KR100282136B1 - Continuous Reciprocating Size Exclusion Chromatography System and Separation Method of Polymeric Material Using the Same - Google Patents

Abstract

The present invention storage 10; Forward pump 31 which provides a driving force for introducing the mixed solution to be separated in the electric reservoir 10 into the size exclusion chromatography column 40, and the solenoid valve 21 for controlling the flow direction of the driven fluid thereby ; A size exclusion chromatography column 40 for separating the mixed solution coming from the reservoir 10 by driving the electric forward pump 31 and adjusting the solenoid valve 21; A solenoid valve 22 for adjusting the flow direction of the fluid flowing out of the electrosizing chromatography column 40 and a reverse pump 32 for providing a reverse driving force of the fluid; Separation vessels 51 and 52 for recovering the separated polymer material and the pure solvent through the control of the electric solenoid valve 22; And a programmable timer for controlling the operation of the electric solenoid valves 21, 22, the forward pump 31 and the reverse pump 32, and separation of the polymeric material using the same. It is about a method. According to the continuous reciprocating size exclusion chromatography system according to the present invention, not only is it possible to continuously separate purely polymer material, but also a large amount of separation is very useful for industrial scale separation process.

Description

Continuous Reciprocating Size Exclusion Chromatography System and Separation Method of Polymeric Material Using the Same

The present invention relates to a continuous reciprocating size exclusion chromatography system and a method for separating the polymer material using the same. More specifically, the present invention relates to a continuous reciprocating size exclusion chromatography system for separating a large amount of polymer material by a shear method and a method of separating the polymer material using the same.

In general, the method of separating the low molecular weight material and the high molecular material in the mixed solution uses the principle of size-exclusion. Separation methods using the principle of size exclusion include membrane separation and size exclusion chromatography.

Among them, membrane separation methods include, for example, reverse osmosis, nano-filtration, ultrafiltration, and microfiltration depending on the size of low molecular weight molecules having a low molecular weight. There is such a membrane separation method, it is possible to mainly separate the low molecular weight low molecular weight material in a pure state. However, when such a membrane separation method is used, it is difficult to purely separate these high molecular materials because the high molecular weight materials are always present in the residual liquid together with the low molecular weight materials having a low molecular weight. Of course, it is possible to ultimately be purely separated by a diafiltration method of supplying a solvent to the mother liquor, but there is a problem that an inefficient repeated filtration process is required for this purpose.

Therefore, in the case of purely separating a high molecular weight material having a high molecular weight for the foregoing reasons, in particular, a size exclusion chromatography method, in which size exclusion is a separation mechanism, is mainly used. The size exclusion chromatography method is further divided into an eluting method and a shearing method. Elution size exclusion chromatography is a method in which a mixture of mother liquor, which is supplied in a pulse form, is transferred and separated along a chromatography tube, forming peaks. This separation method is mainly used in the analysis of samples in which a small amount of mother liquor is used, and there is a problem that is not suitable for large-scale material separation due to the nature of the operation method.

Another method for separating polymers is shear size-exclusion chromatography, which supplies mother liquor in a step form, which forms a front and moves along the chromatography tube. It is separated. In this example, the adsorption method is a method of separating the substances according to the difference in the degree of adsorption of the substances to the adsorbent packed in the column, a representative example is the separation of water and alcohol by activated carbon (see Fig. 1b). The shear-sized chromatographic separation method can be used to process a large amount of mother liquor, and the eluting separation method can be used in an industrial scale that requires a large amount of separation, compared to that mainly used for analyzing samples. have.

However, these size exclusion chromatography methods suffer from the problem of batch size exclusion chromatography methods. Therefore, this batch size exclusion chromatography method has been inadequate for industrial use, especially when the amount of the important mother liquor is large, and there is an urgent need for improvement.

Therefore, the present inventors have made diligent efforts to solve the problems of the above-described size exclusion chromatography of the shear method, and as a result, by improving the size exclusion chromatography, which was a conventional batch type, to the size of the continuous reciprocation exclusion chromatography, It was confirmed that only a polymeric material can be separated more efficiently and neatly with respect to a large amount of mother liquor, and the present invention was completed.

After all, the main object of the present invention is to provide a continuous reciprocating size exclusion chromatography system for separating large quantities of polymeric material by shearing.

