JP2007120972A - Supercritical system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a supercritical system capable of efficiently recovering an elution sample. <P>SOLUTION: The supercritical system 10 is equipped with a liquid sending part 12 for sending a supercritical fluid in the system as a solvent fluid, a sample introducing part 14 for introducing a sample into the solvent fluid from the liquid sending part 12, the separation and detection part 16 provided on the downstream side of the sample introducing part 14 and separating the sample into components to detect the target component in the sample, a back pressure adjusting part 18 provided on the downstream side of the separation and detection part 16 for adjusting the pressure of the fluid between the liquid sending part 12 and the back pressure adjusting part 18, a temperature adjusting part 20 for adjusting the temperature of the fluid from the back pressure adjusting part 18, a valve 22 for selecting the fluid containing the target component in the sample in the fluid from the temperature adjusting part 20 and a demarcation recovery container 24 for recovering the fluid containing the target component in the sample in the fluid from the valve 22. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a supercritical system, and more particularly to an improved eluting sample collection mechanism.

  In recent years, supercritical chromatographs and supercritical extraction have been widely used from scientific research to industrial fields (see, for example, Patent Document 1). In particular, carbon dioxide supercritical chromatography using carbon dioxide as a supercritical fluid and carbon dioxide supercritical extraction have the following merits.

(1) Since the critical point temperature is 31.2 degrees C and the critical point pressure is 7.34 MPa, which is a low temperature and low pressure, it can be easily realized.
(2) Since the diffusion coefficient is large, diffusion into the sample is fast and efficient extraction can be performed.
(3) When considered as an elution solvent, the supercritical fluid characteristics can be controlled by pressure and temperature control, so that it can be applied to many applications using only carbon dioxide.
(4) Supercritical carbon dioxide exhibits the same characteristics as a nonpolar organic solvent. Carbon dioxide is less expensive than these organic solvents.
(5) Since it is non-toxic, no special consideration is required.
(6) Gas at normal temperature and pressure. Removal of the organic solvent generated by organic solvent elution is omitted or facilitated.

Supercritical chromatographs and supercritical extractions are expected to be used in various fields in the medical, agrochemical, and semiconductor-related industries using these characteristics.
Japanese Patent Publication No. 5-25305

However, although there is still room for improvement in the recovery efficiency of the eluted sample even in the conventional method, there has been no appropriate technique that can solve this.
The present invention has been made in view of the above-described problems of the prior art, and an object thereof is to provide a supercritical system that can efficiently recover an eluted sample.

<Invention according to Claim 1>
In order to achieve the above object, a supercritical system according to the present invention includes a liquid feeding unit, a sample introduction unit, a separation detection unit, a back pressure adjustment unit, a temperature adjustment unit, a valve, a fraction collection container, It is characterized by providing.
Here, the liquid feeding section feeds a supercritical fluid or, if desired, a supercritical fluid and a modifier solvent into the system as a solvent fluid.
The sample introduction unit is provided downstream of the liquid feeding unit, and introduces the sample into the solvent fluid.
The separation detection unit is provided downstream of the sample introduction unit, has a temperature higher than a critical temperature of the fluid and higher than a critical pressure, and is under a temperature condition and a pressure condition optimal for fractionation of the sample by the solvent fluid. The sample in the fluid is separated into components, and the target component in the sample is detected.
The upstream back pressure adjustment unit is provided downstream of the separation detection unit, and adjusts the pressure of the fluid between the upstream and the liquid feeding unit within a range that is optimal for the separation of the target component in the sample.
The temperature adjusting unit is provided downstream of the upstream back pressure adjusting unit, and adjusts the temperature of the fluid from the upstream back pressure adjusting unit within a range that is optimal for the separation of the target component in the sample.
The valve is provided downstream of the temperature adjustment unit, and the target component in the sample in the separation detection unit is capable of separating a fluid containing the target component in the sample from the fluid from the temperature adjustment unit. The flow path between the temperature adjusting unit and the downstream is switched in accordance with the detection result.
The fraction collection container is provided downstream of the valve and collects a fluid containing the target component in the sample from the valve under a pressure condition and a temperature condition optimal for the separation of the target component in the sample. To do.

Examples of the supercritical system of the present invention include a supercritical chromatograph and a supercritical extraction device.
Examples of the supercritical fluid of the present invention include water and carbon dioxide.
Supercritical here means supercritical and subcritical.

In the present invention, the following temperature and pressure conditions are very preferable for supercritical carbon dioxide for further efficient recovery of the eluted sample.
(1) Temperature at the separation detection unit: 0 to 120 ° C., Pressure at the separation detection unit: 7 to 35 MPa (2) Temperature at the upstream back pressure adjustment unit: 20 to 120 ° C., the upstream back Pressure at the pressure adjusting unit: 7 to 35 MPa
(3) Temperature at the temperature adjusting unit: 20 to 100 ° C., pressure at the temperature adjusting unit: 1 to 10 MPa
(4) Temperature in the fraction collection container: 0 to 100 ° C., Pressure in the fraction collection container: atmospheric pressure to 7 MPa

<Invention according to Claim 2>
In addition, in this invention, it is suitable to provide a gas-liquid separator.
Here, the gas-liquid separator is provided between the valve and the fraction collection container, and separates the fluid from the valve into a gas component and a liquid component.

<Invention according to claim 3>
Moreover, in this invention, it is suitable to provide a heater.
Here, the heater is provided in the gas-liquid separator, and is supplied from the valve so as to have a desired constant temperature determined based on an optimum temperature for collecting the target component in the sample in the fraction collection container. Adjust the fluid temperature.

<Invention according to claim 4>
In the present invention, the gas-liquid separator includes a separator body and an inert substance. The separator body has a liquid outlet at the bottom of the hollow body and a gas outlet at the top of the hollow body. The inert substance is provided in a state where the pipe from the valve is embedded in the separator main body, and is in a fibrous or porous state inert to the fluid from the valve. The gas-liquid separator is configured to bring a fluid from the valve into contact with the inert substance, drop a liquid component of the fluid from the liquid outlet of the separator main body to the fraction collection container, and gas from the fluid. It is preferable that the components are discharged from the gas outlet of the separator main body to the outside of the gas-liquid separator.

<Invention according to claim 5>
In the present invention, the gas-liquid separator includes an outer cylindrical tube and an inner cylindrical tube. The outer cylindrical tube has a fluid inlet at the top and a liquid accumulation portion at the bottom. The inner cylindrical tube is provided with a gap between it and the inner peripheral wall of the outer cylindrical tube, and has a gas outlet at the lower part. In the gas-liquid separator, the fluid from the valve flows into the space between the outer peripheral wall of the outer cylindrical tube and the outer peripheral wall of the inner cylindrical tube while spirally rotating, and the fluid from the valve is caused by centrifugal force. Among them, the liquid component contacts the inner peripheral wall of the outer cylindrical tube, falls down along the inner peripheral wall of the outer cylindrical tube, and is collected in the liquid accumulation portion at the lower portion of the outer cylindrical tube, and the fraction is separated through the liquid accumulation portion. Drip into the collection container. Further, it is preferable that the gas component from which the liquid component has been removed is discharged from the gas discharge port at the lower part of the inner cylindrical tube to the outside of the gas-liquid separator.

<Invention of Claim 6>
In the present invention, the outer cylindrical tube is provided with a fluid guide including a spiral groove on an inner peripheral wall thereof. It is preferable that the fluid from the valve flows along the fluid guide on the inner peripheral wall of the outer cylindrical tube.

<Invention of Claim 7>
In the present invention, the valve includes an upstream valve and a downstream valve. The upstream valve is provided upstream of the fraction collection container. The downstream valve is provided downstream of the fraction collection container. In the present invention, a gas-liquid separation mechanism is provided. The gas-liquid separation mechanism separates the fluid from the upstream valve into a gas component and a liquid component. The gas-liquid separation mechanism includes the fraction collection container, the upstream valve and the downstream valve, and a downstream back pressure adjusting unit. The fraction collection container has high pressure resistance. The downstream back pressure adjusting unit is provided downstream of the downstream valve, and is used for bringing the pressure in the fraction collection container into a desired constant pressure state. The gas-liquid separation mechanism includes the upstream valve and the downstream valve so that the upstream valve, the desired fraction collection container, the downstream valve, and the downstream back pressure adjusting unit are in a conductive state. Are switched in synchronization with each other, and the desired fraction collection container is brought into a desired constant pressure state, whereby the fluid from the upstream valve is dropped into the desired fraction collection container, and the gas in the fluid is It is preferable to discharge the components from the upper part of the fraction collection container to the outside of the fraction collection container, and further through the downstream valve and the downstream back pressure adjusting unit.

<Invention of Claim 8>
In the present invention, it is preferable to provide a high-pressure stop valve.
Here, the high-pressure stop valve is provided in the fraction collection container and discharges the liquid component collected in the fraction collection container to the outside.

<Invention of Claim 9>
In the present invention, it is preferable to provide a sealed chamber.
Here, at least the valve and the fraction collection container are placed in the sealed chamber, and the periphery thereof is a sealed space.
Here, at least the valve and the fraction collection container are put in, that at least the valve and the fraction collection container are put in a sealed chamber,
At least the upstream valve, the fraction collection container and the downstream valve are placed in a sealed chamber;
It includes that at least the upstream valve, the fraction collection container, the downstream valve, and the high-pressure stop valve are placed in a sealed chamber.

<Invention according to claim 10>
In the present invention, the liquid feeding section includes a plurality of fluid cylinders for the supercritical fluid and a cylinder automatic switching mechanism. The cylinder automatic switching mechanism sequentially switches the fluid cylinders to be the fluid derivation target so that the fluid is continuously supplied to the system downstream from the fluid cylinder to be the fluid derivation target among the plurality of fluid cylinders. The cylinder automatic switching mechanism preferably includes a stop valve, a junction, and a cylinder switching control means.
Here, the stop valve is provided for each of the fluid cylinders, and the flow path from each of the fluid cylinders is brought into a conduction state or a cutoff state.
The junction unit joins the flow paths from the fluid cylinders downstream of the system.
The cylinder switching control means opens and closes each stop valve according to the remaining amount of each fluid cylinder, and fluid is continuously downstream from a fluid cylinder that is one of the plurality of fluid cylinders to which fluid is derived. In order to be supplied, the fluid cylinders to be fluid-derived are sequentially switched.

