid flow can be drained from the extract outlet port.

In this case, the first half of the switching period can be set by Equation (1) below, and the second half of the switching period can be set by Equation (2) below.

[Formula 1]

[Formula 2]

는 스위칭 구간에 대한 전반부의 시간(Δt_A)의 비율을 나타낸다.In the equations (1) and (2),? _{T A} represents the time of the first half of the switching period _,? T _B represents the time of the second half of the switching period, t _sw represents the switching time,

Represents the ratio of the time of the first half of the switching period (Δt _A).

의 영향을 받게된다.In the present invention, the time for adjusting the flow rate of the product discharged from each product discharge port, i.e., the extract discharge port and the raffinate discharge port,

.

의 범위는 특별히 제한되지 않으며, 0.1 내지 0.9, 0.2 내지 0.8, 0.3 내지 0.7, 0.4 내지 0.6, 0.45 내지 0.55 일 수 있으며, 보다 구체적으로 0.5일 수 있다. 상기 값이 0.1 미만이면, 라피네이트 생산 구간이 짧아져 라피네이트 생산물의 생산량이 저하될 수 있고, 컬럼 내 라피네이트 물질의 잔류로 인해 추출물 생산물의 순도가 저하될 수 있다. 마찬가지로 0.9를 초과하면, 추출물 생산 구간이 짧아져 추출물 생산물의 생산량이 저하될 수 있고, 컬럼 내 추출물 물질의 잔류로 인해 라피네이트 생산물의 순도가 저하될 수 있다. 특히,

의 범위가 0.45 내지 0.55인 것이 생산물의 순도 측면에서 바람직하다.Here,

Is not particularly limited and may be 0.1 to 0.9, 0.2 to 0.8, 0.3 to 0.7, 0.4 to 0.6, 0.45 to 0.55, and more specifically 0.5. If the value is less than 0.1, the raffinate production period may be shortened to reduce the yield of the raffinate product, and the purity of the extract product may be lowered due to the residual raffinate material in the column. Likewise, if it exceeds 0.9, the yield of the extract may be shortened and the yield of the extract product may be lowered, and the purity of the raffinate product may be lowered due to the residue of the extract material in the column. Especially,

Is in the range of 0.45 to 0.55 in view of the purity of the product.

는 하기 일반식 3에 의하여 그 범위가 설정될 수 있다.In the separation method according to the present invention, the separation target mixture preferably has adsorption characteristics. When the adsorption characteristic is linear (linear isotherm), the ratio of the time of the first half to the switching interval

The range can be set by the following general formula (3).

[Formula 3]

In the formula (3), ε represents the porosity of the adsorbent in the chromatographic column used in the three-zone three-port similar mobile bed adsorption separation (TT-SMB) process according to the present invention, and m ₂ represents the porosity of TT - represents the flow rate ratio of the Ⅱ chromatographic section of the SMB device, and m ₃ represents the flow rate ratio of the Ⅲ chromatographic section of the three-zone three-port similar mobile bed adsorptive separation (TT-SMB) process as described in the triangular coordinate theory . Also, H _A represents the Henry's constant of the strong adsorbate (extract) of the mixture, and H _B represents the Henry's constant of the weakly adsorbate (raffinate) of the mixture.

In addition, in the method of separating the mixture according to the present invention, in order to control the flow rate of the product discharged from the extract outlet port and the raffinate outlet port, in dividing the switching section into the first half and the second half,

A configuration in which the extract discharge port is locked in the first half of the switching section and the raffinate discharge port is locked in the second half of the switching section,

The node model of the first half of the switching period can be set by the following equations (4) to (11).

At this time, Q represents the flow rate, C represents the concentration, in is used to represent the inlet, and out can represent the outlet. Also, i, used as a subscript, indicates the type of product, which can be an extract or raffinate. E and R, used in the subscripts, can represent extracts and raffinates, respectively.

