JP2005274552A - Dispensing method and dispensing apparatus, and liquefaction determining apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dispensing method, a dispensing apparatus and a liquefaction determining apparatus suitable for dispensing of a sample such as foods and fragrant materials, preventing a contamination of the sample separated by chromatograph, surely implementing the dispensing of the target sample, visually confirming actual liquefaction timing of the separated sample, accurately and surely confirming timing of the dispensing, preventing a delay of the dispensing due to information from the chromatogram only, reliably achieving the dispensing, improving the accuracy and reliability for a visual confirmation, and rationally detecting an introduction and a liquefaction state of the gas sample. <P>SOLUTION: In the dispensing method, a target dispensing component in a sample component separated by a column is introduced into the dispensing apparatus 3, then introduced into predetermined collection pipes 42-48, and the liquefaction and dispensing are implemented. The liquefaction state of the dispensing component introduced into the collection pipe 42-48 is confirmed or detected during the dispensing. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is suitable for, for example, the separation of samples such as foods and fragrances, prevents contamination of the chromatographically separated sample, reliably separates the target sample, and actually separates the sample. Visually check the liquefaction time of the sample, accurately and reliably check the timing of sorting, prevent delays in sorting due to only the information from the chromatogram, realize highly reliable sorting, and check the visual The present invention relates to a fractionation method, a fractionation device, and a liquefaction determination device that can improve the accuracy and reliability of the gas sample and can reasonably detect the introduction or liquefaction state of a gas sample.

In general, a gas chromatograph (GC) fractionator or a liquid chromatograph (LC) fractionator is used to take out each component in a sample and examine its structure or use it for another purpose.
Among these, the LC fractionation device includes a liquid feed pump and a sample injector, a separation column and a detector, a fractionation device, a recorder, and the like (for example, Patent Document 1), and the GC fractionation device includes the liquid feed pump. Instead of using a carrier gas cylinder, the sample components are separated by the GC or LC, and the eluted fluid is taken out at every peak or every holding value interval and separated into each collection container. ing.

  The GC preparative device is suitable for large-scale preparative use in the field of foods and fragrances, and the sample and carrier gas are inorganic gases compared to the LC preparative device requiring a large amount of elution solvent. There are also preferable features from above.

When such a GC or LC sorting device sorts a target sample component, the peak component of the target sample component is detected by the detector as described above, and then the peak component is detected by the sorting device. When the electromagnetic valve is reached, the electromagnetic valve is opened to collect the target component.
However, there is a delay time related to the pipe capacity and flow velocity of the part before the peak component reaches the solenoid valve of the sorting device from the detector, and this tendency is particularly noticeable for the high boiling point component. .
Therefore, it is necessary to operate the solenoid valve in anticipation of the delay time, but it is actually difficult to calculate the delay time accurately and operate the solenoid valve, and the timing of the valve opening timing is inaccurate, There is a problem that the reliability of sorting is lowered.

  In order to solve such problems, a system controller for controlling the operation of the sorting apparatus is provided, and the target volume can be obtained simply by inputting the pipe capacity from the detector to the sorting apparatus to the system controller. When the peak of the sample component is detected, the time when the peak start portion of the target component reaches the solenoid valve of the sorting device is automatically calculated based on the information set in the controller. However, there is one in which the solenoid valve is opened and sorted at this calculation time (for example, Patent Document 1).

  However, the above-mentioned apparatus is expensive and it is difficult to obtain the accuracy of the piping capacity input to the system controller. Moreover, the time when the peak component reaches the solenoid valve from the detector is determined depending on the sorting environment and the sorting. Since there are differences depending on the components, for example, high-boiling components and low-boiling components, there is a limit to the method of operating the solenoid valve uniformly with only the pipe capacity and the flow rate program set in the system controller. I was worried about the accuracy or reliability.