  According to the supercritical system of the present invention, the temperature adjustment unit is provided downstream of the upstream back pressure adjustment unit based on the discovery of the optimum temperature condition and pressure condition for the supercritical system. Can be recovered automatically.

In the present invention, by providing a gas-liquid separator (mechanism), the eluted sample can be collected more efficiently.
In the present invention, the elution sample can be collected more efficiently by providing a heater in the gas-liquid separator.

  In the present invention, the gas-liquid separator performs gas-liquid separation using contact with an inert substance, whereby the eluted sample can be recovered more efficiently.

Moreover, in this invention, a gas-liquid separator can collect | recover an elution sample still more efficiently by performing a gas-liquid separation using a centrifugal force.
Here, in the present invention, the elution sample is collected by providing a fluid guide including a spiral groove on the inner peripheral wall of the outer cylindrical tube of the gas-liquid separator that performs gas-liquid separation using the centrifugal force. Can be done more efficiently.

In the present invention, the elution sample can be collected more efficiently by pressurizing the fraction collection container to perform gas-liquid separation.
In the present invention, the elution sample can be collected more efficiently by providing a high-pressure stop valve at the lower part of the fraction collection container.

In the present invention, the elution sample can be collected more efficiently by placing at least the valve and the fraction collection container in the sealed chamber.
In the present invention, the elution sample can be collected more efficiently by providing the liquid feeding unit with the cylinder automatic switching mechanism.

FIG. 1 shows a schematic configuration of a supercritical system according to an embodiment of the present invention.
A supercritical carbon dioxide chromatograph (supercritical system) 10 shown in FIG. 1 includes a liquid feeding unit 12, a sample introduction unit 14, a separation detection unit 16, an upstream back pressure adjustment unit 18, a temperature adjustment unit 20, and the like. , A valve 22 and a fraction collection container 24.

  The liquid feeding unit 12 includes, for example, a carbon dioxide cylinder 26, a carbon dioxide pump 30 with a cooler 28, and a stop valve 32. The liquid feeding unit 12 includes a modifier solvent tank 34, a modifier pump 36, and a stop valve 32. The liquid feeding unit 12 includes a mixer 38 and a preheat coil 40.

The sample introduction unit 14 includes an injector 42 and a syringe pump 44.
The separation detection unit 16 includes a column oven 46, a column 48, and a detector 50.
The upstream back pressure adjustment unit 18 includes an automatic back pressure adjustment valve 19.
The temperature adjustment unit 20 includes a heating heater (hereinafter referred to as the heating heater 20).
The valve 22 includes a flow path distribution valve such as a six-way valve (hereinafter referred to as a flow path distribution valve 22).
The fraction collection container 24 includes a collection bottle (hereinafter referred to as a collection bottle 24).

Here, the liquid feeding unit 12 sends carbon dioxide (supercritical fluid) or, if desired, carbon dioxide (supercritical fluid) and a modifier solvent as a solvent fluid to the system.
The sample introduction unit 14 is provided downstream of the liquid feeding unit 12 and introduces the sample into the solvent fluid.
The separation detection unit 16 is provided downstream of the sample introduction unit 14, has a temperature condition that is not less than the critical temperature of the carbon dioxide (supercritical fluid) and not less than the critical pressure, and is optimal for fractionation of the sample by the solvent fluid, and Under pressure conditions, the sample in the solvent fluid is separated into components, and the target component in the sample is detected.
The automatic back pressure adjustment valve 19 is provided downstream of the separation detection unit 16, and the pressure of the fluid between the liquid feeding unit 12 and the automatic back pressure adjustment valve 19 is within an optimum range for separating the target component in the sample. adjust.

The warming heater 20 is provided downstream of the automatic back pressure adjustment valve 19, and adjusts the temperature of the fluid from the automatic back pressure adjustment valve 19 within a range optimal for the separation of the target component in the sample.
The flow path distribution valve 22 is provided downstream of the heating heater 20 so that the fluid including the target component in the sample can be separated from the fluid from the heating heater 20. The flow path between the heating heater 20 and the desired fraction collection container 24 is switched according to the detection result of the target component in the sample.
The fraction collection container 24 is provided downstream of the flow path distribution valve 22, and the target medium in the sample out of the fluid from the flow path distribution valve 22 under the optimum pressure and temperature conditions for separating the target component in the sample. Collect the fluid containing the components.

In the present embodiment, the automatic back pressure adjusting valve 19 and the heating heater 20 are connected by a connecting valve 52 between the adjusting valve and the heater.
In the present embodiment, the heater 20 and the flow distribution valve 22 are connected by a heater / valve connection pipe 54.
In the present embodiment, the flow path distribution valve 22 includes ports A, B, C, D, E, and F. The flow path distribution valve 22 connects the port A to the heater and inter-valve connection pipe 54. Further, the flow path distribution valve 22 conducts the port F to the atmosphere. The flow path distribution valve 22 conducts between the ports A and B, between the ports A and C, between the ports A and D, between the ports A and E, or between the ports A and F. The flow path distribution valve 22 and the collection bottle 24 are connected by a valve and inter-container connection pipe 56.

  In the present embodiment, a gas-liquid separator 58 is provided between the flow path distribution valve 22 and the collection bottle 24. The gas-liquid separator 58 is preferably further provided with a heating heater 60.

  In this embodiment, even if mist-like elution solvent or gas leaks to the outside from the gas-liquid separator 58 and the recovery bottle 24, the flow path distribution valve 22 and the recovery bottle 24 are provided to prevent them from leaking to the outside. It is placed in a sealed chamber 62.

  In the present embodiment, a computer 64 that controls the operation of the supercritical carbon dioxide chromatograph 10 is provided. The computer 64 controls, for example, liquid feeding control of the liquid feeding unit 12, operation control of the sample introduction unit 14, processing of data from the separation detection unit 16, and flow of the flow path distribution valve 22 based on measurement results obtained by the data processing. The path switching control, the pressure control of the automatic back pressure adjustment valve 19, the temperature control of the heating heater 20, etc. are performed.

By the way, the carbon dioxide pressure is about 7-30 MPa upstream of the automatic back pressure adjustment valve 19, but becomes atmospheric pressure (0.1 MPa) downstream of the automatic back pressure adjustment valve 19.
Downstream of the automatic back pressure regulating valve 19, when the supercritical carbon dioxide drops to normal pressure, 1 mL of liquid carbon dioxide becomes 500 mL of carbon dioxide gas, so that the volume expands about 500 times. At the same time, adiabatic expansion occurs and the temperature drops rapidly. These rapid temperature and volume changes after the automatic back pressure regulating valve 19 are a major obstacle when recovering the eluted sample.
Many types of HPLC fraction collectors are commercially available, but none of them are compatible with carbon dioxide supercritical chromatographs or carbon dioxide supercritical extraction devices. There was no.

On the other hand, in the carbon dioxide supercritical chromatograph and the carbon dioxide supercritical extraction apparatus of this embodiment, in order to efficiently recover the eluted sample, appropriate pressure conditions and temperature conditions are set according to the elution conditions. ing.
In the present embodiment, in order to further efficiently recover the eluted sample, it is highly preferable that the computer 64 has the following temperature and pressure conditions for supercritical carbon dioxide.
(1) Temperature at the separation detection unit 16: 0 to 120 ° C., pressure at the separation detection unit 16: 7 to 35 MPa
(2) Temperature at the automatic back pressure regulating valve 19: 20 to 120 ° C., pressure at the automatic back pressure regulating valve 19: 7 to 35 MPa
(3) Temperature at the heating heater 20: 20 to 100 ° C., pressure at the heating heater 20: 1 to 10 MPa
(4) Temperature in the recovery bottle 24: 0 to 100 ° C., pressure in the recovery bottle 24: atmospheric pressure to 7 MPa

  Thus, in this embodiment, in the carbon dioxide supercritical chromatograph or the carbon dioxide supercritical extraction apparatus, the recovery rate of the target component in the sample can be improved by automatically setting the appropriate temperature and back pressure according to the elution conditions. improves. In addition, there is no contamination at the time of sample collection, and the target component in the sample can be collected more efficiently.

  Further, in the present embodiment, since the computer 64 can change the pressure and create appropriate elution conditions for the target substance, the target substance can be more efficiently separated.

  Furthermore, in the present embodiment, the computer 64 can separate the target component more favorably by sending the modifier solvent from the modifier solvent tank 34 via the modifier pump 36 as necessary. it can.

Below, the said effect | action is demonstrated more concretely.
That is, carbon dioxide led out from the carbon dioxide cylinder 26 through the pipe 63 is supplied to the heat exchanger of the carbon dioxide pump 30.
The heat exchanger is connected to a circulating constant temperature cooler 28. In order to sufficiently cool carbon dioxide, a copper pipe wound in a coil shape is installed in a refrigerant tank in the circulating thermostatic cooler 28 and carbon dioxide is allowed to pass through the coil. It may be useful in preparative applications where the carbon dioxide flow rate is high. The refrigerant cooled by the circulating constant temperature cooler 28 exchanges heat with carbon dioxide in the heat exchanger, and the carbon dioxide is cooled to about −10 degrees to become complete liquid carbon dioxide. The sufficiently cooled carbon dioxide is introduced into the liquid feeding head portion of the carbon dioxide pump 30 and fed at a high pressure.