Another object of the present invention is to provide a method for separating a polymer material using an electrically continuous reciprocating size exclusion chromatography system.

Figure 1a is a graph showing the elution separation form of the conventional technique of size exclusion chromatography.

Figure 1b is a graph showing the shear separation of the conventional operating method of size exclusion chromatography.

2 is a schematic diagram schematically showing the main components of a continuous reciprocating size exclusion chromatography system according to the present invention.

Figure 3 is a graph showing the shear elution characteristics of continuous reciprocating size exclusion chromatography using nickel nitrate and bluedextran.

4 is a graph showing the recovery rate of bluedextran by a continuous reciprocating chromatography method in a mixed solution of nickel nitrate and bluedextran.

Brief description of the main parts of the drawing

10: reservoir 21, 22: solenoid valve

31: forward pump 32: reverse pump

40: size exclusion chromatography column 51, 52: separation vessel

Hereinafter, with reference to the accompanying drawings, the configuration of the continuous reciprocating size exclusion chromatography system of the present invention will be described in detail.

2 is a schematic diagram schematically showing the main components of the continuous reciprocating size exclusion chromatography system according to the present invention.

Continuous reciprocating size exclusion chromatography system of the present invention is a reservoir (10); Forward pump 31 which provides a driving force for introducing the mixed solution to be separated in the electric reservoir 10 into the size exclusion chromatography column 40, and the solenoid valve 21 for controlling the flow direction of the driven fluid thereby ; A size exclusion chromatography column 40 for separating the mixed solution coming from the reservoir 10 by driving the electric forward pump 31 and adjusting the solenoid valve 21; A solenoid valve 22 for adjusting the flow direction of the fluid flowing out of the electrosizing chromatography column 40 and a reverse pump 32 for providing a reverse driving force of the fluid; Separation vessels 52 and 51 for recovering the pure solvent and the polymer material separated through the control of the electric solenoid valve 22; And a timer (not shown) programmed to regulate the operation of the electric solenoid valves 21, 22 and the forward pump 31 and the reverse pump 32.

Herein, the size exclusion chromatography column 40 is filled with a size exclusion resin therein, and a plunger is mounted at the inlet and the outlet to press the filled resin. In this case, the size exclusion resin is a size exclusion resin commercially available in the art, that is, Sephadex (Pharmacia, Sweden), Bio-Gel P (Bio-Rad, USA) It is possible to use a resin such as), and select and use according to the size of the material to be separated.

In addition, since the solenoid valve used in the present invention does not reciprocate by the accurate timetable based on the retention volume, the recovery rate of the polymer material may be slowed or conversely, the low molecular material may contaminate the polymer material. In order to ensure accurate transfer of system fluids, a multi-directional solenoid valve may also be used.

The principle of the continuous reciprocating size exclusion chromatography system according to the present invention and a method of separating the polymer material using the same will be described in more detail.

Step 1: Forward Flow of Mixed Solution

First, the size exclusion chromatography is filled with a size exclusion resin of a mixed solution made of a low molecular material and a high molecular material stored in the reservoir 10 by controlling the solenoid valve 21 and driving the forward pump 31. Forward flow into the graphics column 40. In this way, the mixed solution introduced into the column forms a front of the polymer material in the column, so that only the polymer material passes through the column at a higher speed than the low molecular material, and flows out of the column prior to the low molecular material.

Second Step: Primary Separation of Polymeric Materials

A portion of the pure solvent is preferentially flowed out before the polymer material that forms the shear in the column in the electrical phase is first collected. The pure solvent is first collected in one separation vessel 52, and the polymer material is separated into another separation vessel ( To 51).

Step 3: Reverse Reflow of Pure Solvent

The solenoid valve 22 is adjusted again by adjusting a timer (not shown) which is already programmed immediately before the separation of the electric phase and the solution of the polymer material and the low molecular material is flowed out, and the reverse pump 32 In the second step, the flow of the eluent in the column is reversed by using a pure solvent in the separation container 52 collected separately before starting the outflow of the polymer material in the second step, and then reintroduced into the size exclusion chromatography column 40, By adjusting the solenoid valve 21 is to back feed into the reservoir (10).

