TWI406697B - Method for separating three ingredients in mixture with simulated moving bed - Google Patents

Abstract

A method for separating three ingredients in mixture with a simulated moving bed (SMB) comprises: (a) providing a SMB device containing three connected sections &agr; , &bgr; and &ggr; with first, second and third flow-rate ratios, respectively; (b) providing a mixture with three ingredients with strong, medium, and weak adsorption, and an adsorption constant Ka, Kb and Kc, respectively; (C1) putting the mixture into the SMB device, with the first flow-rate ratio > Ka, the second and third flow-rate ratios < Kb and > Kc, resulting in the ingredient with weak adsorption to be separated; (C2) putting the mixture into the SMB device, with the first flow-rate ratio > Kb and < Ka, the second and third flow-rate ratios < Kb and > Kc, resulting in the ingredient with medium adsorption to be separated.

Description

Method for simulating moving bed separation of three-component mixture

The present invention relates to a method for simulating a moving bed separation of a three component mixture, and more particularly to a method for separating an adsorption or weak adsorption component of an adsorbent in a mixture of three components.

It is conventional to simulate moving bed separation of components in a mixture. The operator must select a solid adsorbent (Stationary Phase) and a detergent phase (Mobile Phase) suitable for separating the separation. Referring to FIG. 1 , the conventional simulated moving bed system has a four-zone simulated moving bed, wherein the four regions are α, β, γ, and δ regions, respectively, and the detergent flows in the simulated moving bed. The solid adsorbent, on the other hand, exhibits a flow in the opposite direction relative to the detergent. When the strong adsorption component A in the moving bed separation mixture is simulated by the conventional method, the detergent is preliminarily flowed in the simulated moving bed according to the order of the α, β, γ and δ regions, and the component A adsorbs to the solid. The strong adsorption force of the agent, the component A flows to the β region with the solid adsorbent, the remaining components (including the weakly adsorbing component B) and the detergent flow to the γ region, and the weakly adsorbed material is discharged from one of the γ regions O _γ flows out, and the remaining detergent flows out from the δ region and flows to the front end of the α region, and then enters the tandem column for recycling, and the component A retained in the α and β regions is washed away from the α region. One of the strong adsorption discharges O _α flows out, wherein a mode of relative flow between the simulated moving bed detergent and the solid adsorbent utilizes a switching time of the pipeline configuration and the switching valve to simulate the solid adsorbent Reverse flow.

Referring to Figures 2a and 2b, the simulated moving bed includes four segments S91. The column groups of S92, S93 and S94 are connected in sequence, and each section S is provided with at least one column, and the number of columns of each section S is set according to the needs of the user, and each column is provided with Control the opening and closing of the inlet I and the outlet O.

The column of the four sections S is filled with a solid adsorbent system which has strong adsorption to the object to be separated (component A) and weak adsorption to the object to be separated (component B), and the detergent is fed through the feed. The mouth or another set of infusion port enters the simulated moving bed, and the other components adsorbed by the solid adsorbent are not separated, and the solid adsorbent is opposite to the flow of the detergent, thereby separating the component A and the component. The effect of B.

Conventionally, the technique of separating a two-component by moving bed is to change the mixture into a feed position of a conventional simulated moving bed, so that the solid adsorbent simulates a state of moving in a relative direction, more specifically, when the mixture enters the When the simulated moving bed changes direction, the solid adsorbent has a relatively negative movement.

Please refer to the relationship between the discharge point or the feeding position shown in Figure 1 and Table 1 and the area of the simulated moving bed, and cooperate with the pipeline configuration corresponding to the 2a and 2b diagrams and the schematic diagram of the discharge port or the inlet port switch. . Since the mixture changes its position into the simulated moving bed with different time, the conventional four-segment simulated moving bed has four regions, namely α, β, γ and δ regions, respectively, defining a first time t1. The column group of the first segment S91 is an α region, and the end of the α region is provided with a strong adsorption discharge point O _α , the column group of the second segment S92 is a β region, and the third region The column group of the segment S93 is a γ region, and a mixture feed point I _γ and a weak adsorption discharge portion O _{γ are} disposed at a front end of the γ region, and a column group of the fourth segment S94 is a δ region, and After switching to the second time t2 after a period of time, the α, β, γ, and δ regions will move to the next segment until after switching to the fourth time t4, recycling back to the mode of the first time t1, The discharge port position of the desired extract is to be compared with the discharge port O of each section shown in Table 1.

For example, referring to FIG. 2a, when the detergent enters the tandem string group from the feed port I91 of the first section S91, the mixture enters the feed port I93 of the third section S93. The column group is connected in series, and at the same time, the extract liquid having a strong adsorptive component is outputted from the discharge port O92 of the second section S92, and the discharge port O94 of the fourth section S94 outputs the raffinate having a weakly adsorbing component. liquid. Referring again to Figure 2b, after a period of time (switching to the second time T2), the mixture feed I _γ , the strong adsorption discharge O _α and the weak adsorption discharge O _{γ are} simultaneously moved to The next section S, after a period of time (switching to the third time T3), then switching to the next section S, so as to continuously switch the mixture feed point I _γ , the strong adsorption discharge point O _α and the The position of O _γ at the weak adsorption discharge can simulate the behavior of the solid adsorbent flowing in the opposite direction to the switching sequence of the inlet and outlet. Since the detergent and the separator are continuously fed, and the solid adsorbent is again simulated to flow in the opposite direction, the contact of the solid adsorbent with the detergent is similar to the reverse flow.