On the other hand, with supercritical carbon dioxide alone, variations in the separation conditions cannot be changed greatly, so an organic solvent of up to about 50% of the supercritical carbon dioxide flow rate is simultaneously sent as a modifier solvent, and the supercritical carbon dioxide is sent. A mixed solvent of carbon dioxide and an organic solvent can also be used as a developing solvent for the chromatograph.
The modifier solvent is fed by the modifier solvent pump 36 and mixed by the mixer 38. Stop valves 32a and 32b are installed between the carbon dioxide pump 30 and the mixer 38 and between the modifier solvent pump 36 and the mixer 38, respectively, to enhance convenience during system maintenance. The mixed solvent mixed by the mixer 38 reaches the injector 42 via the preheat coil 40.

The preheat coil 40 is used to bring the liquid carbon dioxide cooled by the circulating constant temperature cooler 28 to a temperature suitable for chromatographic development. The computer 64 adjusts the temperature of the fluid so that the fluid temperature after passing through the preheat coil 40 substantially matches the temperature of the column 48. The injector 42 employs a loop introduction type sample introduction valve. In the injector 42, a sample is introduced as appropriate. In some cases, the temperature of the sample loop is adjusted so as to substantially match the temperature of the column 18.
The sample introduced by the injector 42 is separated by the column 48 in the column oven 46. The developing solvent eluted from the column 48 is monitored by the detector 50 for its characteristics such as absorbance. The developing solvent that has passed through the detector 50 reaches the automatic back pressure adjusting valve 19. The pressure between the system between the carbon dioxide pump 30 and the modifier solvent pump 36 (liquid feeding unit 12) and the automatic back pressure adjusting valve 19 is adjusted by the automatic back pressure adjusting valve 19. Since the properties of carbon dioxide in the supercritical state change with pressure and temperature, elution conditions can be changed by changing the pressure gradually or stepwise. In this system, parameters for changing the elution conditions include mixed solvent temperature of carbon dioxide and modifier solvent, pressure, modifier solvent species, mixing ratio of carbon dioxide and modifier solvent, total liquid delivery amount, etc. A highly flexible system with a very large degree of freedom can be constructed.

The carbon dioxide pressure is about 7-30 MPa upstream of the automatic back pressure adjustment valve 19, but is near atmospheric pressure downstream of the automatic back pressure adjustment valve 19. At this time, since the sample dissolving power of carbon dioxide and the modifier solvent greatly decreases, the sample tends to dissolve in the modifier solvent. However, when the ratio of the modifier solvent is low, the modifier solvent is slightly added to the sample. It becomes a mixed state. Therefore, the liquid with a very high sample concentration flows through the flow path downstream of the automatic back pressure regulating valve 19.
The physical properties of carbon dioxide at this point are confirmed as follows.

  In the case of carbon dioxide, when the pressure is 1/10 and the volume is 10 times, the temperature of carbon dioxide is reduced by about 150 degrees near normal temperature. Further, downstream of the automatic back pressure regulating valve 19, when the supercritical carbon dioxide drops to normal pressure, the volume expands several hundred times. It has been found that such a rapid temperature and volume change downstream of the automatic back pressure regulating valve 19 is a major obstacle when recovering the eluted sample. For example, it has been confirmed that the following phenomenon occurs when the adjusting valve connected to the outlet of the automatic back pressure adjusting valve 19 and the connecting pipe 52 between heaters are extended and introduced into the flask.

(1) Due to dry ice generation by adiabatic expansion and modifier solvent coagulation (which may be below the coagulation temperature of the modifier solvent), the piping 52 to the flask is very likely to be clogged.
(2) It overflows immediately due to the formation of dry ice and modifier solvent coagulum in the flask.
(3) Spattering due to volume expansion, especially at the outlet of the pipe 52, the carbon dioxide gas flow rate becomes very high, so the modifier solvent in it is sprayed in the form of a mist, and many modifier solvents are outside the flask. Will be released.
(4) When the pipe 52 starts to clog, the pressure increases and the pipe 52 can be clogged. However, since the gas flow rate at the moment when the pipe 52 is removed becomes higher, the clogging of the pipe 52 further promotes the scattering of the modifier solvent. .

Therefore, when only the analysis of the sample is performed, the pipe 52 from the automatic back pressure regulating valve 19 is usually submerged in, for example, a large volume of water (if the water is warmed, it is solidified. It is possible to prevent the splattering and splattering), and to discharge to a container with a large heated capacity.
However, when recovering the separated sample, the above-described obstacles cannot be achieved by simply introducing a pipe used for recovery in a liquid chromatograph to a test tube or a flask, and satisfactory recovery cannot be performed. Many types of HPLC fraction collectors are commercially available, but all of them are structured to receive droplets that fall from the piping due to gravity drops in a test tube or flask. It could not be used in graphs and carbon dioxide supercritical extraction, and there was virtually no automatic fraction collection device.

The above is an explanation of the case where a modifier solvent is added to the elution solvent. However, the same situation as described below is obtained when the modifier solvent is not added to the elution solvent.
(5) Carbon dioxide dry ice is generated by adiabatic expansion, and the piping 52 to the flask is very easily clogged.
(6) The recovery container is damaged or overflows immediately due to dry ice in the flask.
(7) Spattering due to volume expansion, especially at the outlet of the pipe 52, the carbon dioxide gas flow rate becomes very high, so the target component in the sample (which may be liquid or solid) is sprayed in the form of a mist. In many samples, the target component is released to the outside from the flask.
(8) When the pipe 52 starts to clog, the pressure increases and the pipe 52 can be clogged. However, since the gas flow velocity at the moment when the pipe 52 is removed becomes higher, the clogging of the pipe 52 is caused by the target component (liquid or solid) in the sample. (In some cases) further encourage the scattering.

Here, recovery of the modifier solvent dissolved in carbon dioxide and recovery of the sample (liquid state) are the same in terms of increasing the recovery rate of the eluted sample, and recovery of the liquid component of the eluted fluid Increasing the rate increases the recovery rate of the eluted sample.
Therefore, in any case, measures against cooling by adiabatic expansion of carbon dioxide and efficient separation of gaseous carbon dioxide flowing out at high speed from the target component contained in the sample are preparative. This is a very important matter for supercritical extraction and preparative supercritical chromatography.

Therefore, in the present embodiment, in order to take measures against cooling by adiabatic expansion of carbon dioxide, and to efficiently separate the gaseous carbon dioxide flowing out at high speed from the target component contained in the sample, automatic It is also very important to use the following heating heater 20 at the outlet of the back pressure regulating valve 19.
In the present embodiment, it is preferable that the heating heater 20 includes a heater 66, a temperature sensor 68, and a computer (temperature control means) 64.
Here, the heater 66 is provided in the pipe 52 from the automatic back pressure regulating valve 19 and heats the fluid flowing through the pipe 52.
The temperature sensor 68 detects the temperature of the fluid in the pipe 52 from the automatic back pressure regulating valve 19.
The computer 64 adjusts the fluid temperature of the heater 66 so that the temperature information obtained by the temperature sensor 68 becomes a desired constant temperature determined based on the optimum temperature for collecting the target component in the sample by the collection bottle 24. Take control.

Below, the said heating heater 20 is demonstrated more concretely, referring FIG.
FIG. 4A is a longitudinal sectional view, and FIG. 4B is a transverse sectional view.
As the heating heater 20, the piping 52 from the automatic back pressure adjustment valve 19 has a mobile phase heating function. The pipe 52 from the automatic back pressure regulating valve 19 is wound around a cylindrical aluminum material 72 having a spiral groove cut into a cylinder as shown in FIG. A heater 66 is provided on the cylindrical aluminum material 72 around which the pipe 52 is wound. A rubber heater is wound around the cylindrical aluminum material 72 as a heater 66, or a cartridge heater is inserted. Thereby, since the cylindrical aluminum material 72 can be heated, the piping 52 wound around the cylindrical aluminum material 72 can also be heated.

  Further, in the heating heater 20, a temperature sensor 68 is provided at a position (cylindrical aluminum material 72) corresponding to the most downstream side of the pipe 52 wound around the cylindrical aluminum material 72, and the temperature value of the temperature sensor 68 is used as a reference. The temperature of the elution fluid from the automatic back pressure regulating valve 19 is adjusted. This set temperature varies greatly depending on the target component in the sample to be recovered.

If the target component in the sample to be collected is resistant to high temperatures, the computer 64 adjusts the set temperature of the heating heater 20 to a temperature much higher than room temperature, thereby condensing, coagulating, and modifying moisture in the air in the pipe. It is possible to prevent coagulation of the solvent and carbon dioxide (dry ice production). For this reason, although the flow rate of carbon dioxide and the target component in the sample or the mixture (elution fluid) of carbon dioxide, the organic solvent, and the target component in the sample is fast, a stable flow rate can be obtained. From the viewpoint of recovery of the target component in the sample, the intermittent flow due to clogging of piping due to dry ice generation will hinder stable recovery in the subsequent recovery process, so it is important to obtain a stable flow. It is a thing.
Further, the computer 64 sets the temperature setting of the heating heater 20 to a temperature as low as a lower limit at which piping clogging does not occur when the target component in the sample to be collected is unstable or easily volatilized (for example, In addition, a step of stepwise pressure reduction and heating for heating after the flow path distribution valve 22 described below is required.

  An aluminum cylindrical tube 74 is provided on the outer periphery of the cylindrical aluminum material 72. A heat insulating material 76 such as fluorine resin (polytetrafluoroethylene resin) or bakelite is provided on the outer periphery of the aluminum cylindrical tube 74.

In the present embodiment, in order to distribute the eluted fluid and to efficiently collect the eluted sample, it is very important to improve the efficiency of the sorting operation. Is preferred.
That is, in the preparative chromatograph, it is necessary to divide the eluted sample into a plurality of fractions according to the peak intensity. In this embodiment, the outlet of the pipe 54 via the heating heater 20 is connected to the inlet of the disk valve type flow distribution valve 22.
Examples of such a flow distribution valve 22 include an inlet port 1 and an outlet port 6, an inlet port 1 and an outlet port 8, an inlet port 1 and an outlet port 10, and the like.
The eluted fluid that has passed through the heating heater 20 is distributed by a disk valve type flow path distribution valve 22. Since the outflow fluid has a very high flow rate, a pressure of about several MPa is applied in the pipe. Generally, however, the disc valve type has pressure resistance against such pressure. It is used as a distribution valve 22.