  On the other hand, in the GC fractionator, the target component eluted from the separation column is liquefied and fractionated, and it is necessary to open the solenoid valve of the fractionator at this liquefaction time to separate the target component. As a liquefaction identification means that can be used in such a method, an optically transparent body, a light source, and a photodetector that receives reflected light from the optically transparent body are provided, and the refractive index of the liquid is determined from the detection signal. By doing this, there is one that detects the presence / absence, type, concentration, etc. of the liquid of the subject (for example, Patent Document 2).

  However, the liquid identification device requires special optical equipment such as a prism, and the liquid identification device is identified due to variations in manufacturing of the device, variations due to temperature, external force, etc., changes in the refractive index of the liquid due to temperature, variations in the light source level, etc. There was a problem that the reliability of the system deteriorated.

  By the way, in the fractionation device, when the target component eluted from the separation column is separated into a plurality of containers, a branch pipe is provided between the separation column and the plurality of containers, and a fluid is supplied from the downstream side of the branch pipe. A pressurizing means for applying a gas pressure (back pressure) of an inert gas or the like is provided in a flow channel that is not desired to flow. For example, when separating the liquid in the reagent liquid reservoir, the inert gas is fed into one waste liquid container, and the container After applying back pressure to the branch pipe communicating with the liquid, the liquid in the reagent solution reservoir is guided to the branch pipe, and the liquid is stored in the other recovery container via the reagent flow path where no back pressure is applied. -Is prevented (for example, Patent Document 3).

However, although the apparatus applies back pressure from one side, for example, the downstream side of the flow path where the fluid is not desired to flow, to prevent contamination of the chemical solution, a special means is provided on the upstream side. Therefore, there is a risk of contamination flowing in from this upstream path.
In addition, since the inert gas is sent to the recovery container through the waste liquid container, the inert gas is contaminated and comes into contact with the chemical liquid in the recovery container, so that the recovered chemical liquid is contaminated by the inert gas, There was a problem that reliability could not be obtained.

JP-A-5-302918 Japanese Utility Model Publication No. 60-29271 JP-A-6-138128

  The present invention solves such a problem, and is suitable for, for example, the separation of samples such as foods and fragrances, prevents contamination of the sample separated by chromatography, and reliably separates the target sample. , The actual liquefaction time of the separated sample is visually confirmed, the timing of fractionation is confirmed accurately and reliably, the delay in fractionation due to only the information from the chromatogram is prevented, and reliable fractionation is achieved. An object of the present invention is to provide a fractionation method, a fractionation device, and a liquefaction determination device that can be realized, improve the accuracy and reliability of the visual confirmation, and can reasonably detect the liquefaction state of a gas sample. .

According to the first aspect of the present invention, a target fraction component in a sample component separated by a column is introduced into a fractionation device, and the target fraction component is introduced into a predetermined collection tube to be liquefied and fractionated. In the collection method, the liquefaction state of the preparative component introduced into the collection tube is confirmed or detected, and the fractionation is performed by determining the fractionation timing uniformly only by chromatogram information. The conventional problem that the timing was apt to be delayed is solved, and the sample is accurately sorted under the actual liquefied condition to obtain its reliability.
In the invention of claim 2, the liquefaction state of the preparative component is visually confirmed or detected by a liquefaction detection sensor so that the liquefaction state can be confirmed accurately and easily.
According to a third aspect of the present invention, the preparative component introduced into the collection tube is adiabatically expanded and liquefied, and is liquefied surely and easily by simple means.

In the invention of claim 4, after confirming or detecting the completion of liquefaction of the preparative component introduced into the collection tube, the collection channel for the next preparative component is opened, and the next preparative component is placed in a predetermined collection tube. In this way, the current fractionation is stopped and switched to the fractionation of the next fractionation component so that contamination can be prevented.
According to a fifth aspect of the present invention, contamination is prevented by introducing a carrier gas having a predetermined pressure from the upstream side of the collection tube and plugging the upstream side of the collection tube with a carrier gas. Yes. In addition, by introducing fresh carrier gas at that time, contamination of the sample to be collected by the carrier gas is prevented, and the reliability of the sorting is improved.
The invention of claim 6 introduces a carrier gas of a predetermined pressure from the upstream side of the collection tube and introduces a carrier gas of a predetermined pressure from the downstream side of the collection tube. By plugging, contamination is surely prevented.