However, the simulated moving bed shown in Figure 1 can only separate the two-component mixture. If you want to separate the three components A, B and C from the mixture, you must use two sets of simulated moving beds as shown in Figure 3. In order to achieve the separation of the three components A, B, C, wherein the adsorption of the three components to the solid adsorbent is from strong to weak as component A (strong adsorption), component B (medium adsorption) and component C (weak adsorption force).

Referring to FIG. 3, two sets of the above four-zone simulated moving bed are combined, and the first group of simulated moving beds includes four regions, namely, 1α, 1β, 1γ, and 1δ regions, and the second group of simulated moving beds. There are also four regions, namely 2α, 2β, 2γ and 2δ regions, respectively, and the two sets of simulated moving beds are respectively provided with a strong adsorption discharge point O _1α , O _2α , a mixture feed point I _1γ , I _2γ and one Weak adsorption of O _1γ and O _2γ at the discharge.

The detergent enters any region of the 1α, 1β, 1γ, and 1δ regions of the first group of simulated moving beds, and then sequentially flows in each region, and at the same time, the detergent enters the 2α of the second group of simulated moving beds. After any of the 2β, 2γ, and 2δ regions, the cells flow sequentially in each region, and are circulated in each of the four regions to stabilize the washing conditions of the two sets of simulated moving beds.

When the mixture containing the components A, B, and C enters the 1γ region through the strong adsorption and discharge portion O _{1α of} the first group of simulated moving beds, the component A flows to the 1β region along with the solid adsorbent, and the components B and C And the detergent flows to the 1γ region, and the components B and C are discharged from the weakly adsorbed material O _1γ , and the component A is retained in the 1α and 1β regions and washed by the clean detergent. The strongly adsorbed discharge O _1α flows out.

The components B and C are discharged from the weak adsorption and discharge material O _1γ of the first group, and enter the mixture feeding point I _{2γ of} the second group of simulated moving beds. At this time, the component B adsorbs the solid adsorbent. The force is greater than the component C, the component B flows to the 2β region along with the solid adsorbent, the component C and the detergent flow to the 2γ region, and the component C is from the weakly adsorbed material at the O _2γ , and the component is at this time B is retained in the 2α and 2β regions and washed away by a clean detergent. The O _{2α is} discharged from the strongly adsorbed discharge, and the separation of the three components is completed.

It can be seen from the above that the conventional method for separating a three-component mixture by using a simulated moving bed must first separate the component A of the strong adsorption force in the three components A, B, and C, and then separate the component B of the adsorption force or the weak adsorption. The composition of force C. More specifically, the conventional separation method cannot directly separate the adsorption force component B or the weak adsorption force component C in the desired separation, and must be separated according to the adsorption strength of the three components A, B, and C. Ingredient A can separate component B; or component A and B can be separated in order to separate component C. Therefore, the procedure for separating component B or C is complicated and cumbersome, and the separation procedure must pass through multiple sets of columns. The time required is also longer; in addition, since the separation component B or C must additionally use a plurality of sets of columns, the conventional method is expensive, and the component of the adsorption component B or the low adsorption component C cannot be avoided. Problems such as expensive column charges.

The main object of the present invention is to provide a method for simulating a moving bed separation three-component mixture, which can directly separate the components of the three-component mixture into the adsorption or weak adsorption force of the solid adsorbent to shorten the adsorption force in the separation or Operating time of components with weak adsorption.

A second object of the present invention is to provide a method for simulating a moving bed separation three-component mixture, which can separate the adsorption or weak adsorption force of the solid adsorbent in the three-component mixture by using only the three-zone simulated moving bed. Ingredients to reduce the cost of its separation.

In order to achieve the foregoing object, the technical content of the present invention comprises: a method for simulating a moving bed separation three-component mixture, the method comprising: (a) providing a three-zone simulated moving bed device, sequentially connected The α, β and γ regions, the end of the α region is provided with a strong adsorption discharge, the front end of the γ region is provided with a mixture feed, and the rear end of the γ region is provided with a weak adsorption discharge; (b) The three-zone simulated moving bed contains an adsorbent, and a flushing agent flows in the α, β, and γ regions to contact the adsorbent, and the α, β, and γ regions respectively have a first flow rate ratio and a second flow rate ratio. And a third flow rate ratio; and (c) injecting a three-component mixture from the feed to the three-zone simulated moving bed, the three-component mixture comprising a strong adsorption component relative to the adsorbent, An adsorption component and a weak adsorption component, the strong, medium and weak adsorption components respectively having a Henry adsorption constant Ka, Kb and Kc; (d) the three component mixture is input into the three-section simulated moving bed device, And The first flow rate ratio is greater than the Henry adsorption constant Ka, and the second flow rate ratio and the third flow rate ratio are less than the Henry adsorption constant Kb and greater than the Henry adsorption constant Kc, then the weak adsorption component of the three component mixture is The weakly adsorbed discharge is concentrated and separated.