  On the other hand, an inexpensive solenoid-driven diaphragm valve is commercially available, but it is difficult to use it in the supercritical system according to the present embodiment because the pressure resistance against the pressure is insufficient. The switching timing of the flow distribution valve 22 of the disk valve is determined based on the time determined from the chromatograph measured in advance and the detection signal of the outflow fluid (for example, the absorbance signal from the detector 50). The flow path distribution valve 22 is switched.

  The elution fluid passes through the detector 50 and then reaches the flow path distribution valve 22. Therefore, in order to appropriately fractionate the elution fluid by the flow path distribution valve 22, the time difference is calculated from the piping capacity between the detector 50 and the flow path distribution valve 22 and the elution fluid flow velocity, and a predetermined amount is determined. It is necessary to add the time difference to the image start / end time or the fraction start / end time determined by the output signal from the detector 50. The computer 64 switches the flow path distribution valve 22 according to such added time.

The elution fluid distributed by the flow path distribution valve 22 is ejected to each recovery bottle 24 via each valve connected to the flow path distribution valve 22 and the inter-container connection pipe 56.
For example, when the flow rate of liquid carbon dioxide fed by the carbon dioxide pump 26 is 100 mL / min, the flow rate of gaseous carbon dioxide is 50 L / min. Since the internal diameter of the pipe that is normally used is about 0.8 to 2.0 mm, the line flow velocity is generally 1660 to 270 m / sec at normal pressure.
Therefore, since the gas flow velocity is very high at the outlet of the connection pipe 56 between the valve and the container, the modifier solvent component in which the target component in the sample in the elution fluid is dissolved is simply ejected to the recovery bottle 24 as it is. It may be scattered together with gaseous carbon dioxide (because it is in an aerosol state) and discharged together outside the collection bottle 24. For this reason, the recovery rate of the target component in the sample may be reduced.

Gas-liquid separator Therefore, in order to more efficiently recover the target component in the sample, it is important to devise the structure of the outlet 56a (spout portion) of the valve and inter-container connection pipe 56.
The present invention further improves the recovery rate of the eluted sample by appropriately setting the appropriate temperature and back pressure according to the elution conditions, and selecting the shape of the outlet 56a (spout portion) of the following valve and inter-container connection pipe 56. And more efficient recovery without contamination during sample recovery.

  That is, in order to suppress the reduction in the recovery rate of the target component in the sample in the recovery bottle 24, it depends on how efficiently gas-liquid separation can be realized at the outlet 56a of the valve and inter-container connection pipe 56. In terms of form, it is highly preferred to use the following gas-liquid separation method.

In the gas-liquid separation method of the present embodiment, the modification component in the elution fluid is increased by increasing the chance of contacting the elution fluid with a substance having a surface area as large as possible and inert to the sample, modifier solvent, and carbon dioxide. (Liquid) is preferably adhered to the surface of the inert material.
Examples of such a gas-liquid separation method by contact include the following methods.
(1) Modifier component (liquid) adhering to the surface of the inert material gradually accumulates and increases on the surface of the inert material, and finally flows down (hereinafter referred to as the inert material method).
(2) A method that requires contrivance in the direction of the outlet 56a (spouting portion) of the connecting pipe 56 between the valve and the container so that the eluted fluid spirally rotates on the inner surface of the cylindrical tube material (hereinafter referred to as the centrifugal force method).
Below, the said inert material method and the said centrifugal force method are demonstrated concretely.

(1) Inert Material Method FIG. 3 shows a schematic configuration of a gas-liquid separator using the inert material method.
The gas-liquid separator 58 shown in the figure includes a separator body 76 and an inert substance 78.
Here, the separator body 76 has a liquid outlet 80 at the lower part of the hollow body and a gas outlet 82 at the upper part of the hollow body.
The inert substance 78 is provided in a state in which the outlet 56 a of the valve and inter-container connection pipe 56 is embedded, and is made of a fibrous or porous substance that is inert to the elution fluid from the flow path distribution valve 22.
And the gas-liquid separator 58 makes the elution fluid from the flow-path distribution valve 22 contact the inert substance 78, discharges the liquid component from the liquid outlet 80 of the separator main body 76, and discharges the gas component to the separation gas outlet. 82 to the outside.

Hereinafter, the gas-liquid separator using the inert material method will be described more specifically.
As shown in the figure, the gas-liquid separator 58 using the contact of the elution fluid with the inert substance 78 has a device for increasing the chance of contact between the elution fluid and the inert substance 78 as much as possible. Alternatively, the outlet 56 a of the valve and container connection pipe 56 is embedded in the porous inert material 78.
Examples of the inert substance 78 include glass wool, ceramic sintered filter, stainless steel sintered filter, and a solidified fluororesin (polytetrafluoroethylene resin) powder.
The elution solvent that has come out from the outlet 56a of the connection pipe 56 between the valve and the container comes into contact with the inert substance 78, the liquid component is dropped into the recovery bottle 24 from the lower liquid outlet 80, and the gaseous component is the upper gas outlet. It is discharged from the hole 82 to the outside.
The distribution ratio of the gas component in the space A is distributed by (the combined resistance of the liquid outlet side channel resistance and the inert substance channel resistance) and the gas outlet side channel resistance. The liquid outlet side channel diameter is opened as large as possible, the linear flow rate of (liquid and gas) is reduced, and the liquid is dripped along the edge of the outlet. As the liquid outlet 80, it is preferable to use a tube material cut obliquely so that dripping is stably performed.

  In this embodiment, a cylindrical separator body 76 having a diameter of about 30 mm is filled with about 1 cm of an inert substance 78 such as glass wool or a sintered filter, the diameter of the liquid outlet 80 is 10-20 mm, and the gas outlet 82. When a pipe with an inner diameter ID = 0.8 mm is connected to about 5 cm, if the carbon dioxide flow rate is about 10-100 mL / min and the modifier solvent is about 10 mL / min, the generation of aerosol is suppressed and a stable liquid Dripping could be obtained.

The reason why the back pressure valve 84 provides flow resistance at the gas outlet 82 and applies pressure is that the slight pressure is applied to the space A to suppress the upward movement of the liquid component in the inert substance 78. Because there is. Thereby, since the liquid component in the elution fluid is sequentially sent out from the upper side to the lower side in the inert substance 78, the retention of the liquid component in the inert substance 78 can be prevented in advance.
In the present embodiment, a relief valve 86 may be provided in order to prevent a pressure exceeding a specified level from being applied in the space A.

In the present embodiment, adiabatic expansion may occur at the outlet 56 a of the valve and inter-container connection pipe 56. For this reason, when the liquid carbon dioxide flow rate is 5 mL / min or more, a heater 60 is installed on the outer peripheral wall of the separator main body 76 to prevent generation of solid carbon dioxide (dry ice) or a coagulated substance of the modifier solvent. Is preferred.
In such a structure, it is possible to exchange only the inert substance 78, or it is possible to exchange the inert substance 78 for each separator body 76 holding the inert substance 78.
In addition, as described above, since the inert substance 78 has a fibrous or porous structure in order to increase the chance of contact with the elution fluid, complete cleaning may be difficult.

On the other hand, when performing fractionation of another type of sample, it is necessary to replace this inert substance 78, so it is important that the replacement work can be simplified.
Therefore, in this embodiment, the inert material 78 can be easily replaced by adopting a simple structure in which the inert material 78 such as glass wool or sintered filter is dropped into the separator main body 76 from above. is there.
In the present embodiment, the liquid outlet 80 is inserted into a recovery bottle lid 88 made of an elastic material (silicon rubber) and the sample is dissolved in the modifier solvent in the solvent bottle 24 by being attached to the solvent bottle 24. The middle target component can be reliably recovered.

(2) Centrifugal Force Method FIG. 4 shows a schematic configuration of a gas-liquid separator that employs the centrifugal force method. 4A is a longitudinal sectional view of the gas-liquid separator, and FIG. 4B is a transverse sectional view of a rectifying unit suitable for the gas-liquid separator.
The gas-liquid separator 58 shown in the figure includes a first cylindrical tube (outer cylindrical tube) 90 and a second cylindrical tube (inner cylindrical tube) 92.
Here, the first cylindrical tube 90 has a fluid inlet 94 formed in the upper joint 93 and a liquid accumulation portion 96 in the lower part.
The second cylindrical tube 92 is inserted with a gap between the inner peripheral wall of the first cylindrical tube 90 and has a gas discharge port 98 in the lower part.

The elution fluid from the flow path distribution valve flows into the space formed between the inner peripheral wall of the first cylindrical tube 90 and the outer peripheral wall of the second cylindrical tube 92 while rotating spirally, and the elution fluid is generated by centrifugal force. Among them, the liquid component 99 a contacts the inner peripheral wall of the first cylindrical tube 90, falls down along the inner peripheral wall of the first cylindrical tube 90, and is collected in the liquid accumulation portion 96 below the second cylindrical tube 92.
Further, it is preferable that the gas component 99b from which the liquid component 99a is removed out of the elution fluid flows out from the gas discharge port 98 at the lower part of the second cylindrical tube 92.

Hereinafter, the centrifugal force method will be described more specifically.
In the gas-liquid separator 58 shown in the figure, since the aerosol rotates at high speed in the annular space, the liquid component has a high density, so that it is easy to come into contact with the outer peripheral wall surface by centrifugal force. .
In the figure, an inner diameter selected from a range of 30 to 80 mm according to the flow rate of carbon dioxide (a tube having a larger inner diameter is used according to the flow rate of carbon dioxide) and a first cylindrical tube 90 having a wall thickness of 2 mm. Inside, a second cylindrical tube 92 having an inner diameter of 8 mm and a wall thickness of 1 mm is inserted.