Step 4: Re-Separation of Polymeric Material by Reciprocating Stroke

The mixed solution re-introduced in the reverse direction in the previous step is stored in the reservoir 10 again, the mixed solution in the reservoir 10 is introduced into the column again to be separated into a high molecular material and a low molecular material. That is, the flow of the mixed solution is changed to the forward direction again by the operation of the solenoid valve 21 and the forward pump 31 in accordance with the adjustment of the time programmed in the timer as in the first electrical step, and the size exclusion chromatography column 40 The first to third steps are repeated several times to collect only the liquid containing the polymer material by passing through). By repeating the electric stroke several times, it is possible to purely separate and recover the pure polymer material from the mixed solution.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention, it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples.

Example: Continuous Separation by Reciprocating Chromatography

Size Exclusion Chromatography using Sephadex G-200 (Pharmacia, Sweden) as size exclusion resin and bluedextran and nickel nitrate with molecular weight of 2,000,000 and 291 as polymer and low molecular weight, respectively Was carried out to separate the polymer material. As a result, as shown in Figure 3, it was confirmed that the blue dextran (-) and nickel nitrate (...) is separated by forming a shear, and after about 20 minutes after the blue dextran began to flow out, the nickel nitrate The rate began to elute, indicating a difference of about 20 minutes. Therefore, it was confirmed that only bluedextran having a high molecular weight could be selectively separated by recovering the solution from the time when bluedextran began to flow out until just before the nickel nitrate flowed out. The polymer material was separated by seven round trip strokes using the round trip chromatography system of the present invention. The results of the first round trip to the seventh round trip strokes are summarized as a graph in FIG. 4, respectively. As shown in FIG. 4, the blue dextran in the reservoir of the first round trip stroke was separated and recovered only about 15%, while the result of the seven round trip stroke was separated by 75% and recovered as a pure polymer solution. Nickel nitrate was maintained at a constant concentration in the reservoir. In FIG. 4, (-●-) indicates the amount of bluedextran in the reservoir, (-○-) indicates the amount of nickel nitrate in the reservoir, and (-▼-) indicates the amount of bluedextran in the separated solution. (-I-) indicates the amount of nickel nitrate in the separated solution. As a result, it was possible to purely separate and recover the polymer material from the mixture by a shearing cyclic reciprocating size exclusion chromatography technique.

As described and demonstrated in detail above, the present invention provides a continuous reciprocating size exclusion chromatography system and a method for separating a polymer material using the same. According to the continuous reciprocating size exclusion chromatography system according to the present invention, not only is it possible to continuously separate purely polymer material, but also a large amount of separation is very useful for industrial scale separation process.

Claims (2)

Storage 10; Forward pump 31 which provides a driving force for introducing the mixed solution to be separated in the electric reservoir 10 into the size exclusion chromatography column 40, and the solenoid valve 21 for controlling the flow direction of the driven fluid thereby ; A size exclusion chromatography column 40 for separating the mixed solution coming from the reservoir 10 by driving the electric forward pump 31 and adjusting the solenoid valve 21; A solenoid valve 22 for adjusting the flow direction of the fluid flowing out of the electrosizing chromatography column 40 and a reverse pump 32 for providing a reverse driving force of the fluid; Separation vessels 52 and 51 for recovering the pure solvent and the polymer material separated through the control of the electric solenoid valve 22; And, Continuous reciprocating size exclusion chromatography system comprising an electric solenoid valve (21, 22) and a timer programmed to regulate the operation of the forward pump (31) and the reverse pump (32). (Iii) a forward inflow step in which the mixed solution to be separated from the reservoir 10 is introduced into the size exclusion chromatography column 40 through the operation of the forward pump 31 and the adjustment of the solenoid valve 21; (Ii) collecting the pure solvent and the polymer material in the mixed solution discharged from the electrosizing chromatography column 40 into the separation vessel 52 and the separation vessel 51 through the control of the solenoid valve 22; (Iii) the size exclusion chromatography column by controlling the solenoid valve 22 adjusted by a programmable timer for the pure solvent in the separation vessel 52 in which the pure solvent has been collected in the past and driving the reverse pump 32 A reverse inlet step of reintroduction into 40); And, (Iii) repeating steps (iii) to (iii) at time intervals adjusted by a programmable timer using a mixed solution in a reservoir 10 containing pure solvent reflowed in the reverse direction from electricity Separation method of a polymeric material by a continuous reciprocating size exclusion chromatography system comprising a.