A method for simulating a moving bed separation three-component mixture, the method comprising: (a) providing a three-zone simulated moving bed device, in sequence, a connected alpha, beta and gamma region, the alpha region having a strong end At the adsorption discharge, a gamma region is provided with a mixture feed at the front end, and a weak adsorption discharge is provided at the rear end of the γ region; (b) the three-zone simulated moving bed contains a sorbent, and a rinsing agent flows through The alpha, beta and gamma regions are in contact with the adsorbent, the alpha, beta and gamma regions respectively having a first flow rate ratio, a second flow rate ratio and a third flow rate ratio; (c) from the mixture feed Injecting a three-component mixture into the three-zone simulated moving bed, the three-component mixture comprising a strong adsorption component, a medium adsorption component and a weak adsorption component, respectively, relative to the adsorbent, the strong, medium and weak adsorption The force components respectively have a Henry adsorption constant Ka, Kb and Kc; and (d) a device for inputting the three component mixture into the three-section simulated moving bed, and the first flow rate ratio is greater than the Henry adsorption constant Kb and less than the Henry suck a constant Ka, the second flow rate ratio and the third flow rate ratio being less than the Henry adsorption constant Kb and greater than the Henry adsorption constant Kc, wherein an adsorption component of the three component mixture is concentrated by the strong adsorption output and Separation.

The above and other objects, features and advantages of the present invention will become more <RTIgt; The method of the specific component, in particular, is a method for separating a three-component mixture by a simulated moving bed, wherein the three components are component A, component B and component C, respectively, and the adsorption of the three components on the adsorption column is The order from strong to weak is component A (strong adsorption), component B (medium adsorption) and component C (weak adsorption).

Referring to FIG. 4, it is a schematic diagram of a configuration of a simulated moving bed pipeline used in the present invention. The simulated moving bed is sequentially provided with one of the first section S1 and the second zone. a column group of the segment S2 and the third segment S3, the column group comprising a sorbent (ie, a stationary phase, abbreviated as SP) and a device (ie, a mobile phase, referred to as MP), wherein the adsorption The agent is filled in a column, and the flow of the adsorbent and the detergent in the column are opposite to each other. Each of the sections S in the simulated moving bed used in the present invention is provided with at least one column (the column of the first section S1 of the embodiment is c11 and c12, and the column of the second section S2 is c21). And c22, the column of the third section S3 is c31 and c32), the columns in each section S are connected in series and the detergent can be sequentially flowed to the next section S, when each zone The more the number of columns of the segment S, the better the separation effect on the component to be separated (abbreviated as the extract). The three columns have pores therein, so that the detergent can flow from one end of the first section S1 to the other end, and flow to the second section S2 and then to the third section S3. A first inlet port I1 and a first outlet port O1 are respectively disposed at the front end and the rear end of the first section S1, and a second inlet port I2 and a second portion are respectively disposed at the front end and the rear end of the second section S2. The discharge port O2 is provided with a third feed port I3 and a third discharge port O3 before and at the rear end of the third section S3.

The simulated moving bed used in the present invention is provided with at least one switching valve to control the switch of the feeding port and the discharging port of each section S, and each metering section S is provided with a metering liquid pump P to match different time T control. The adsorbent volume flow rate Qsp and the detergent volume flow rate Qmp of each section S, in particular, the shift valve controls the movement of the feed port, thereby regulating the adsorbent volume flow rate Qsp, and the metering liquid pump P of each section S The detergent volume flow rate Qmp can then be controlled.

As shown in the first table, the concept of the relative relationship between the discharge point or the feed point and the area of the simulated moving bed, as shown in Fig. 5, the simulated moving bed used in the present invention also has three regions, which are sequentially connected. The solvent is circulated through the α, β and γ regions, and the end of the α region is provided with a strong adsorption output O _α , which is an outlet for the component having strong adsorption force to the adsorbent; the γ region The front end is provided with a mixture feed point I _γ for the mixture to enter the inlet of the simulated moving bed; the weak end of the γ area is provided with a weak adsorption discharge O _γ for the component having a weak adsorption force to the adsorbent Export. The movement of the mixture feed I _{γ is} controlled by the simulated moving bed line configuration and switching valve shown in Fig. 4 to simulate the relative flow of the detergent and the adsorbent.

The invention defines that the flow direction of the adsorbent (SP) is negative (flow from the γ region toward the α region), and the flow direction of the detergent (MP) is positive (from the α region toward the γ region) The volumetric flow rate Q refers to the volume through which the detergent or adsorbent passes during a unit time; the alpha region has a adsorbent volume flow rate Qsp1 and a flush volume flow rate Qmp1, the beta region having a The adsorbent volume flow rate Qsp2 and a flushing agent volume flow rate Qmp2 have a sorbent volume flow rate Qsp3 and a flushing agent volume flow rate Qmp3.

The adsorbent refers to a substance having adsorption characteristics to the three components, and the adsorbent has an adsorption force between the adsorbent and the extract to cause the adsorbent to adsorb the extract, and the adsorption force can be anion and cation, polarity and non- Polarization and other adsorption, the adsorbent can be selected from activated carbon, activated carbon fiber, carbon molecular sieve, carbon nanotube, tannin, cerium oxide, alumina, zeolite, resin, pillared clay, etc. An adsorbent has a specific Henry adsorption coefficient K, which determines the adsorption strength between the extract and the adsorbent. For the same adsorbent, the higher the Henry adsorption coefficient K of each component, the The stronger the adsorption strength of the adsorbent.

The detergent is a substance that can flow in the column to wash away other components of the mixture that are not adsorbed by the adsorbent (collectively referred to as raffinate), and the raffinate is carried away from the column. The effect of separating the desired extract is achieved.