Desorption agent node (inlet port of zone I)

[Formula 4]

[Formula 5]

Extract node (exhaust port in zone I)

[Formula 6]

[Formula 7]

Mixed node (inlet port between zone II and zone III)

[Formula 8]

[Formula 9]

Raffinate node (exhaust port in zone III)

[Formula 10]

[Formula 11]

As shown in the above general formulas 4 to 11, in the first half of the switching section, the flow rate of the first zone is equal to the flow rate of the desorbent (refer to the general formula 4), and since it has the open loop of the present invention, The concentration of the resulting product becomes zero (see Formula 5). In addition, since the extract outlet port is locked in the first half, the flow rate of the Ⅱ zone is equal to the flow rate of the Ⅰ zone, the flow rate of the extract is 0, and the concentration of the product introduced into the Ⅱ zone is the concentration of the product discharged from the zone I (See formulas 6 to 7). Between Zone II and Zone III, the mixture enters the process. Therefore, the flow rate in the zone III is the sum of the flow rate in the zone II and the flow rate of the mixture (see equation 8). Also, the product concentration of the product entering the zone III multiplied by the flow rate of the zone III is the product of the concentration of the product discharged in zone II multiplied by the flow rate in zone II, the product of the concentration of the mixture and the injection flow rate of the mixture See equation 9). Thus, the flow rate of the raffinate discharged from the process is the flow rate of the zone III, and the concentration of the raffinate is the concentration of the product discharged from the zone III.

The node model of the latter half of the switching period may be set by the following equations (12) to (19).

Desorption node (inlet port in zone II)

[Formula 12]

[Formula 13]

Mixed node (inlet port between zone II and zone III)

[Formula 14]

[Formula 15]

Raffinate node (exhaust port in zone III)

[Formula 16]

[Formula 17]

Extract node (exhaust port in zone I)

[Formula 18]

[Formula 19]

As shown in the above general formulas 12 to 19, in the latter half of the switching section, the flow rate of the zone II is equal to the flow rate of the desorbent (refer to the general formula 12), and since it has the open loop of the present invention, The concentration of the resulting product is zero (see Formula 13). Between Zone II and Zone III, the mixture enters the process. Therefore, the flow rate in the zone III is the sum of the flow rate in the zone II and the flow rate of the mixture introduction (see equation 14). Also, the product concentration of the product entering the zone III multiplied by the flow rate of the zone III is the product of the concentration of the product discharged in zone II multiplied by the flow rate in zone II, the product of the concentration of the mixture and the injection flow rate of the mixture See equation 15). Also, since the raffinate outlet port is locked, the flow rate in zone I is equal to the flow in zone III, and the concentration of product introduced into zone I is the concentration of the product discharged in zone III (see formulas 16-17). In addition, the flow rate of the extract from the process is equal to the flow rate in zone I, and the concentration of the extract is the same as the concentration of the product discharged in zone I (see formulas 18 to 19).

Hereinafter, a method for separating a mixture using a three-port three-zone SMB (TT-SMB) process according to the present invention will be described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.

The separation method of the mixture using the "three-port in three-zone SMB (TT-SMB) process" according to the present invention can be carried out by, for example, separation of a mixture of aromatic hydrocarbons, Separation process of chiral compounds, and the like, and may be applied to a separation process of a racemic mixed medicament, which is a final product or an intermediate product in a pharmaceutical manufacturing process.

FIG. 2 is a graph showing the concentration gradient at each port in a conventional similar moving bed adsorption separation (SMB) process, wherein the concentration gradient at the extract outlet port (FIG. 2 (a) In other words, it can be seen that most of the raffinate exists in the first half of one switching period, and the concentration gradient (Fig. 2 (b)) at the raffinate discharge port shows that the substance It can be seen that most of the extract is present in the latter half of one switching period.

Most of the impurities present in the early part of the extract product are raffinates flowing into the latter half of one switching period. The raffinate entering the latter half of one switching section immediately meets the switching time of the similar moving bed adsorption separation apparatus, so that sufficient time for moving forward with the desorbing agent is not secured. Therefore, the raffinate, which becomes an impurity, is discharged from the extract outlet port since the extract outlet port meets the time for moving to the position before the column before moving.

In addition, most of the impurities present in the latter half of the raffinate product are extracts that enter the first half of one switching period. The raffinate entering the first half of one switching section moves with the desorbent toward the raffinate outlet port for a relatively long time and the extract is discharged from the raffinate outlet port at the latter half.

In the " three-port in three-zone SMB (TT-SMB) process " according to the embodiment of the present invention, the switching section is divided into a first half portion and a second half portion, and three chromatographic regions Three ports are used, and an extract discharge port is not used in the first half and a raffinate discharge port is not used in the second half.

With this method, the flow rate of the product of the section containing less impurities can be made higher than that of the conventional " fourth zone-like moving bed adsorption separation (four-zone SMB process) ".