  According to a seventh aspect of the present invention, the liquefaction detection sensor is a photosensor capable of detecting reflected light in the liquefaction part of the collection tube, or a temperature measurement sensor capable of detecting a temperature change in the liquefaction part of the collection tube as an electrical signal. Yes, an optimum liquefaction detection sensor can be selected according to the fractionation component or the fractionation conditions. The invention of claim 8 is provided with a collection tube capable of introducing a target fractionated component in a sample component separated by a column through a carrier gas, liquefying the fractionated component, and collecting the liquefied component. In this sorter, a liquefaction part having a slot is provided in at least one place of the collection tube, and the sorter component that moves through the slot can be insulated, so that the sorter can be separated with a simple structure. Liquefaction is promoted to streamline sorting and improve efficiency. According to the ninth aspect of the present invention, the liquefaction portion can be seen through from the outside so that the liquefied state of the preparative component can be easily confirmed visually from the outside.

In a tenth aspect of the present invention, a viewing window or a viewing space is provided facing the liquefying section so that visual observation of the liquefied state can be realized.
The invention of claim 11 is provided with a monolithic liquefaction detection piece in the slot portion, and when the liquefied detection piece holds a liquefied fractionated component, it can be discolored, and depending on whether the liquefaction detection piece is discolored, The liquefied state can be easily confirmed. Moreover, the efficiency of adiabatic expansion is increased and the surface area is increased by the through-holes of several μm to 40 μm inside the monolithic liquefaction detection piece, thereby increasing the collection efficiency.
According to a twelfth aspect of the present invention, a light source or a liquefaction detection sensor is installed in the vicinity of the liquefaction unit so that the liquefaction state of the preparative component can be easily and reliably confirmed.
According to a thirteenth aspect of the present invention, the liquefaction detection sensor is a photosensor capable of detecting reflected light in the liquefaction portion of the collection tube, or a temperature measurement sensor capable of detecting a temperature change in the liquefaction portion of the collection tube as an electrical signal. An optimum liquefaction detection sensor can be selected in accordance with the fractionation component or the fractionation conditions.

According to a fourteenth aspect of the present invention, the photosensor includes a light emitter capable of irradiating light to the liquefaction detection piece, and a light receiver capable of detecting reflected light from the liquefaction detection piece, and is separated by a detection signal of the light receiver. Calculate the reflectivity of the liquefaction detection piece under the preparative component introduction, and when the liquefaction of the preparative component is detected via the calculated reflectivity, the flow path of the next preparative component is opened to enable the preparative component. The liquefaction detection can be accurately and automatically performed, and it can be used in place of a conventional detector such as FID to automate sorting and reduce the cost of the sorting apparatus.
According to a fifteenth aspect of the present invention, the temperature measuring sensor is provided so as to be able to detect a temperature change of the temperature measuring section as an electric signal, and is provided with an arithmetic unit capable of inputting the detection signal. The flow of the next fractionation component is opened via the detection signal, enabling the fractionation, and the liquefaction state of the fractionation component can be accurately and reliably detected, and the detection signal can be used accurately and easily. Like

According to a sixteenth aspect of the present invention, an open / close valve inserted in the flow path of the preparative component can be opened and closed via the liquefaction detection signal, and the flow path is opened accurately and surely to improve the accuracy of sorting. I am doing so. According to a seventeenth aspect of the present invention, a mid-low temperature oven is provided inside the viewing window, a defroster fan is disposed outside the viewing window, and air can be blown to the outer surface of the viewing window, thereby clouding the viewing window. It can be solved.
In the invention of claim 18, after the visual confirmation of the liquefaction completion time of the fractionated component, the on-off valve can be opened, the residue of the fractionated component remaining in the flow path of the collecting pipe is actually confirmed, To prevent the occurrence of accidents.
According to a nineteenth aspect of the present invention, the light source can be turned on when the on-off valve is opened so that the liquefied state can be easily confirmed.

