JPS62293160A - Liquid chromatography - Google Patents

Abstract

PURPOSE:To concentrate an effluent which contains the objective component and is discharged from a liquid chromatograph and to prevent the deposition of the objective component by subjecting said effluent to a sepn. treatment by pervaporation having semipermable membrane. CONSTITUTION:A sample is developed in a column in which a packing material is packed and the effluent contg. the objective component is discharged therefrom. The effluent is fed through an objective component recovering line B to a pervaporization device 7. The semipermable membrane 8 is provided to the device 7 to segment the device to a liquid passage chamber 7 and a permeation chamber 7b. The chamber 7b is connected to a vacuum pump 12 to reduce the pressure in said chamber. The part of the solvent in the effluent is passed through the semipermable membrane 8 and is evaporated. The vapor is cooled 10 and is put into a container 11. On the other hand, the soln. in the chamber 7a is separated of the solvent and is, therefore, concd. The concn. soln. is stored in a container 9. The deposition of the objective component is prevented by adjusting the kind, sepn. conditions, etc. of the semipermable membrane 8 in such a manner that the effluent is not supersatd. Since the effluent is subjected to the pervaporation in the above-mentioned manner, the concn. of the effluent and the recovery of the solvent are executed.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a liquid chromatography method that improves the method of separating and treating an effluent such as an eluent from a liquid chromatography apparatus.

[Prior Art] As is well known in the liquid chromatography method,
Generally, a sample solution is passed through a column filled with a packing material, and a developing solution is passed through to develop the target component, and then an elution solvent is passed through to elute the target component from the packed column. .

When the elution solvent is a mixed solvent, it is common to use a distillation device as a separation device in the process of concentrating and recovering the target component from the solution, or in the process of recovering the solvent from the eluent. It was a target.

[Problems to be Solved by the Invention] However, when the molten liquid obtained by passing a mixed solvent through a column is distilled, the solvent is distilled off in sequence starting from the low boiling point solvent, and the composition of the concentrated liquid gradually changes. Precipitates often form in concentrated solutions. This precipitate causes problems such as making it difficult to take out the concentrated liquid and reducing heating efficiency.

This precipitation may be caused by, for example, low solubility in high-boiling solvents, or droplets of the concentrated liquid adhering to the vessel wall and undergoing concentration or drying, resulting in at least a partially supersaturated state. Primarily occurs.

[Means for Solving the Problems] In the present invention, a liquid effluent from liquid chromatography, such as an eluent, is separated by pervaporation.

[Working In a copper vaporization device, a solution containing a solute is passed through one side of a semipermeable membrane, and the other side is placed under reduced pressure. A portion of the solvent in the solution selectively passes through the membrane, reaches the other side, and is vaporized. On the other hand, on the one side, the solution is concentrated by the amount that has passed through the membrane and been separated, and becomes a concentrated liquid.

Note that the vaporized gas is cooled by a cooler and returned to a liquid, and becomes a recovered solvent.

In such separation by pervaporation, by selecting the concentration ratio, the liquid chromatography effluent can be concentrated under conditions that do not produce any supersaturation or deafness that would cause the precipitation of target components or impurities.・It is possible to separate and recover.

[Example] Examples of the present invention will be described in detail below with reference to a liquid chromatography apparatus shown in the drawings.

FIG. 4 is a system diagram of the main body of the liquid chromatography apparatus, in which a container 1 storing a mobile phase and a container 2 storing a stock solution can supply liquid to a column 5 via a valve 3 and a pump 4. It is connected.

This column 5 is filled with an appropriate packing material.

A detector 6 is connected to the liquid outflow side of the column 5, and the downstream line branches into a target component non-recovery line A and a target component recovery line B.

FIG. 1 shows a pervaporation processing system connected to these lines A and B, and includes a pervaporation device 7. As shown in FIG.

The pervaporation device 7 has a semipermeable membrane 8 inside, and this membrane 8 separates the liquid flow chamber 7a and the permeation chamber 7.
It is divided into b. The liquid flow chamber 7a is connected to the line A.
Or B is connected to the container 9 for storing concentrated liquid.

The permeation chamber 7b includes a cooler 10 and a container 1 for storing recovered solvent.
1 to a vacuum pump 12.

In such a configuration, when the eluent is introduced into the liquid distribution chamber 7a from line A or B and the vacuum pump 12 and cooler 11 are operated, the solvent in the solution flowing in the liquid distribution chamber 7a flows into the membrane 8. permeates and vaporizes and enters the permeation chamber 7b.

Since this permeation chamber 7b is placed in a reduced pressure state by the vacuum pump 12, the solvent that has entered the permeation chamber 7b is vaporized. The generated gas is cooled by the cooler 10 to become a condensed liquid, which is stored in the container 11.

On the other hand, the solution concentrated by separating a portion of the solvent in this manner is stored in the container 9 as a concentrated liquid.

In this way, the eluent fed from line A or B can be separated! ! It becomes possible to process, obtain a concentrated solution, or recover the solvent. In this separation process, by adjusting the type of semipermeable membrane, the rate of supply of liquid to the liquid distribution chamber 7a, the liquid temperature, or the degree of vacuum in the permeation chamber 7b, the liquid distribution chamber can be adjusted. The eluent flowing through 7a can be prevented from becoming supersaturated, and precipitation of target components and impurities can be reliably prevented in this separation and recovery process or concentration process.