A schematic diagram of the " three-port three-port similar mobile bed adsorption separation (TT-SMB) process " according to the present invention can be seen in FIG.

The separation method of the mixture using the "three-port three-port similar moving bed adsorption separation (TT-SMB) apparatus" according to the present invention differs from the conventional SMB operation method in the following points.

First, two arrangements of "three zone-like mobile bed adsorption separation (three-zone SMB) process" are used during a switching period. In the "three-port three-port similar mobile bed adsorption separation (TT-SMB) process" according to the present invention, the switching section is divided into a first half portion and a second half portion. Quot; and " SMB without zone I process " in the latter half. That is, the desorbent flows into the zone I in the first half of the switching period and into the zone II in the latter half of the switching period. In the first half of the switching period, all of the fluid discharged from the third region is obtained as a raffinate product, and in the latter half, the fluid discharged from the first region is obtained as an extract product.

Second, compared with the conventional case where the "three zone-like moving bed adsorption separation (three-zone SMB) process" was used, the switching period using the "fourth zone without SMB without zone IV process" Does not produce the extract product in the first half and does not produce the raffinate product in the latter half of the switching period using the " SMB without zone I process ".

Thirdly, the flow rate of the raffinate discharge port increases in the first half of the switching section and the flow rate of the extract discharge port increases in the latter half of the switching section than in the conventional "four-zone SMB process".

Fourth, since three ports are used in the "three-port three-port similar moving bed adsorption separation (TT-SMB) process", the number of pumps is reduced compared to the process in which four ports are used . This not only makes it possible to reduce the cost of constructing the pump, but also allows the flow rate to be simply controlled during the operation compared to the conventional similar moving bed adsorption separation (SMB) process.

Example  And Comparative Example

의 값은 0.26 내지 0.74 로 계산되었다.In the method of separating a mixture using an SMB device according to the embodiment, the "three zone-like moving bed adsorption separation (three-zone SMB) process", which has one column per zone, Simulation studies were conducted to verify the improved performance when the "Three-port in Three-zone SMB (TMB) process" was used. (3) is applied by applying the linear adsorption coefficient of Table 1

Was calculated to be 0.26 to 0.74.

의 값이 0.26 미만이면, 라피네이트 생산 구간이 짧아져 라피네이트 생산물의 생산량이 저하될 수 있고, 컬럼 내 라피네이트 물질의 잔류로 인해 추출물 생산물의 순도가 저하될 수 있다. 마찬가지로 0.74보다 큰 값을 가지게 되면, 추출물 생산 구간이 짧아져 추출물 생산물의 생산량이 저하될 수 있고, 컬럼 내 추출물 물질의 잔류로 인해 라피네이트 생산물의 순도가 저하될 수 있다. 본 실시예에서는

의 값은 0.3, 0.5 및 0.7을 사용하였다.At this time,

Is less than 0.26, the raffinate production interval may be shortened to reduce the yield of the raffinate product, and the purity of the extract product may be lowered due to the residual raffinate material in the column. Likewise, if the value is larger than 0.74, the production yield of the extract may be shortened and the yield of the extract product may be lowered, and the purity of the raffinate product may be lowered due to the residue of the extract material in the column. In this embodiment,

The values of 0.3, 0.5, and 0.7 were used.

As a comparative example, the " SMB without zone IV process " and the " first zone excluded process ", which are the conventional "three zone-like mobile bed adsorption separation (three- A separation process using the "SMB without zone I process" and a "four zone-like mobile bed adsorption separation process (four-zone SMB process)" were used.

In the examples and the comparative examples according to the present invention, a process having one column per chromatographic area was designed. Conventionally, " four zone-based SMB process " 1110 " and " SMB without zone I process " is designated as 0111 arrangement.

The mixture to be separated in the above Examples and Comparative Examples was set to have a relatively low selectivity of 1.5. At this time, the substance having a low selectivity is not particularly limited. For example, racemic mixed medicines and the like can be used. In the case of the racemic mixed medicines, one of the isomeric forms (R-form or S-form) has a medicinal effect, while the other type has no medicinal effect or causes adverse effects such as fetal malformations and carcinogenic effects. There is a need to separate them in high purity. Since these isomers have similar physical and chemical properties such as solubility, boiling point, and melting point, it is difficult to separate the two types by a general separation method, and using the adsorption separation method according to the present invention can separate the isomers with high purity have.