According to a twentieth aspect of the present invention, it is possible to introduce a carrier gas having a predetermined pressure from the upstream side of the collecting pipe, and to prevent contamination by upstreamly plugging the upstream side of the collecting pipe with the carrier gas. ing. In addition, by introducing fresh carrier gas at that time, contamination of the sample to be collected by the carrier gas is prevented, and the reliability of the sorting is improved.
The invention of claim 21 enables introduction of a carrier gas of a predetermined pressure from the upstream side of the collection tube, and introduction of a carrier gas of a predetermined pressure from the downstream side of the collection tube. The side is also plugged so that contamination is reliably prevented.

According to the invention of claim 22, a conduit capable of introducing a gas sample is arranged vertically, a liquefying portion having a slot portion is provided at at least one location of the conduit, and the gas sample moving through the slot portion is insulated. A liquefaction detection sensor is arranged facing the liquefaction section so as to be inflatable, and the gas sample can be reliably liquefied with a simple configuration, and the liquefaction state can be reliably detected. According to a twenty-third aspect of the present invention, a liquefaction detection piece having a monolith structure is provided in the slot portion to further promote liquefaction of the gas sample and improve accuracy of liquefaction determination.
According to a twenty-fourth aspect of the present invention, the liquefying portion is provided so as to be seen through from the outside so that the liquefied state can be confirmed visually. According to a twenty-fifth aspect of the present invention, the liquefaction detection sensor is a photosensor capable of detecting reflected light in the liquefaction part of the collection tube, or a temperature measurement sensor capable of detecting a temperature change in the liquefaction part of the collection tube as an electrical signal. An optimum liquefaction detection sensor can be selected in accordance with the fractionation component or the fractionation conditions. According to a twenty-sixth aspect of the present invention, the temperature measuring sensor is disposed immediately below the liquefaction detection piece so as to reliably come into contact with the liquefied liquid droplet so that the liquefaction state can be reliably detected.

In the invention of claim 1, since the liquefaction state of the preparative component introduced into the collection tube is confirmed or detected, the fractionation is uniformly determined only by chromatogram information. Thus, it is possible to solve the conventional problem that the timing of sorting tends to be delayed, to accurately sort under actual liquefied conditions, and to obtain the reliability thereof.
In the invention of claim 2, since the liquefaction state of the fractionated component is visually confirmed or detected by a liquefaction detection sensor, the liquefaction state can be confirmed accurately and simply.
In the invention of claim 3, since the fractionated component introduced into the collecting tube is adiabatically expanded and liquefied, it can be liquefied surely and easily by a simple means.

In the invention of claim 4, after confirming or detecting the completion of liquefaction of the preparative component introduced into the collection tube, the collection channel for the next preparative component is opened, and the next preparative component is placed in a predetermined collection tube. Since it is introduced, it is possible to stop the current fractionation and switch to the fractionation of the next fractionation component to prevent its contamination. In the invention of claim 5, since the carrier gas having a predetermined pressure is introduced from the upstream side of the collection tube, contamination is prevented by plugging the upstream side of the collection tube with the carrier gas. be able to. In addition, by introducing a fresh carrier gas at that time, contamination of the sample to be collected by the carrier gas can be prevented, and the reliability of the sorting can be improved.
According to the sixth aspect of the present invention, since the carrier gas having a predetermined pressure is introduced from the upstream side of the collection tube and the carrier gas having a predetermined pressure is introduced from the downstream side of the collection tube, Contamination can be reliably prevented by plugging the downstream side portion.