The effect of separating the extracts from the multi-component mixture can be improved by selecting adsorbents and detergents of different properties according to the characteristics of the components to be separated. The "separation" of the present invention refers to the use of appropriate adsorbents and detergents for multiple components. The separation of a component, in particular, the concentration of the component to increase the concentration of the component for subsequent analysis or utilization. The present invention provides a separation method that allows the operator to separate (or concentrate) according to the method. One of the three component mixtures.

The present invention is directed to a separation of a specific component A, B or C comprising a mixture of components A, B or C, wherein the Henry adsorption constant K of the component A, B or C for the adsorbent is Ka>Kb>Kc, respectively. Therefore, the adsorption strength of the component A, B or C for the adsorbent is A>B>C, respectively.

According to the theory of triangle (Yu, HW, CB Ching, "Optimization of a simulated moving bed based on an approximated Langmuir Model" AIChE J. 48 (2002) 2240-2246), the adsorbent and the washing agent of each area of the simulated moving bed are defined. The volumetric flow rate of the agent is Qsp and Qmp, respectively, and the net flux F of the extract in each region must satisfy the formula I, and the net mass flux F refers to the passage of the desired material through the region. Net mass flux, when the net mass flux F is greater than zero, indicating that the component A, B or C is moving with the flow of the detergent, and when the net mass flux F is less than zero, indicating that the component A, B or The C system moves with the flow direction of the adsorbent.

Where ε is the porosity, which refers to the proportion of the pores in the column of the region, that is, the portion through which the detergent can flow, and 1-ε refers to the ratio of the voids in the column, that is, the adsorbent Where n is the flow rate ratio n of the adsorbent to the detergent in the same region; C is the concentration of the detergent in the region; q is the concentration of the adsorbent in the region. The retention strengths of components A, B and C in this example are A>B>C, which means that the net mass flux F of each component A, B and C should be Fa<Fb<Fc.

For the definition of the flow rate ratio n, refer to Formula II, which is the ratio of the volume of the detergent flowing through the column in the unit time T to the volume of the adsorbent flowing negatively through the column, where V represents the column volume. Vε is the column volume V multiplied by the porosity ε (pore volume), ie the volume of the detergent, and V(1-ε) is the column volume V multiplied by the column deducted porosity (1-ε) The ratio represents the volume occupied by the adsorbent; V ^D represents the dead volume in the column. For example, the connecting line between the two columns of the V ^D system does not contain the adsorbent, so the communication The detergent in the pipeline volume does not have a separation effect and should be deducted. When the volume flow rate Qmp of the detergent is multiplied by the unit time T, which is the volume of the detergent in the unit time T, the volume is subtracted from the second constant value Vε (because the switching between the feed port and the discharge port is made, In addition to the negative flow of the solid adsorbent, the liquid in the pores of the solid adsorbent is also carried to the negative flow and V ^D , the actual volume of the detergent in the unit time T is obtained.

Dividing the formula II by the unit time T can obtain the formula III, where Vε/T and V ^D /T are constant values. Therefore, it can be derived from the formula III that the flow rate ratio n represents the washing in the same region. The ratio of the volumetric flow rate Qmp to the adsorbent volumetric flow rate Qsp (i.e., V(1-ε)/T) in the region.

It can be inferred from the triangulation theory and formulas I, II and III that the ratio of the flow rate ratio n in each region determines the regulation of the adsorption between the adsorbent and the components in the region. More specifically, if the desired mass is to move in the forward direction, then the net mass flux F of the extract should be greater than zero:

F=Qsp(1-ε)(nC-q)> 0 (I.1)

Wherein, when the net mass flux F is greater than zero, Qsp>0, and (1-ε)>0, the formula (I.2) is obtained:

→ nC-q> 0 (I.2)

get

According to the definition of the Henry adsorption constant K, the formula I.4 is obtained:

When the adsorbent adsorbs the phenomenon of the extract, the linear relationship is obtained, and the formula I.5 is obtained.

Combining the formulas I.3 and I.5, the formulas I.6 and I.7 are obtained, and the net mass flux of each component A, B and C in each region is obtained by the relationship between the flow rate ratio n and the Henry adsorption constant K. F can meet the conditions of separation or concentration.

If the desired mass is to be moved in the negative direction, then the net mass flux F of the extract should be less than zero. With the above derivation, formula I.7 can be obtained:

Thereby, the relationship between the flow rate ratio n of each of the regions α, β, and γ regions shown in Table 2 and the Henry adsorption constant K of the extract to be extracted is obtained. For example, if the component A is to be separated, as shown in Fig. 5, in order to cause the component A to flow out at the strong adsorption discharge O _{α of} the α region, the net mass of the component A in the α region is The amount Fa should be less than zero, indicating that the first flow rate ratio n1 of the alpha region is less than the Henry adsorption constant Ka of the component A, and the component A is adsorbed by the adsorbent of the alpha region without being carried away by the detergent. And flowing out of the α region; when the first flow rate ratio n1 of the α region is greater than the Henry adsorption constant Ka of the component A, the component A is carried away from the α region by the detergent, and the first discharge port O1 When flowing out, the net mass fluxes Fb and Fc of the components B and C in the β and γ regions should be greater than zero, that is, the flow rate ratios n2 and n3 of the β and γ regions should be greater than the Henry adsorption constant Kb and less than the Henry adsorption constant. Ka to prevent the component A from moving in the positive direction of the β and γ regions.