FIG. 2 is a system diagram of different pervaporation processing systems. In the example shown in FIG. 2, line A or B is connected to a container 9 for storing concentrated liquid, and a pump 13 is used to circulate the liquid between this container 9 and the liquid distribution chamber 7a. . The rest of the structure is the same as that in FIG. 1, and the same members are given the same reference numerals and their explanations will be omitted.

In the system shown in Fig. 2, the liquid to be treated circulates and
Since it undergoes double pervaporation treatment, it is possible to increase the degree of concentration and increase the number of solvent recovery cycles.

FIG. 3 is a system diagram of yet another pervaporation processing system. In the system shown in FIG. 3, the eluent from line A or B is first fractionated in distillation device 14 and then introduced into pervaporation device 7. Therefore, in this system, the solvent L-
1 and solvent L recovered by pervaporation treatment
There are two types of recovery solvents: -2. In the system shown in FIG. 3, thermal efficiency can be improved by using a distillation device in combination. Note that in this system, the distillation operation and the pervaporation operation may be performed simultaneously.

In FIG. 3, reference numeral 15 indicates a condenser for liquefying the vapor from the distillation apparatus 14, and 14a indicates a heater of the distillation apparatus 14. The other configurations are the same as those shown in FIG. 1.2.

In this embodiment shown in FIG. 3, the concentrated liquid from the pervaporation device 7 is returned to the distillation device 14 and repeatedly subjected to pervaporation treatment to achieve high concentration. The concentrated liquid from step 7 may be directly taken out of the system as a concentrated liquid.

In the above description, an eluent is used as the liquid to be treated, but various types of effluents from a liquid chromatography column, such as a stock solution and a developing solution, can be treated in the same manner as described above.

Specific examples will be described below.

Example 1 A liquid chromatography apparatus having the configuration shown in FIG. 4 was used to perform liquid chromatography on the stock solution (2) below to obtain the eluent (2) below. In addition, the column,
The motion phase and detector are as shown in (■) to (■) below. Furthermore, a chromatogram during elution is shown in FIG. (In the following explanation, MeOH indicates methanol.) ■Column: 20mmφX 1000100O SUS
Chemically bonded silica gel (CLB) particle size 40-6 in column
Filled with 180g of 61.

■Mobile phase: MeO) 1/) 120-70/30, flow rate 40mJ! /win ■ Detector: Ultraviolet absorbance meter (used wavelength 245 mm) ■ Stock solution: 70% MeO containing 2117V% of MeOH-soluble antibiotics (component B) with a purity of 65%
200 mfL of H solution.

(2) Eluent: The elution fraction (x) from 35 to 80 minutes in the chromatogram in Figure 5, 1800 mJ2 was collected.

The eluate thus obtained was concentrated according to the system shown in FIG.

That is, as a semipermeable membrane, M e OH/H20 = 70
Separation coefficient (H20 transmittance/M
Using a PMLG film (poly(γ-methyl)-glutamate film) with an OH transmittance of 1.96 to 1.76,
The fractions were pervaporatively concentrated. Meal (concentration increased with concentration and was concentrated to 20 times (90 ml), but no precipitate was observed. At this time, the MeOH concentration of the concentrated solution was 9.
It was 5%.

Comparative Example The X fraction of the same eluent as that treated in Example 1 was heated at 30°C and 85 torr using a rotary concentrator
It was concentrated under reduced pressure. When concentrated to 1250 mλ, dissolved components precipitated and adhered to the wall of the concentrator. M at this time
The eOH concentration was 60%. Further concentrate to 900ml
However, the amount of precipitation also increased. To recover the precipitated components, MeOH was added to dissolve them, and the mixture was taken out from the concentrator.

[Effect] As is clear from the above Examples and Comparative Examples, according to the present invention, it is possible to concentrate the liquid chromatography effluent and recover the solvent while preventing the precipitation of dissolved components.

Therefore, it is possible to obtain a concentrated liquid having a high flA concentration and to improve the solvent recovery efficiency very easily.

[Brief explanation of the drawing]

Figures 1, 2, and 3 are system diagrams showing the configuration of the pervaporation processing apparatus, Figure 4 is a system diagram showing the configuration of the liquid chromatography apparatus main body, and Figure 5 is the system diagram showing the configuration of the liquid chromatography apparatus. Gram. 5... Column, 6... Detector, 7...
・Pervaporation device, 10... Cooler, 12... Vacuum pump,
14... Distillation device. Agent Patent Attorney Tsuyoshi Shigeno Figure 1 Figure 3

Claims (4)

[Claims] (1) A liquid chromatography method characterized in that an effluent discharged from a liquid chromatography device is separated by pervaporation. (2) After distilling the effluent to remove some of the solvent,
2. The liquid chromatography method according to claim 1, wherein the remaining liquid is separated by pervaporation. (3) The liquid chromatography method according to claim 1 or 2, wherein the effluent is an eluent. (4) The liquid chromatography method according to claim 3, wherein the eluent contains a target component.