  The upper part of the second cylindrical tube 92 becomes an exhaust port for external discharge as it is. An introduction port 94 is provided in the upper part of the first cylindrical tube 90 via an introduction part gasket 95. When the elution fluid flows into the internal gap from the introduction port 94, the introduction port 94 is made to flow in a tangential direction with respect to the inner wall of the first cylindrical tube 90, for example, so as to be a high-speed rotational flow around the center of the cylindrical tube. As shown in the figure, a guide 100 is provided so that the elution fluid advances while rotating at high speed. The fluid that has flowed out flows while rotating at high speed in an annular space formed by the inside of the first cylinder 90 and the outside of the second cylinder 92, and a liquid having a large specific gravity adheres to the outer wall of the first cylinder 90. The gas component 99b from which the liquid component 99a has been removed flows out of the second circular tube 92. On the other hand, the liquid component 99a adhering to the wall surface gradually increases in amount to form a droplet, falls along the inner wall surface of the first cylindrical tube 90, and reaches the liquid accumulation part 96 provided at the lower portion of the first cylindrical tube 90. To do. The liquid component 99a is collected by the liquid accumulation unit 96 and dropped downward from a liquid dripping hole opened in the liquid accumulation unit 96. A pipe connection port (lower lid 102) is provided at the outlet of the liquid accumulation unit 96, and the gas-liquid separator 58 and the recovery bottle 24 are connected via the lower lid 102 below the liquid accumulation unit 96. Yes.

A liquid recovery unit gasket 104 is provided between the lower lid 102 and the gas-liquid separator 58. Between the lower lid 102 and the collection bottle 24, a separator fixed lid collection bottle cover 106 and a collection bottle gasket 108 are provided.
The collection conduit 112 is attached to the pipe connection port (lower lid 102) via the joint 110 so that the liquid component 99a from the outlet of the liquid accumulation unit 96 falls down to the wall surface of the collection bottle 24. Further, the liquid accumulation part 96 is provided with an exhaust and overflow hole joint 114 provided with a hole 113. This through hole 113 suppresses an abnormal increase in the internal pressure of the recovery bottle 24 and functions as a through hole when the recovered liquid overflows.

<Rectification unit>
A rectifying unit 116 as shown in FIG. 4B is fixed to the second cylindrical tube 92. A plurality of gas circulation holes 118 are opened on the circumference of the rectifying unit 116, and the gas component 99b passes through these portions. The flow of the gas component is changed from the flow in the rotation direction to the flow in the vertical direction by the rectifying unit 116. Thereby, there is also an effect that the droplet 99a adhering to the bottom of the second cylindrical tube 92 is scattered downward.

On the other hand, the gap between the rectifying unit 116 and the inner wall of the first cylindrical tube 90 is a liquid circulation unit 120 through which liquid passes, and reaches from the liquid accumulation unit 96 to the collection bottle 24 through the collection conduit 112. The collection guiding pipe 112 is installed so as to be in contact with the inner wall surface of the collection bottle 24 at a shallow angle so that the liquid component 99 a flows down the inner wall surface of the collection bottle 24.
At the bottom of the second cylindrical tube 92, there is an exhaust flow rate control unit 122 for controlling the flow rate of the exhaust gas. The size of the hole formed in the exhaust flow rate control unit 122 is changed in accordance with a desired exhaust flow rate. This portion also serves to prevent the liquid droplets attached to the bottom of the second cylindrical tube 92 from reaching the second cylindrical tube 92.

In order to avoid cooling due to adiabatic expansion, a heater 60 including a heating heater block 124 is provided outside the first cylindrical tube 90, and the temperature is adjusted to an appropriate temperature. Normally, since a plurality of fractions are taken, the heater 60 of the gas-liquid separator 58 that is not being recovered can be switched between the start and end of temperature control in synchronization with the control program of the computer 64 and valve operation.
An upper lid 126 is provided on the upper part of the first cylindrical tube 90, and a female screw for fixing the inner tube fixing push screw 128 is cut. The second cylindrical tube 92 is fixed to the upper lid 126 by tightening the inner tube fixing push screw 128. Since the pressure in the separator is slightly higher than atmospheric pressure, a push screw type fixing method that can realize such a sealed state is adopted.

An exhaust tube 130 for leading the exhaust gas to the exhaust facility is fixed to the second cylindrical tube 92.
A separator fixing lid recovery bottle lid 106 is provided outside the liquid accumulation unit 96. The separator fixing lid recovery bottle lid 106 is formed with a screw corresponding to the male screw at the top of the recovery bottle 24. In addition, the upper part of the separator fixed recovery bottle lid 106 is constricted so as to press the liquid accumulation part 96 downward. By adopting such a constricted shape, when the separator fixing lid recovery bottle lid 106 is tightened, the liquid accumulation part 96 is fixed to the recovery bottle 24. Further, when the collection of the substance is completed, the separator fixing lid collection bottle lid 106 is loosened, the gas-liquid separation unit 58 is removed, and the collection bottle 24 can be taken out.

<Modification>
In the configuration described above, an example in which the liquid circulation unit 120 is used as the gas-liquid separator using the centrifugal force method and the second cylindrical tube 92 descends to the lower portion has been described. However, when the composition ratio of the modifier solvent is larger, it is also very preferable to use the type shown in FIG.
In the figure, the liquid circulation part 120 is omitted, and the second cylindrical tube 92 is positioned above the lower portion of the first cylindrical tube 90 without being lowered.

Further, as shown in FIG. 5, in the gas-liquid separator 58 in which the second cylindrical tube 92 is not inserted to the inside of the first cylindrical tube 90, separation of gas and liquid is performed using centrifugal force, for example, When the carbon dioxide flow rate is 30 mL / min or more, it is very preferable to provide a fluid guide 133 as shown in FIGS. 6 and 7 in order to further improve the gas-liquid separation efficiency.
6 is a cross-sectional front view of a gas-liquid separator 58 having a fluid guide 133, and FIG. 7 is a cross-sectional oblique view of the same gas-liquid separator 58.

That is, in the figure, a first cylindrical tube (outer cylindrical tube) 90 is provided with a fluid guide 133 including a spiral groove 131 on its inner peripheral wall.
The fluid flowing into the gas-liquid separator 58 (fluid from the valve) preferably flows along the fluid guide 133 including the spiral groove 131 on the inner peripheral wall of the first cylindrical tube 90.

Hereinafter, the fluid guide 133 will be described more specifically.
In the drawing, a spiral fluid guide 133 is formed on the inner peripheral wall of the first cylinder 90 forming the space A. The liquid component flows along the guide 131.
A spiral groove 131 is formed in the liquid guide 131. Since the outflow liquid flows along the spiral groove 131, the space A becomes a high-speed rotated flow along the inner peripheral wall of the first cylindrical tube 90.

  Here, in the absence of the fluid guide 133 as described above, a part of the liquid component of the outflow fluid is dragged by the flow in which the gas rotating at high speed is guided to the gas exhaust port 98, and is guided to the gas exhaust port 98. The gas may be discharged from the gas discharge port 98.

  Therefore, by providing a fluid guide 133 including a spiral groove 131 as shown in the figure, a flow rotating downward is created. At the same time, the liquid component in the inner peripheral wall of the first cylindrical tube 90 is prevented from being dragged by the exhaust gas and ascending the inner peripheral wall of the first cylindrical tube 90. That is, since the liquid component exists in the inner wall of the first cylindrical tube 90, the liquid component is less likely to rise on the inner peripheral wall of the first cylindrical tube 90 by providing the fluid guide 133 on the wall surface.

  As described above, in the same figure, in the gas-liquid separator 58 shown in FIG. 5, the fluid guide 133 including the spiral groove 131 is further provided on the inner peripheral wall of the first cylindrical tube 90. Gas-liquid separation efficiency when performing gas-liquid separation at 30 mL / min or more is greatly improved.

In the figure, an upper lid 126 and a lower lid 102 are provided above and below the first cylindrical tube 90, respectively.
The upper lid 126 is provided with an inner tube fixing push screw 128 for hermetically fixing the second cylindrical tube 92, and a second cylindrical tube 92 such as a stainless steel pipe is inserted into that portion to discharge gas.
When the upper lid 126 is provided for the first cylindrical tube 90, the pressure guide of about 1 MPa can be reliably provided by screwing the upper lid 126 after the fluid guide 133 is first installed.

The lower lid 102 is provided with a liquid outlet hole 135. The size of the liquid outlet hole 135 is sufficiently smaller than the second cylindrical tube 92. In the present embodiment, when the inner diameter of the second cylindrical tube 92 is 8 mm, the inner diameter of the liquid outlet hole 135 is 2 mm.
The lower lid 102 is provided with a separator fixing / recovery bottle lid 106, and a gas-liquid separator 58 is fixed to the recovery bottle 24 in a substantially sealed manner.
A block heater 124 is provided on the outer peripheral wall of the first cylindrical tube 90 to prevent the outflow fluid from solidifying due to adiabatic expansion of carbon dioxide.

<Appearance>
FIG. 8 is an external perspective view in which a plurality of recovery bottles 24 and gas-liquid separators 58 are combined.
In the figure, a recovery bottle stand 132 that holds three recovery bottles 24 is used.
During recovery, the gas-liquid separator 58 securely closes the recovery bottle 24 and the gas-liquid separator 58 by closing the female screw provided in the gas-liquid separator 58 with respect to the male screw at the top of the recovery bottle 24. At the same time, the contact portion between the recovery bottle 24 and the gas-liquid separator 58 comes into close contact with each other, so that leakage from the contact portion between the two is reduced.
When the collection is completed, the gas-liquid separator 58 is placed on the gas-liquid separator place 134 in the collection bottle stand 132, and the collection bottle 24 is taken out and collected.