Please refer to the condition setting of Table 2 and the schematic diagram of the simulated moving bed line in Figure 5, that is, a set of three-zone simulated moving bed can be used to separate the desired material such as component A, B or C.

Referring to Figure 6, the first embodiment of the present invention separates the component A by a three-zone simulated moving bed separation method containing a mixture of three components A, B and C (the Henry adsorption constant Ka system three component A) , the largest of B or C), the simulated moving bed system includes a sorbent moving in a negative direction thereof, and a detergent moving toward the forward direction, the detergent entering the alpha region of the simulated moving bed, The mixture enters the simulated moving bed from the feed point I _γ , wherein the first flow rate ratio n1 of the α region is greater than the Henry adsorption constant Ka, and the flow rate ratios n2 and n3 of the β region and the γ region are It is smaller than the Henry adsorption constant Ka and larger than the Henry adsorption constant Kb.

More specifically, after the mixture enters the simulated moving bed from the feed I _γ , the flow rate ratio n of the three regions is greater than the Henry adsorption constant Kb or Kc, and therefore, the detergent has the component B and C or other impurities are moved away from the adsorbent toward the simulated moving bed, and O _γ flows out at the weakly adsorbed discharge; and the flow rate ratios n2 and n3 of the β and γ regions are smaller than the Henry adsorption constant Ka Therefore, the adsorbent of the β and γ regions adsorbs the component A, and the adsorbent moves toward the negative direction of the simulated moving bed. When the component A moves to the α region, the first flow rate ratio n1 of the α region Henry system is greater than the adsorption constant Ka, the component A is washed away from the adsorbent adsorbing the detergent at the outfeed flows from the strong _O α.

It can be seen from the above that the present invention can utilize the simulated moving bed of the three regions to separate the component A of strong adsorption force, in particular, by adjusting the flow rate ratio n1 of the α region to be greater than Ka, and the flow rate ratio n2 to the β region is smaller than Ka, so that The component A moves in a negative direction, and the remaining adsorption force is moved toward the positive direction compared with the component A, and the component A is separated at the strong adsorption discharge point O _α .

Referring to Figure 7, the second embodiment of the present invention is also a method for separating a mixture containing three components A, B and C by a simulated moving bed of three zones, directly to the component C (the Henry adsorption constant Kc system) The third largest component of the three components A, B or C is concentrated and separated without first separating the components A and B. The mixture enters the simulated moving bed from the feed I _γ , wherein the first flow rate ratio n1 of the α region is greater than the Henry adsorption constant Ka; the flow rate ratios n2 and n3 of the β and γ regions are less than the Henry The adsorption constant Kb is greater than the Henry adsorption constant Kc.

More specifically, after the mixture enters the simulated moving bed from the feed point I _γ , the flow rate ratio n of the three regions is greater than the Henry adsorption constant Kc, and therefore, the detergent takes the component C away from the The adsorbent moves toward the positive moving bed and exits O _γ at the weak adsorption output; and the second flow rate ratio n2 of the β region is smaller than the Henry adsorption constants Ka and Kb (but greater than the Henry adsorption constant) Kc), therefore, the adsorbent of the beta region adsorbs the components A and B, and the adsorbent moves toward the negative direction of the simulated moving bed, and when the components A and B move to the alpha region, the alpha region a flow rate greater than the ratio n1-based adsorption Henry constant Ka and Kb, the component a and B are to be washed away from the adsorbent adsorbing the detergent at the outfeed flows from the strong _O α.

As can be seen from the above, the present invention is to adjust the flow rate ratio n2, n3 of the β and γ regions, S3 is greater than Kc and less than Kb, and the flow rate ratio n1 of the α region is greater than Ka, so that the component C moves in the positive direction, and the rest If the adsorption force is stronger than the component C, it moves in a negative direction, and the component C can be obtained at the weak adsorption output O _γ , and the effect of saving the adsorbent (the number of columns) can be achieved; in addition, the present invention separates the component C. When the component A or B having a strong adsorption force to the adsorbent is not removed in advance, the time course of separation is short, and the effect of saving time can be achieved.

Referring to Fig. 8, the third embodiment of the present invention is also a method for separating a mixture containing three components A, B and C by a three-zone simulated moving bed, the component B (the Henry adsorption constant Kb system III) The second largest of the components A, B or C) is concentrated and separated without first separating the component A. The mixture enters the simulated moving bed from the feed point I _γ , wherein the first flow rate ratio n1 of the α region is greater than the Henry adsorption constant Kb and less than the Henry's constant Ka, and the flow rate ratio n2 of the β and γ regions And n3, which is greater than the Henry adsorption constant Kc and less than the Henry adsorption constant Kb.

More specifically, after the mixture enters the simulated moving bed from the feed I _γ , the flow rate ratios n2 and n3 of the β and γ regions are both greater than the Henry adsorption constant Kc and less than the Henry adsorption constant Kb, thus The adsorbent adsorbs the components A and B and moves toward the negative direction of the simulated moving bed. When the components A and B move to the alpha region, the first flow rate ratio n1 of the alpha region is greater than the Henry adsorption constant. Kb, but less than the Henry adsorption constant Ka, the component B is carried away from the adsorbent by the detergent and flows out from the strong adsorbent discharge O _α ; the adsorbent will continue to adsorb the component A and move toward the simulation The negative movement of the bed cannot be rushed out. Therefore, when separation is carried out for a period of time, the component A adsorbed by the adsorbent needs to be washed away to avoid contamination of the concentration of component B of O _α at the strong adsorption output. And the velocity ratios n1, n2, and n3 of the three regions are greater than the Henry adsorption constant Kc, and therefore, the detergent moves the component C away from the adsorbent toward the positive moving bed, and from the weak O _{γ is} discharged from the adsorbed discharge.