In the present invention, a "three-zone similar mobile layer adsorption separation (three-zone SMB) process" simulator capable of predicting the concentration gradient in the product discharge port, mixture inlet port and column using the commercial program gPROMS Modelbuilder (TT-SMB) process ", and the separation performance of each process result is shown in terms of purity, Recovery, productivity, and solvent consumption (eluent consumption).

Two mathematical models are needed to create a simulator for these processes. One is a column model expressing the adsorption and separation behavior of each component in a single column and the other is a node model connecting multiple columns in a similar mobile layer adsorption separation process configuration .

The mathematical model equation used in the column model of the examples and comparative examples according to the present invention is equilibrium-dispersive model equation. The model equation consists of a differential mass balance equation, equilibrium isotherm and initial and boundary conditions for each material. The node model also consists of material knowledge of the flow and concentration relationships in each column and port connection to represent the configuration of a similar mobile bed sorbent separation (SMB) device.

As described above, the SMB system and the SMB system and operating parameters for performing a general SMB process simulator using mathematical model equations are shown in Tables 1 and 2 below.

값이 0.3, 0.5 및 0.7인 경우로 나누어, 각각 TT1, TT2 및 TT3로 명명하였다. 스위칭 구간의 전반부와 후반부는 각각 step A와 step B로 나타내었다. Table 1 shows the SMB system parameters for a typical SMB process. Table 2 shows the four-zone SMB process, the three-zone SMB process, &Quot; and " three zone three port similar mobile bed adsorptive separation (TT-SMB) process ". Each of the above steps was set so that the maximum flow rate of one column was 30 ml / min. The concentration of the feed to be separated in all processes was set at 3 g / l. The switching section length was set to 1.12 minutes (min) for SMB1111 and SMB1110, and to 1.24 minutes (min) for the remaining processes . The length of the switching section is calculated from the triangle theory. The reason for this difference is that the flow rate of the first zone is 30 ml / min in the SMB1111 and SMB1110 processes, The "three zone-like mobile bed adsorption separation (three-zone SMB) process" is a "three-zone SMB without zone IV process" and a " And the "SMB without zone I process" (except for the first zone). In the " three-zone three-port similar moving bed adsorption separation (TT-SMB) process "

Values were 0.3, 0.5, and 0.7, respectively, and were named TT1, TT2, and TT3, respectively. The first half and the second half of the switching period are represented by step A and step B, respectively.

The results of the separation process according to Examples and Comparative Examples according to the present invention are shown in Table 3 below.

값이 0.5인 TT2 공정은 순도(purity) 및 회수율(recovery)면에서 SMB1111, SMB1110, SMB0111 공정에 비해 뛰어난 분리 성능을 보임을 확인할 수 있다. TT1, TT2, TT3의 결과에서

값이 증가할수록 추출물 생산물의 순도, 라피네이트 생산물의 회수율, 생산성, 용매사용량이 향상됨을 확인할 수 있고, 반대로

값이 감소할수록 라피네이트 생산물의 순도와 추출물 생산물의 회수율, 생산성, 용매사용량이 향상되는 것을 확인할 수 있다. As shown in Table 3, the results of the SMB1110, SMB0111, TT1, TT2 and TT3 processes composed of only three zones in the SMB1111 process show excellent results in terms of productivity, while the eluent consumption is high . This is because the use of the adsorbent is reduced because only three zones constitute a similar mobile bed adsorption separation (SMB) process, and the use of the open loop eliminates the step of reusing the solvent. Also

It can be seen that the TT2 process with a value of 0.5 shows excellent separation performance compared to the SMB1111, SMB1110 and SMB0111 processes in terms of purity and recovery. From the results of TT1, TT2, TT3

As the value increases, it can be confirmed that the purity of the extract product, the recovery rate of the raffinate product, the productivity, and the solvent consumption are improved,

As the value decreases, the purity of the raffinate product and the recovery rate, productivity and solvent consumption of the extract product are improved.

As a result, the " three-zone three-port similar mobile bed adsorptive separation (TT-SMB) process " It is possible to produce materials of higher purity than the " four-zone SMB process ".

5 to 7 show graphs of concentration gradients of the products in the SMB1110, SMB0111, and TT2 process results of Tables 2 and 3 above. FIGS. 5 to 7 (a) show the concentration gradient of the product at the extract outlet port, and (b) show the concentration gradient of the product at the raffinate outlet port.