By the way, when fractionating a sample with high volatility, the sample is often collected at a lower temperature while suppressing volatilization of the sample. In such a case, the recovery bottle 24 may be recovered by being submerged in a low temperature constant temperature bath. When used in such applications, the recovery bottle stand 132 is provided with a recovery bottle stopper 136 because the recovery bottle 24 floats when the recovery bottle stand 132 is submerged in the low-temperature circulating liquid.
The collection bottle stand 132 is provided with a guide 138 for passing piping, heater wiring, exhaust pipes and the like, for example.

Gas-liquid separation mechanism using a high-pressure method.In this embodiment, it is dependent on how efficiently gas-liquid separation can be realized in order to suppress a decrease in the recovery rate of the target component in the sample in the fraction collection container. It is also preferable to use a gas-liquid separation mechanism using a high-pressure method as shown in FIG. 9 instead of the gas-liquid separation method by contact.

FIG. 9 shows a schematic configuration of a supercritical system using a gas-liquid separation mechanism.
FIG. 10 shows a schematic configuration of the gas-liquid separation mechanism shown in FIG.
In the gas-liquid separation method under high pressure of the present embodiment, the organic solvent component in which the target substance contained in the eluted component is dissolved is stepwise at the outlet 56a (spout port) of the connection pipe 56 between the valve and the container. The pressure is reduced. During decompression, for example, under a pressure of 1 to 5 MPa, the gas flow rate becomes slow. Therefore, the organic solvent component in which the target substance contained in the elution component is dissolved is dissolved in the elution fluid at the outlet 56a of the connection pipe 56 between the valve and the container. Since it can be dripped as a liquid component contained in the liquid, gas-liquid separation can be easily performed.

The gas-liquid separation mechanism 58 of this embodiment includes a first flow path distribution valve (upstream valve) 22a, a second flow path distribution valve (downstream valve) 22b, and a downstream back pressure adjustment valve (downstream back pressure). Adjustment unit) 140.
Here, the first flow path distribution valve 22 a is provided upstream of the fraction collection container 24 having high pressure resistance, and the second flow path distribution valve 22 b is provided downstream of the fraction collection container 24.
The downstream back pressure adjustment valve 140 is provided downstream of the second flow path distribution valve 22b, and gradually reduces the outlet 56a of the valve-to-container connection pipe 56 so that the desired fraction collection container 24 has a desired inside. It shall be for constant pressure.
In the gas-liquid separation mechanism 58 shown in the figure, the first flow distribution valve 22a, the desired fraction collection container 24, the second flow distribution valve 22b, and the like according to the desired fraction collection container 24. The first flow path distribution valve 22a and the second flow path distribution valve 22b are switched synchronously so that the downstream side back pressure adjustment valve 140 is in a conductive state, and the outlet 56a of the pipe 56 is gradually reduced. Then, a desired constant pressure state (for example, 1-5 MPa) is set in the desired fraction collection container 24.

  As a result, in the gas-liquid separation mechanism 58 shown in the figure, the eluted fluid is dropped into the fraction collection container 24 from the outlet 56a of the valve and inter-container connection pipe 56. The target component or modifier solvent in the sample in the elution fluid is stored in the bottom of the fraction collection container 24 as a liquid. Carbon dioxide in the elution fluid is discharged as gas in the fraction collection container 24 from the upper part of the fraction collection container 24 to the outside via the pipe 141, and further, the second flow path distribution valve 22 b and the downstream side back pressure adjustment valve 140. It is discharged through.

Hereinafter, the gas-liquid separation mechanism using the high-pressure method will be described more specifically.
In the gas-liquid separation using the high-pressure method as shown in FIG. 10A, two flow path distribution valves 22a and 22b and a downstream back pressure adjustment valve 140 are installed. The computer 64 moves the flow distribution valves 22a and 22b in synchronism so that the inside of the fraction collection container 24 having high pressure resistance is under pressure (for example, 1-5 MPa) and realizes gas-liquid separation of the eluted fluid. .
The timing at which the flow path distribution valves 22a and 22b are moved synchronously depends on a predetermined time and the signal level of the detector 50, and the computer 64 switches the flow paths of the flow path distribution valves 22a and 22b.

For example, when the target component in the sample is not flowing out, the port position of the first flow path distribution valve 22a is P50, the port position of the second flow path distribution valve 22b is port P51, and the fluid is discarded. When the first target component flows out, the first flow path distribution valve 22a is set to the port P10, and the second flow path distribution valve 22b is set to the valve position of the port P11. Further, the high-pressure stop valve 142 (V1) attached below the fraction collection container 24 (for example, the container A) is kept closed. In this state, the elution fluid flows into the container A. However, since the downstream back pressure adjustment valve 140 is downstream of the second flow path distribution valve 22b, the inside of the container A has the downstream back pressure adjustment valve 140. Pressurization is performed until the set pressure reaches 4 MPa, for example.
Under sufficient pressure, for example, at 3 MPa or more, the mixture of carbon dioxide and modifier solvent does not become an aerosol, but drops as a liquid from the valve 56 in the container A and the outlet 56 a of the inter-container connection pipe 56. For this reason, the modifier solvent is stored in the container A as a liquid.
On the other hand, carbon dioxide becomes gas and is discharged from the container A-port P11-downstream back pressure regulating valve 140.

When there is an elution fluid to be discarded between the first target component and the second target component, the port position of the first flow path distribution valve 22a is P50, and the port position of the second flow path distribution valve 22b is P51. Discard the elution fluid to be discarded.
On the other hand, when there is no elution fluid to be exhausted (for example, when the first component and the second component are eluted in duplicate), when the second target component flows out, the first flow path distribution valve 22a is connected to the port P20. The second flow distribution valve 22b is set to the valve position of the port P21.
Further, the high-pressure stop valve 142 (V2) attached below the container B is kept closed.

In the following process, the second component dissolved in the modifier solvent is recovered in the container B in the same manner as that performed in the container A. The container D can sequentially collect the target components 3 and 4 in the same manner.
Here, the first flow path distribution valve 22a from the valve position of the port P10, the second flow path distribution valve 22b from the valve position of the port P11, the first flow path distribution valve 22a as the port P20, and the second flow path distribution valve 22b as the port P21. A state where the valve position is set, that is, a state where the collection of the container A is completed and the container B is switched to is considered.
At this time, since the first flow path distribution valve 22a and the second automatic distribution 2 valve 22b are switched instantaneously, the pressure in the container A is maintained at a level controlled by the downstream back pressure adjustment valve 140. It has become. When the high-pressure stop valve 142 (V1) is opened in this state, the modifier solvent in which the target component accumulated under the container A is dissolved is pushed down, and then the carbon dioxide in the container A is discharged and the container A The internal pressure is normal pressure. Since this process can be performed in parallel with the process of introducing the modifier solvent into the container B, an efficient system can be realized without reducing the processing speed of the entire process.

  In such a process, when the second flow path distribution valve 22b is not provided, for example, when the second flow path distribution valve 22b is used as a simple junction, when the first flow path distribution valve 22a is switched, the internal pressure of each container is initially set. Is normal pressure, for example, even if the first flow path distribution valve 22a is set at the position of the port P10, it flows into the remaining containers B, C, and D via the container A and the junction. When the internal pressure of each container increases and reaches the set value of the downstream side back pressure regulating valve 140, the flow starts from the outlet of the downstream side back pressure regulating valve 140.

In summary, in the case of only the first flow path distribution valve 22a, the first fraction component flows into each container 24 and causes contamination, so two valves are necessary. In addition, when the two valves 22a and 22b are used in this way, each container can be kept at a high pressure, so that it is possible to advantageously discharge the fractionated solvent accumulated in the container.
When the volume of the container is increased, a very expensive high-pressure collection container (fraction collection container 24) is prepared for the required number of fractions. Thus, the high-pressure collection container (fraction collection container 24) is prepared for each analysis. If the fraction liquid can be derived outside, a high-pressure collection container (fraction collection container 24) having a small volume of, for example, about 200 ml can be used, which is advantageous in terms of cost.

FIG. 10 shows an example in which the piping method of the first flow path distribution valve 22a is further improved.
In FIG. 10A, the flow path distribution valve 22a adopts a rotary disk type structure.
For this reason, the position selection of the flow path distribution valve 22a is performed in a certain order, for example, in the case of an 8-way valve, the ports 1, 2, 3,... The port 2 is always opened for a moment. If the disposal position is set to one port P50, the rotary disk type flow distribution valve 22a needs to be rotated in order to set the flow distribution valve 22a to the position of the port P50 every time the fractional component is switched. is there. At this time, since the flow paths P20, P30, and P40 for collecting other components are in an open state, components other than the target flow into these flow paths although they are in a small amount.

  Therefore, in this embodiment, when the discard positions W1 to W3 of the flow path distribution valve 22a are provided so as to be sandwiched one by one for each fraction as shown in FIG. By performing the valve control of the flow path distribution valve as shown in (2), it is possible to collect and discard only the target component in the desired container without pouring the target component into another container.

Sealed chamber, exhaust In the figure, all of the first flow path distribution valve 22a, the second flow path distribution valve 22b, each fraction collection container 24, and each automatic stop valve 142 (V1 to V4) are contained in the sealed chamber 62. It is preferable that the elution solvent, the elution solvent and the carbon dioxide mixed with the sample components are prevented from leaking out of the system by forcibly discarding or spontaneously exhausting the atmosphere in the sealed chamber 62.

High-pressure stop valve In addition, each fraction collection container 24 is provided with a high-pressure stop valve 142 (V1 to V4) for more efficient recovery of the eluted sample, and the solvent stored in the fraction collection container 24 is automatically collected. It is also preferable to discharge to the outside.

Actual System Arrangement FIG. 11 shows an actual arrangement of the supercritical system of this embodiment.
In the figure, fluid flows generally from the left side to the right side of the apparatus. The overall configuration includes a liquid delivery unit 12, a sample introduction unit 14, a separation detection unit 16, a back pressure unit 18, a collection unit 143 including, for example, a flow path distribution valve 22, a collection bottle 24, and the like, a downstream back pressure. It is constituted by a recovery heating and back pressure unit 147 including a regulating valve 140, a heater switch 145 used for the gas-liquid separation mechanism, and the like.