As can be seen from the above, the present invention is characterized in that the flow rate ratio n1 of the α-region is larger than Kb and smaller than Ka, and the flow rate ratios n2 and n3 of the β and γ regions are larger than Kc and smaller than Kb, so that the component B moves in a negative direction and adsorbs. The component C whose force is less than the component B moves in the forward direction, and the flow rate ratio n of the three regions is smaller than the Henry adsorption constant Ka of the component A, so that the component A is not concentrated in any region and is discharged from any of the materials. O flows out, and the component B is obtained at the strong adsorption discharge O _α , and the component C is obtained by the O _γ at the weak adsorption discharge; in addition, the separation of the component B by the invention does not require prior removal of the adsorbent. The component A of strong adsorption force, therefore, the time course of separation is short, and the effect of saving time can be achieved.

As can be understood from the foregoing second and third embodiments, the present invention can control the forward or negative flow of the extract by using the condition that the flow rate ratio n in each region is adjusted to meet the conditions of the first table. The direct separation of the medium adsorption or weak adsorption components, thereby achieving the effect of saving the number of columns (cost) and shortening the separation time.

In order to confirm that the method of simulating the moving bed separation of the three-component mixture of the present invention can indeed separate or concentrate the component having the second strongest adsorption or the third strongest, a three-component mixture is separated for the organic solvent extract of the fragrant ruthenium.

"Preparation of ethyl acetate extract of fragrant ruthenium"

Xiangru (also known as staghorn) contains a variety of classified compounds with anti-inflammatory, anti-hepatitis B virus and immune regulation, such as Oleanolic acid, Luteolin, luteolin - Luteolin-7-glucoside and other unidentified ingredients, of which luteolin has been proven to be an important flavonoid compound with antioxidant, anti-inflammatory, anti-cancer and immune regulation, oleanolic acid And luteolin-7-glucoside can inhibit the expression of iNOS and COX-2 genes induced by endotoxin LPS secreted by bacteria, and inhibit the proinflammatory cytokines released by NF-κB (such as TNF-α, IL). The efficacy of -1β, IL-6 and IL-12).

The fragrant ruthenium is ground into a fragrant powder, which can be extracted by alcohol through a screen size of 200#, the fragrant powder: alcohol is about 1:4, and the extraction time is 24 After ±2 hours, the residue was filtered and concentrated to give an alcohol extract powder. The alcohol extract powder is dissolved back into a viscous substance by 95% alcohol (the alcohol extract powder: 95% alcohol is about 4:1), and subjected to ultrasonic shock extraction with ethyl acetate (Ethyl acetate) for 24 ± 2 hours. This was concentrated to dryness to give an ethyl acetate extract containing luteolin and luteolin-7-glucoside. When separating the ethyl acetate extract with luteolin and luteolin-7-glucoside by high performance liquid chromatography, please refer to Figure 9 for the HPLC chromatogram. As an impurity, the component A is luteolin-7-glucoside, and the component C and A still contain the component B (luteolin), wherein the chromatographic time of the component C falls within 2 to 5 minutes, and the composition The chromatographic time of B is about 10 minutes, and the chromatographic time of component A is about 12 minutes. By the separation method of the present invention, the component C can be obtained without separating the components A and B in advance.

"Configuration and Condition Setting of Simulated Moving Bed Used in the Invention"

In this embodiment, the separation of the components A (luteolin-7-glucoside), component B (luteolin) and component C of the fragrant ruthenium is selected by a three-section simulated moving bed, wherein each segment S The number of the columns is two, and the column is made of tannin as a adsorbent (Merck Lichrospher 100 RP-18, 250 × 4.6 mm, pore size 5 μm), and the detergent is a volume ratio of 0.1% acetic acid solution to methanol. Formulated at 7:13, the detergent should be prepared before use and vortexed for 30 minutes to remove air bubbles from the solution. Wherein the crucible column has a porosity ε = 0.412, and the simulated moving bed has a dead angle volume V ^D = 0.117 cm ³ .

Please refer to the condition 1 shown in Table 3, which is the first embodiment of the present invention, according to the Henry adsorption constant K of the component A, the component B and the component C of the fragrant ru, 5.304, 4.179 and 0.222 to 2.196, respectively. The first flow rate ratio n1 of the α region set in the condition 1 is 11.81, and the second flow rate ratio n2 of the β region is 3.05, and the third flow rate ratio n3 of the γ region is 3.65. In this embodiment, all of n1, n2 and n3 are greater than Kc (0.222 to 2.196), wherein the n2 and n3 are smaller than Kb (4.179), and the component C flows out at the weakly adsorbed discharge O _γ , and the component Both A and B are carried to the negative direction by the detergent. When the components A and B flow to the alpha region, the n1 is greater than the Ka, so that the components A and B both flow out from the strong adsorption discharge O _{α .} And a higher purity component C is obtained.