  According to a seventh aspect of the present invention, the liquefaction detection sensor is a photosensor capable of detecting reflected light in the liquefaction part of the collection tube, or a temperature measurement sensor capable of detecting a temperature change in the liquefaction part of the collection tube as an electrical signal. Therefore, an optimal liquefaction detection sensor can be selected according to the fractionation component or the fractionation conditions. In the invention of claim 8, since a liquefying portion having a slot portion is provided in at least one place of the collecting tube, and the fractionation component moving through the slot portion can be insulated, it is possible to sort with a simple structure. It is possible to promote liquefaction of components, rationalize sorting and improve efficiency. According to the ninth aspect of the present invention, since the liquefying portion can be seen through from the outside, the liquefied state of the fractionated component can be easily confirmed from the outside visually.

According to the tenth aspect of the present invention, the observation window or the observation space is provided so as to face the liquefaction portion, so that visual observation of the liquefied state can be realized.
According to the eleventh aspect of the present invention, since the liquefaction detection piece having a monolith structure is provided in the slot portion, and the liquefaction detection piece holds the liquefied preparative component, it is possible to change the color. Thus, the liquefied state can be easily confirmed. Moreover, the efficiency of adiabatic expansion can be increased and the surface area can be increased by the through-holes of several μm to 40 μm inside the monolithic liquefaction detection piece, thereby increasing the collection efficiency.
In the twelfth aspect of the present invention, since the light source or the liquefaction detection sensor is installed in the vicinity of the liquefaction unit, the liquefaction state of the fractionated component can be easily and reliably confirmed.
According to a thirteenth aspect of the present invention, the liquefaction detection sensor is a photosensor capable of detecting reflected light in the liquefaction part of the collection tube, or a temperature measurement sensor capable of detecting a temperature change in the liquefaction part of the collection tube as an electrical signal; Therefore, an optimal liquefaction detection sensor can be selected according to the fractionation component or the fractionation conditions.

According to a fourteenth aspect of the present invention, the photosensor includes a light emitter capable of irradiating light to the liquefaction detection piece, and a light receiver capable of detecting reflected light from the liquefaction detection piece, and is separated by a detection signal of the light receiver. Since the reflectance of the liquefaction detection piece under the preparative component introduction is calculated, and when the liquefaction of the preparative component is detected via the calculated reflectivity, the flow of the next preparative component is opened to enable the preparative separation. While component liquefaction can be detected accurately and automatically, it can be used in place of a conventional detector such as an FID to automate sorting and reduce the cost of a sorting apparatus.
According to a fifteenth aspect of the present invention, the temperature measuring sensor is provided so as to be able to detect a temperature change of the temperature measuring section as an electric signal, and is provided with an arithmetic unit capable of inputting the detection signal. Since the flow of the next fractionation component is opened via the detection signal, and the fractionation is possible, the liquefaction state of the fractionation component is accurately and reliably detected, and the detection signal is used accurately and easily. In the invention of claim 16, since the on-off valve inserted in the flow path of the preparative component can be opened and closed via the liquefaction detection signal, the flow path is opened accurately and surely, Accuracy can be achieved.

In the invention of claim 17, a mid-low temperature oven is provided inside the viewing window, a defroster fan is disposed outside the viewing window, and air can be blown to the outer surface of the viewing window. Can be eliminated.
Since the invention according to claim 18 allows the opening / closing valve to be opened after visually confirming the end of liquefaction of the preparative component, the residual of the preparative component in the flow path of the collecting pipe is actually confirmed, It is possible to reliably prevent the occurrence of contamination.
According to the nineteenth aspect of the present invention, since the light source can be turned on when the on-off valve is opened, the liquefied state can be easily confirmed.

According to the invention of claim 20, since the carrier gas having a predetermined pressure can be introduced from the upstream side of the collection tube, contamination is prevented by sealing the upstream side of the collection tube with carrier gas. be able to. In addition, by introducing a fresh carrier gas at that time, contamination of the sample to be collected by the carrier gas can be prevented, and the reliability of the sorting can be improved.
The invention of claim 21 enables introduction of a carrier gas of a predetermined pressure from the upstream side of the collection tube and introduction of a carrier gas of a predetermined pressure from the downstream side of the collection tube. Contamination can be surely prevented by plugging the upstream and downstream sides.