  A carbon dioxide stop valve 32a is provided at the left end of the system of the liquid feeding section 12 to open and close the carbon dioxide flow channel introduced into the system. A carbon dioxide pump 26 is disposed on the lower left side. In the figure, two carbon dioxide pumps 26 are arranged. A modifier solvent pump 36 and a modifier solvent switching valve 32b are installed on the upper left side, and a modifier solvent is selected in accordance with elution conditions. On the right side of such a modifier liquid feeding unit, a control unit (computer 64) for performing temperature display and heating of the fluid and a heating heater 40 are installed. Further, a mixer 38 is installed on the right side.

The sample introduction unit 14 is provided with a syringe pump 44 that introduces the sample into the sample loop and an injector 42 that introduces the sample into the high-pressure channel.
The separation detection unit 16 is provided with a column oven 46 for constant temperature, a detector 50, and a rinse solvent pump 146 for eluting a sample that may be deposited in the recovery flow path.
The back pressure unit 18 is provided with an automatic back pressure adjusting valve 19 and a heating heater 20 located downstream thereof.
In the collection unit 143, the flow path distribution valve 22, the gas-liquid separation mechanism 58, and the collection bottle 24 are installed. When performing high pressure recovery, an automatic stop valve 142 is further installed in the recovery unit 143.

The sealed chamber 12 is a side view of the recovery unit 143 of the supercritical system shown in FIG. 11 is shown.
In the drawing, the recovery unit 143 can be covered with a transparent acrylic plate 150 so that the front surface can be covered, and has a structure that maintains substantially confidentiality.
When the acrylic plate 150 is opened, the acrylic plate 150 is inserted into the ceiling of the recovery unit 143, and a wide opening space can be secured so that the recovery bottle 24 can be easily installed and removed from the recovery unit 143. It is like that.
The acrylic plate 150 is connected to a slider 156 by a hinge 154, and the slider 156 is connected to a weight 160 by a wire 158.
The wire 158 is supported by a bearing 162. This is because the weight of the acrylic plate 150 becomes heavy, so that the weight of the weight 160 and the acrylic plate 150 are balanced and the acrylic plate 150 can be easily opened and closed.

An opening 164 for attaching an exhaust duct is provided on the right side surface of the collection unit 143. Thereby, the collection | recovery part 143 is kept substantially secret with external air. The system configuration is useful when collecting harmful samples as well as suppressing the outflow of carbon dioxide into the installation environment of the system.
The recovery warming / back pressure unit 147 includes a heater controller for heating the gas-liquid separator (mechanism), and a back pressure generation unit for performing high pressure recovery.

Test sample collection amount were then carried out recovering caffeine using supercritical system of the present embodiment. A list of sorting conditions and recovery rates at that time is shown below.
Sample: Caffeine Carbon dioxide flow rate: 70 mL / min
Modifier solvent: ethanol Modifier solvent flow rate: 5 mL / min
column:
Size: ID20mm × L250mm
Filler: Silica
Measurement method: Ten fractions were collected and fractions of caffeine elution were collected.
The recovery rate was calculated by the following formula: recovery amount = sample recovery amount / total sample introduction amount.

Condition Condition 1 Condition 2 Condition 3

Recovery rate 68% 99% 99%

Condition 1: When the elution solvent that has come out of the automatic back pressure regulating valve 19 is directly inserted into a 1 L bottle through a pipe having an inner diameter of 0.5 mm, an outer diameter of 1.6 mm, and a length of 1 m and collected (the elution fluid Distribution)
Condition 2: When recovered with “gas-liquid separator using centrifugal force as shown in FIG. 4” Condition 3: When recovered with “gas-liquid separator as shown in FIG. 9”

  As is clear from the above test results, more efficient recovery of the eluted sample can be performed by using the supercritical system of the present embodiment.

  Also, in this embodiment, in any supercritical system, it is very important to automate the system for more efficient recovery, and it is also very important to use the following automatic cylinder switching mechanism and mixer. is there.

Automatic cylinder switching mechanism FIG. 13 shows a schematic configuration of an automatic cylinder switching mechanism suitable for the supercritical system of this embodiment.
The cylinder automatic switching mechanism 168 shown in the figure includes a plurality of carbon dioxide cylinders 26a, 26b, 26c, stop valves 176a, 176b, 176c provided for the carbon dioxide cylinders 26a, 26b, 26c, and each carbon dioxide cylinder. A merging portion 172 for merging the flow paths from 26a, 26b, and 26c to the downstream flow path, and a computer (cylinder switching control means) 64 are provided.
Then, the computer 64 opens and closes the corresponding stop valves 176a, 176b, and 176c in accordance with the carbon dioxide remaining amount of the cylinders 26a, 26b, and 26c, and sequentially supplies the carbon dioxide from one cylinder to the junction 172.

That is, when a large amount of carbon dioxide is used, as shown in FIG. 13, a plurality of carbon dioxide cylinders 26a, 26b, and 26c are prepared, and the carbon dioxide cylinders 26a to 26c that derive carbon dioxide are sequentially switched. There is a need.
If the plurality of carbon dioxide cylinders 26a to 26c are merged at the junction 172 and the carbon dioxide is simply drawn out, the cylinder is reduced by one (the amount of carbon dioxide reduction varies from cylinder to cylinder). The cylinder used for extracting liquid carbon dioxide is called siphon type, and the carbon dioxide intake is located at the bottom of the cylinder. When partial reduction occurs in this type of cylinder, suction of gaseous carbon dioxide by the pump is started from the carbon dioxide intake port of the cylinder that is the fastest to decrease.
Since gas is usually easier to suck than liquid, only gaseous carbon dioxide will be sucked thereafter.

Therefore, it is necessary to switch the carbon dioxide cylinders 26a to 26c by the stop valves 176a to 176c.
In order to perform unmanned operation for a long time, the computer 64 automatically switches the carbon dioxide cylinders 26a to 26c by the stop valves 176a to 176c, that is, opens and closes the stop valves 176a to 176c. It is necessary to switch according to the remaining amount.

There are the following methods for measuring the remaining amount of carbon dioxide.
Measurement 1) Method in which the computer 64 predicts the remaining amount of carbon dioxide in the cylinder based on the carbon dioxide feed flow rate and switches the stop valves 176a to 176c. Measurement 2) The computer 64 is a weighing scale 170a to 170c, and each of the cylinders 26a to 26c itself. There is a method of measuring the weight, filling the cylinder with carbon dioxide, measuring the weight of the cylinder and carbon dioxide, and calculating the remaining amount of carbon dioxide.
Here, the measurement 1 has an advantage that it is necessary to always manage the accumulated amount of carbon dioxide used, but it is not necessary to measure the weight of each cylinder.

<Measurement 1>
A specific example of measurement 1 is shown below.
1) Carbon dioxide cylinders are used in the order of carbon dioxide cylinder 26a-> carbon dioxide cylinder 26b-> carbon dioxide cylinder 26c.
2) The amount of carbon dioxide charged in each of the two cylinders 26a, 26b, 26c is stored (C-1, C-2, C-3).
3) Since a constant flow rate pump is used for sending carbon dioxide, the amount of liquid sent per hour is clear. For this reason, based on the operation time of the system, it is possible to calculate the carbon dioxide consumption, and further the remaining amount of carbon dioxide = carbon dioxide filling amount−carbon dioxide consumption. It is always checked whether or not the remaining amount of carbon dioxide falls below a certain threshold, for example, 1 kg.
4) When the remaining amount of carbon dioxide in the cylinder 26a falls below the threshold value, a signal is output from the computer 64 to the stop valve 176b to open the cylinder 26a. Further, a signal is output from the computer 64 to the stop valve 176a, and the closed state is established. After the stop valve 176b is first opened, the carbon dioxide can be continuously supplied by closing the stop valve 176a.
5) The carbon dioxide cylinder 26b-> carbon dioxide cylinder 26c is switched in the same procedure.

<Measurement 2>
A specific example of measurement 2 is shown below.
1) The cylinders are used in the order of carbon dioxide cylinder 26a-> carbon dioxide cylinder 26b-> carbon dioxide cylinder 26c.
2) The empty weight of the carbon dioxide cylinder to be used is stored (Ew1, Ew2, Ew3).
3) The cylinders 26a, 26b, and 26c filled with carbon dioxide are placed on the weighing scales 170a, 170b, and 170c, respectively, the system is operated, and the weight of the cylinder 26a is measured as needed.
4) Calculate Aw1-Ew1. Since this value is the remaining amount of carbon dioxide, it is always checked whether this value is below a threshold of, for example, 1 kg.
5) When the value falls below the threshold value, a signal is output from the computer 64 to the stop valve 176b, and the valve is opened. Further, a signal is output from the computer 64 to the stop valve 176a, and the closed state is established. After the stop valve 176b is first opened, the carbon dioxide can be continuously supplied by closing the stop valve 176a.
6) The carbon dioxide cylinder 26b-> the carbon dioxide cylinder 26c is switched in the same procedure.

Mixer In any system, it is an indispensable element to perform preparative chromatography stably to sufficiently mix carbon dioxide and a modifier solvent.
Here, we introduce a static mixer aimed at solvent diffusion by flow velocity. Since this mixer does not require external power, there is no risk of failure, and the mixer operates stably for a long period of time, so it is useful in any system.
14 and 15 show a schematic configuration of the mixer 38. FIG.
FIG. 14 is a longitudinal sectional view of the mixer, and FIG. 15 is a transverse sectional view of the mixer.