*Ka=5.304, Kb=4.179 and Kc=0.222~2.196

Referring to Tables 4 and 10, the components A, B, and C separated by the simulated moving bed used in the present invention are respectively at the strong adsorption discharge O _α and the weak adsorption discharge O _{γ .} Concentration and chromatographic signal, and O _γ at the weakly adsorbed discharge can obtain high-purity component C, and there is no signal of component A or B, which proves that the first embodiment of the present invention can indeed be at the weak adsorption output The concentration of the low-adsorption component C in the three-component mixture is increased in O _γ , in particular, the component C having high purity in the extract, and the components A and B are separated at the strong adsorption output O _α Instead of contaminating the component C of the O _γ at the weakly adsorbed discharge.

Referring to Table 5, in the first embodiment of the present invention, the product obtained by the O _γ at the weakly adsorbed discharge contains the high-purity component C, and the product obtained by the O _γ at the weakly adsorbed discharge contains the starting material. 58.83% of the component C in the feed, therefore, the separation conditions of this example can indeed concentrate and separate component C.

Referring to Condition 2 shown in Table 6, the second embodiment of the present invention sets the first flow rate ratio n1 of the α region to 5.29, and the second flow rate ratio n2 of the β region is 3.05. The third flow rate ratio n3 of the gamma region is 3.65. In this embodiment, all of n1, n2 and n3 are greater than Kc (0.222 to 2.196), wherein the n2 and n3 are smaller than Kb (4.179), and the component C flows out at the weakly adsorbed discharge O _γ , and the component Both A and B are carried to the negative direction by the detergent. When the components A and B flow to the first section S1, the n1 is greater than the Kb (4.179) but less than Ka (5.304), so that the component B is self-contained. The strong adsorption discharge O _α flows out, and the component A is adsorbed by the adsorbent and continues to move in the negative direction of the simulated moving bed.

*Ka=5.304, Kb=4.179 and Kc=0.222~2.196

Referring to Table 7, the concentrations of components A, B, and C separated by the simulated moving bed used in the present invention are respectively at the strong adsorption discharge O _α and the concentration of O _γ at the weak adsorption discharge, wherein The test group consisted of five groups. The initial concentration of the components in each group was 156.3 ppm, the concentration of component B was 200.9 ppm, the concentration of component C was 73.8 ppm, and the concentration of each component B was 114.12 ppm on average. In a second embodiment of the invention, the concentration of the adsorbing component B in the three component mixture can be increased in the extract of the strongly adsorbed material O _?.

Referring to Table 8, in the second embodiment of the present invention, the product obtained by O _α at the strong adsorption discharge contains a higher concentration of component B, and the product obtained by O _α at the strong adsorption discharge contains 56.80% of the component B in the initial feed, please refer to Figure 11, the chromatogram of the component B at the strong adsorption discharge O _α is greater than the chromatogram of the component A at the strong adsorption discharge O _α And the strong adsorption output O _α does not contain the signal of the component C, and the weak adsorption output O _γ can chromatize the component A, further increasing the concentration of the component B at the strong adsorption output O _α , confirming The separation conditions of this example can indeed concentrate to increase the concentration of component B of O _α at the strongly adsorbed discharge.

It can be seen from the above that the method for separating the three-component mixture in the simulated moving bed of the present invention is to adjust the ratio of the flow rate of the adsorbent to the detergent in each region to concentrate the extract of the three-component mixture and improve The concentration of the extract in the product obtained from each of the discharge ports.

Therefore, the method for separating the three-component mixture by the simulated moving bed of the present invention does not need to first separate the component A of the strong adsorption force, thereby obtaining the component B of the medium adsorption force or the component C of the weak adsorption force, thereby achieving the shortening separation. The efficacy of the adsorption time or the operating time of the weakly adsorbing component among the three component mixtures.

The method for separating a three-component mixture in the simulated moving bed of the present invention can separate the adsorption force or the weak adsorption force component of the three-component mixture by using only a three-section simulated moving bed, and has the column required to be reduced. Quantity to reduce cost.

While the invention has been described in connection with the preferred embodiments described above, it is not intended to limit the scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims.

[this invention]

A, B, C. . . Ingredients

α. . . Alpha region

β. . . Beta region

γ. . . Gamma region

O _α . . . Strong adsorption discharge

I _γ . . . Mixture feed

O _γ . . . Weak adsorption discharge

S1. . . First section

S2. . . Second section

S3. . . Third section

C11, c12, c21, c22, c31, c32. . . Column

I1. . . First feed port

I2. . . Second feed port

I3. . . Third feed port

O1. . . First discharge port

O2. . . Second discharge port

O3. . . Third discharge port

P. . . Metering fluid pump

[知知]

A, B, C. . . Ingredients

α,1α,2α. . . Alpha region

,, 1β, 2β. . . Beta region

γ, 1γ, 2γ. . . Gamma region

δ, 1δ, 2δ. . . Delta region

O _α , O _1α , O _2α . . . Strong adsorption discharge

I _γ , I _1γ , I _2γ . . . Mixture feed

O _γ , O _1γ , O _2γ . . . Weak adsorption discharge

S91. . . First section

S92. . . Second section

S93. . . Third section

S94. . . Fourth section

I91, I92, I93, I94. . . Inlet

O91, O92, O93, O94. . . Outlet

Figure 1: A diagram showing the relative relationship between the discharge or feed of a set of four-section simulated moving beds and the area of the simulated moving bed.