FIG. 5 is a graph showing the product concentration gradient when the "SMB without zone IV process" (SMB1110) is used in the "three zone-like moving bed adsorption separation (three-zone SMB) to be. The raffinate product in the first half of the switching section is almost pure desorbent, which can be interpreted as the consumption of unnecessary solvent.

값이 0.5였을 때(TT2)의 생산물 농도구배 그래프이다. 두 그래프의 농도구배는 비슷해 보이지만, 표 3에서와 같이 TT2 공정의 순도가 훨씬 높은 것을 확인할 수 있다. 이는 “세 구역 세 포트 유사 이동층 흡착 분리(TT-SMB) 공정”에서는 도 6에 도시한 것과 같이 불순물이 거의 포함되지 않은 순수한 부분만 생산물로 생산하고, 나머지 부분은 생산 노드의 밸브를 닫아 생산물로 얻지 않기 때문이다.6, when the " SMB without zone I process " (SMB0111) is used in the "three zone-like mobile bed adsorption separation (three-zone SMB process) Quot; three-port three-port similar mobile bed adsorptive separation (TT-SMB) process "

(TT2) when the value is 0.5. The concentration gradients of the two graphs are similar, but the purity of the TT2 process is much higher as shown in Table 3. In the " three-port three-port similar moving bed adsorption separation (TT-SMB) process ", only pure portions substantially free from impurities are produced as shown in FIG. 6, .

In conclusion, the three-zone three-zone SMB process according to the present invention can be applied to the three-zone SMB process, SMB) process ", it can be said that the separation performance is effectively improved by controlling the flow rate.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to provide further explanation of the invention as claimed. Such modifications, alterations, and additions should be regarded as falling within the scope of the following claims.

Claims (4)

_A similar mobile bed adsorptive separation (SMB) apparatus comprising three chromatographic zones defined by a first to a third chromatographic zone, the switching zone comprising a switching section defined by a Δt _A section and a Δt _B section,
In the interval Δt _A ,
A chromatograhy zone I in fluid communication with the desorbent inlet port; A second chromatography chromatographic region fluidly connected to the first chromatographic region; And a third chromatography zone fluidly connected to the second chromatography zone, the separation subject mixture inlet port and the raffinate outlet port being fluidly connected,
In the? T _B section,
A chromatography chromatographic section fluidly connected to the Ⅲ chromatographic section and fluidly connected to the extract outlet port; A chromatographic region II fluidly connected to the desolvating agent inlet port in fluid communication with the first chromatographic section; A third chromatographic region fluidly connected to the second chromatographic region, the separation subject mixture inlet port being in fluid communication with the second chromatographic region,
A similar moving bed adsorptive separation apparatus satisfying the following general formulas 1 to 2:
[Formula 1]

[Formula 2]

In the equations (1) and (2),? _{T A} represents the time of the first half of the switching period _,? T _B represents the time of the second half of the switching period, t _sw represents the switching time,

Represents the ratio of the time of the first half of the switching period (Δt _A).
The method according to claim 1,
Wherein the switching section including the? _{T A} section and the? _{T B} section is repeatedly performed in the entire switching section.
_A method for separating a mixture using a similar moving bed adsorption separation (SMB) apparatus comprising three chromatographic zones defined by the chromatographic zones I to III, comprising a switching section defined by a section Δt _{A and a} section Δt _B ,
In the interval Δt _A ,
The fluid is transferred in the order of the first, the second, the third and the third chromatography zone, and the desorbent is introduced into the first chromatographic zone; The step of introducing the mixture to be separated into the Ⅲ chromatographic section; And discharging the raffinate product in the third chromatographic zone,
In the? T _B section,
II, III, and I chromatographic zones, and introducing desorbent into the second chromatographic zone; The step of introducing the mixture to be separated into the Ⅲ chromatographic section; And discharging the extract product in said I chromatography zone,
A method for separating a mixture satisfying the following general formulas 1 to 2:
[Formula 1]

[Formula 2]

In the equations (1) and (2),? _{T A} represents the time of the first half of the switching period _,? T _B represents the time of the second half of the switching period, t _sw represents the switching time,

Represents the ratio of the time of the first half of the switching period (Δt _A).
The method of claim 3,
The separation subject mixture is an aromatic hydrocarbon, ethylbenzene, chiral compound or racemic mixture.

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