The mixer 38 shown in the figure operates very effectively when the linear flow rate of carbon dioxide into the mixer 38 is sufficiently high, for example, 10 cm / sec or more.
The mixer 38 is composed of three containers, and a first container 180a, a second container 180b, and a third container 180c are formed from the bottom side of the mixer 38.
A conical liquid mixture outlet 182 is provided at the top of the mixer 38, and the mixed solvent is introduced downstream from an outlet 183 of the conical liquid outlet 182.
The mixer 38 has such a structure of three containers 180a to 180c in order to easily switch the number of containers to be used depending on the carbon dioxide flow rate or the modifier solvent flow rate. A lid is possible at the bottom of each container, and when it is not necessary, the solvent does not leak into the lower container.

Each container 180a-180c is provided with a carbon dioxide inlet 184a, 184b, 184c and a modifier solvent inlet 186a, 186b, 186c, respectively. The carbon dioxide inlets 184a, 184b, and 184c are provided so that carbon dioxide flows in from the tangential direction of the circumference of the container.
The modifier solvent inlets 186a, 186b, 186c are installed in the vicinity of the carbon dioxide inlets 184a, 184b, 184c.
Since the outlet 183 of the mixed liquid outlet 182 is located above the mixer 38, the carbon dioxide that has flowed into the mixer 38 at a high speed moves upward while entraining the modifier solvent and swirling in each container.

Each of the containers 180a to 180c can be filled with a filling 185 of a sphere (stainless steel, fluorine resin, etc.) having a diameter of 3 to 10 mm.
For example, such a filler 185 is used when it is difficult to mix depending on the type of modifier solvent by using a mixing mode different from that of the first container 180a.
In the case of filling the filler 185, a sill plate 190 having a large number of holes 188 having a diameter of about 2.5 to 3.0 mm as shown in FIG. It is also preferable to prevent the filler 185 from leaking into other containers. The sill plate 190 also serves as a rectifying plate that regulates the flow of fluid.

As a guideline for the containers 180a to 180c to be used, when the carbon dioxide flow rate is 5-50 mL / min, the bottom of the third container 180c is covered, and carbon dioxide and a modifier solvent are introduced into the third container 180c. The solvent mixed by the mixer 38 is taken out from the outlet 183 of the conical mixed liquid outlet 182 at the top.
When the carbon dioxide flow rate is 50-120 mL / min, the bottom of the second container 180b is covered, carbon dioxide and the modifier solvent are introduced into the second container 180b, and after passing through the third container 180c, The solvent mixed by the mixer 38 is taken out from the outlet 183 of the conical mixed liquid outlet 182 at the top.
When the carbon dioxide flow rate is 120 to 200 mL / min, the bottom of the first container 180a is covered, carbon dioxide and a modifier solvent are introduced into the first container 180a, and the second container 180b and the third container 180c are installed. After passing, the solvent mixed by the mixer 38 is taken out from the outlet 183 of the mixed liquid outlet 182 at the top.

It is explanatory drawing of schematic structure of the supercritical system concerning one Embodiment of this invention. It is explanatory drawing of a suitable temperature control part in this embodiment. It is explanatory drawing of a suitable gas-liquid separator in this embodiment. It is a modification of a gas-liquid separation part suitable in this embodiment. 5 is a modification of the gas-liquid separator shown in FIG. FIG. 6 is a cross-sectional illumination view of a preferred fluid guide in the gas-liquid separator shown in FIG. 5. It is a cross-sectional perspective view of a suitable fluid guide in the gas-liquid separator shown in FIG. FIG. 6 is an external perspective view of the gas-liquid separator shown in FIGS. 4 to 5. It is explanatory drawing of schematic structure of the supercritical system using the suitable gas-liquid separation mechanism in this embodiment. It is an enlarged view of the gas-liquid separation mechanism shown in FIG. 1 is an overall view of a supercritical system of the present embodiment. It is a side view of the collection | recovery part shown in FIG. It is explanatory drawing of the cylinder automatic switching mechanism suitable in this embodiment. It is a longitudinal cross-sectional view of a suitable mixer in this embodiment. It is a cross-sectional view of a mixer suitable in this embodiment. It is explanatory drawing of a suitable sill board in the mixer of this embodiment.

Explanation of symbols

10 Supercritical carbon dioxide chromatograph (supercritical system)
DESCRIPTION OF SYMBOLS 12 Liquid sending part 14 Sample introduction part 16 Separation detection part 18 Upstream side back pressure adjustment part 19 Automatic back pressure adjustment valve 20 Heating heater (temperature adjustment part)
22 Channel distribution valve (valve)
24 Collection bottle (fraction collection container)

Claims (10)

A supercritical fluid or, if desired, a supercritical fluid and a modifier solvent to be fed into the system as a solvent fluid; and
A sample introduction unit that is provided downstream of the liquid feeding unit and introduces the sample into the solvent fluid;
The sample in the solvent fluid is provided under a temperature condition and a pressure condition which are provided downstream of the sample introduction part and are above the critical temperature and the critical pressure of the fluid and optimal for fractionation of the sample by the solvent fluid. Separating and detecting the target component in the sample,
An upstream-side back pressure adjustment unit that is provided downstream of the separation detection unit and adjusts the pressure of the fluid between the separation unit and the liquid feeding unit within a range that is optimal for the separation of the target component in the sample;
A temperature adjustment unit that is provided downstream of the upstream back pressure adjustment unit, and that adjusts the temperature of the fluid from the upstream back pressure adjustment unit within a range that is optimal for fractionation of the target component in the sample;
The detection result of the target component in the sample in the separation detection unit is provided downstream of the temperature adjustment unit so that the fluid containing the target component in the sample can be separated from the fluid from the temperature adjustment unit. And a valve for switching the flow path between the temperature adjusting unit and the downstream,
A fraction collection container that is provided downstream of the valve and collects a fluid containing the target component in the sample out of the fluid from the valve under a pressure condition and a temperature condition optimal for the collection of the target component in the sample;
A supercritical system characterized by comprising The supercritical system according to claim 1,
A supercritical system comprising a gas-liquid separator provided between the valve and the fraction collection container and separating a fluid from the valve into a gas component and a liquid component. The supercritical system according to claim 2,
Adjusting the temperature of the fluid from the valve so as to obtain a desired constant temperature determined based on the optimum temperature for collecting the target component in the sample in the fraction collection container provided in the gas-liquid separator A supercritical system characterized by having a heater for performing The supercritical system according to claim 2 or 3,
The gas-liquid separator is
A separator body having a liquid outlet at the bottom of the hollow body and a gas outlet at the top of the hollow body;
Provided in a state where piping from the valve is embedded in the separator body, and a fibrous or porous inert substance that is inert to the fluid from the valve;
With
The fluid from the valve is brought into contact with the inert substance, and the liquid component of the fluid is dropped from the separator main body liquid outlet to the fraction collection container, and the gas component of the fluid is discharged from the separator main body gas outlet. A supercritical system, wherein the gas-liquid separator is discharged to the outside. The supercritical system according to claim 2 or 3,
The gas-liquid separator is
An outer cylindrical tube having a fluid inlet at the top and a liquid collecting portion at the bottom;
An inner cylindrical tube provided with a gap between the outer peripheral wall of the outer cylindrical tube and having a gas outlet at the bottom;
With
The fluid from the valve flows while spirally rotating into the space between the outer peripheral wall of the outer cylindrical tube and the outer peripheral wall of the inner cylindrical tube, and the liquid component of the fluid from the valve is caused to be centrifugally by the centrifugal force. It contacts the inner peripheral wall of the outer cylindrical tube, falls down along the inner peripheral wall of the outer cylindrical tube, is collected in the liquid collecting portion at the lower portion of the outer cylindrical tube, and is dropped into the fraction collection container through the liquid collecting portion. ,
The gas component from which the liquid component has been removed is discharged to the outside of the gas-liquid separator from the gas discharge port at the lower part of the inner cylindrical tube. The supercritical system according to claim 5,
The outer cylindrical tube is provided with a fluid guide including a spiral groove on its inner peripheral wall,
The supercritical system, wherein the fluid from the valve flows along the fluid guide on the inner peripheral wall of the outer cylindrical tube. The supercritical system according to claim 1,
The valve includes an upstream valve provided upstream of the fraction collection container and a downstream valve provided downstream of the fraction collection container,
In addition, a gas-liquid separation mechanism that separates the fluid from the upstream valve into a gas component and a liquid component,
The gas-liquid separation mechanism is
The fraction collection container having high pressure resistance;
The upstream valve and the downstream valve;
A downstream back pressure adjusting unit provided downstream of the downstream valve for adjusting the pressure in the fraction collection container;
With
The upstream side valve and the downstream side valve are switched synchronously so that the upstream side valve, the desired fraction collection container, the downstream side valve, and the downstream side back pressure adjustment unit are in a conductive state. By letting the inside of the fraction collection container to be in a constant pressurized state, the fluid from the upstream valve is dropped into the desired fraction collection container,
A supercritical system characterized in that a gas component in the fluid is discharged to the outside of the fraction collection container, and further discharged via a downstream valve and the downstream back pressure adjusting unit. The supercritical system according to claim 7,
A supercritical system comprising a high-pressure stop valve provided in the fraction collection container and for discharging the liquid component collected in the fraction collection container to the outside. In the supercritical system according to any one of claims 1 to 8,
A supercritical system comprising a sealed chamber in which at least the valve and the fraction collection container are placed, and a space around the valve is enclosed. In the supercritical system according to any one of claims 1 to 9,
The liquid feeding part is
A plurality of fluid cylinders for the supercritical fluid;
A cylinder automatic switching mechanism that sequentially switches the fluid cylinders to be fluid derived so that the fluid is continuously supplied to the downstream of the system from the fluid cylinder that is one of the plurality of fluid cylinders;
With
The cylinder automatic switching mechanism is
A stop valve provided for each cylinder,
A merging section for merging the flow paths from the cylinders downstream of the system;
Opening and closing each stop valve according to the remaining amount of each cylinder, sequentially so that fluid is continuously supplied to the downstream of the system from the fluid cylinder that is one of the plurality of cylinders, A cylinder switching control means for switching a fluid cylinder to be a fluid derivation target;
A supercritical system characterized by comprising

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