Figure 2a: A schematic diagram of a set of four-segment simulated moving bed pipelines (first time t1).

Figure 2b: A schematic diagram of a set of four-segment simulated moving bed lines (second time t2).

Fig. 3: A diagram showing the relative relationship between the discharge point or the feed point of the two-group four-section simulated moving bed and the area of the simulated moving bed.

Figure 4: Schematic diagram of the pipeline configuration of the three-zone simulated moving bed of the present invention.

Fig. 5 is a diagram showing the relationship between the discharge point or the feed point of the three-zone simulated moving bed of the present invention and the area of the simulated moving bed.

Figure 6: Schematic diagram of the separation of the strong adsorption component A in a three-zone simulated moving bed.

Figure 7: Schematic diagram of the separation of the weakly adsorbing component C from a three-zone simulated moving bed.

Figure 8: Schematic diagram of the adsorption component B in the separation of the moving bed in a three-zone simulation.

Figure 9: HPLC chromatogram of Xiangru in this example.

Figure 10: HPLC chromatogram of each component of each discharge port of the first embodiment.

Figure 11: HPLC chromatogram of each component of each discharge port of the second embodiment.

α. . . Alpha region

β. . . Beta region

γ. . . Gamma region

O _α . . . Strong adsorption discharge

I _γ . . . Mixture feed

O _γ . . . Weak adsorption discharge

Claims (8)

A method for simulating a moving bed separation three-component mixture, the method comprising: (a) providing a three-zone simulated moving bed device, in sequence, a connected alpha, beta and gamma region, the alpha region having a strong end At the adsorption discharge, a gamma region is provided with a mixture feed at the front end, and a weak adsorption discharge is provided at the rear end of the γ region; (b) the three-zone simulated moving bed contains a sorbent, and a rinsing agent flows through The alpha, beta and gamma regions are in contact with the adsorbent, the alpha, beta and gamma regions respectively having a first flow rate ratio, a second flow rate ratio and a third flow rate ratio; and (c) feeding from the mixture The three-component mixture is injected into the three-zone simulated moving bed, and the three-component mixture comprises a strong adsorption component, a medium adsorption component and a weak adsorption component respectively with respect to the adsorbent, the strong adsorption force, The components of the adsorption force and the weak adsorption force respectively have a Henry adsorption constant Ka, Kb and Kc; (d) the three-component mixture is input into the three-section simulated moving bed device, and the first flow rate ratio is greater than the Henry adsorption Constant Ka The second flow rate ratio and the third flow rate ratio are less than the Henry's adsorption constant Kb and greater than the Henry's adsorption constant Kc, and the weakly adsorbing force component of the three-component mixture is concentrated by the gamma region and the weakly adsorbed material is discharged. The place was separated. According to the method for separating a three-component mixture by the simulated moving bed according to the first aspect of the patent application, the adsorbent and the detergent in each region respectively have a sorbent volume flow rate and a flush volume flow rate. The method for separating a three-component mixture by a simulated moving bed according to the second aspect of the patent application, wherein the flow rate ratio of each region is a ratio of a volume flow rate of the detergent in the respective regions to a volume flow rate of the adsorbent. The method for separating a three-component mixture by a simulated moving bed according to claim 1 of the patent application, wherein the strong or medium adsorbing component is concentrated by the α-region and separated at the strong adsorbed discharge. A method for simulating a moving bed separation three-component mixture, the method comprising: (a) providing a three-zone simulated moving bed device, in sequence, a connected alpha, beta and gamma region, the alpha region having a strong end At the adsorption discharge, a gamma region is provided with a mixture feed at the front end, and a weak adsorption discharge is provided at the rear end of the γ region; (b) the three-zone simulated moving bed contains a sorbent, and a rinsing agent flows through The alpha, beta and gamma regions are in contact with the adsorbent, the alpha, beta and gamma regions respectively having a first flow rate ratio, a second flow rate ratio and a third flow rate ratio; (c) from the mixture feed Injecting a three-component mixture into the three-zone simulated moving bed, the three-component mixture comprising a strong adsorption component, a medium adsorption component and a weak adsorption component respectively with respect to the adsorbent, the strong adsorption force and the medium adsorption The force and weak adsorption components respectively have a Henry adsorption constant Ka, Kb and Kc; and (d) a device for inputting the three component mixture into the three-section simulated moving bed, and the first flow rate ratio is greater than the Henry adsorption constant Kb and In the Henry adsorption constant Ka, the second flow rate ratio and the third flow rate ratio are less than the Henry adsorption constant Kb and greater than the Henry adsorption constant Kc, the adsorption component of the three component mixture is strongly influenced by the α region Concentrated and separated at the strong adsorption output. According to the method for simulating a moving bed separation three-component mixture according to the fourth aspect of the patent application, the adsorbent and the detergent in each region respectively have a sorbent volume flow rate and a flush volume flow rate. A method for separating a three-component mixture by a simulated moving bed according to claim 6 of the patent application, wherein the flow rate ratio of each zone is a ratio of a volume flow rate of the detergent in each zone to a volume flow rate of the adsorbent. The method for separating a three-component mixture by a simulated moving bed according to the fourth aspect of the patent application, wherein the weak adsorption component is concentrated by the gamma region and separated at the weak adsorption discharge.