According to the invention of claim 22, a conduit capable of introducing a gas sample is arranged vertically, a liquefying portion having a slot portion is provided at at least one location of the conduit, and the gas sample moving through the slot portion is insulated. Since the liquefaction detection sensor is disposed facing the liquefaction portion so as to be expandable, the gas sample can be reliably liquefied with a simple configuration, and the liquefaction state can be reliably detected. In the invention of claim 23, since the liquefaction detection piece having the monolith structure is provided in the slot portion, it is possible to further promote the liquefaction of the gas sample and improve the accuracy of the liquefaction determination.
In the invention of claim 24, since the liquefying portion is provided so as to be seen through from the outside, the liquefied state by visual observation can be confirmed.

  According to a twenty-fifth aspect of the present invention, the liquefaction detection sensor is a photosensor capable of detecting reflected light in the liquefaction part of the collection tube, or a temperature measurement sensor capable of detecting a temperature change in the liquefaction part of the collection tube as an electrical signal; Therefore, an optimal liquefaction detection sensor can be selected according to the fractionation component or the fractionation conditions. In the twenty-sixth aspect of the present invention, since the temperature sensor is disposed directly below the liquefaction detection piece, the liquefied liquid droplet can be reliably contacted and the liquefied state can be reliably detected.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an illustrated embodiment in which the present invention is applied to a sorting method and a GC sorting apparatus suitable for sorting samples such as foods and fragrances will be described. In FIGS. 1 to 10, 1 is a GC, and a carrier gas cylinder A sample injector, a separation column and detector, a recorder (not shown) and the like are provided, and the sample components eluted in the separation column are introduced into the fractionation device 3 via the transfer line 2.
In the embodiment, an FID (hydrogen flame ion detector) is used as the detector, and this is arranged after the separation column.
The sorting device 3 is installed on a work table 4, a personal computer 5 is installed at a position close to the sorting device 3, and sample components displayed on the display 6 by the recorder. The chromatogram 7 similar to the chromatogram can be monitored.

The sorting device 3 is formed in a substantially vertically long box shape, and a door 8 can be opened forward through a handle 9 at a middle high portion of the front surface thereof, so that a collecting tube described later can be taken in and out. In the center of the door 8, a wide rectangular window 10 that is a viewing window made of a glass plate or an acrylic resin plate is provided.
A medium / low temperature oven 11 closed by the door 8 and a high temperature oven 12 immediately above the compartment are formed in the middle and upper part of the sorting device 3, and a heat insulating space is formed therebetween. 21 is interposed.

  Among them, a cooling fan 13 with a Peltier element is provided as a cooling means on the back of the medium / low temperature oven 11, and the interior can be cooled to a minimum of 0 ° C. or by introducing a refrigerant such as liquid nitrogen to a lower temperature. ing. In addition, a heater 14 is provided in the lower part of the high-temperature oven 12 so that the inside can be heated up to 300 ° C.

A lower portion of the medium / low temperature oven 11 is formed to project forward, and a defroster fan 15 is provided at an upper end of the projecting portion directly below the see-through window 10, so that warm air as room air is supplied to the see-through window 10. The air can be directed.
In the figure, reference numeral 16 denotes a plurality of fraction change-over switches provided in the middle part of the projecting portion, which are arranged in the number corresponding to the number of collection flow paths or solenoid valves, which will be described later, and correspond by pressing the change-over switch 16. The solenoid valve is opened so that the corresponding collecting flow path can be switched.

At that time, the pressing time (time) of the switch 16 can be recorded in a recording device (not shown) inside the sorting device 3, and the recorded operation time of the change-over switch 16 is recorded at the next sorting of the same sample. Based on this, each collection channel is automatically switched to enable automated sorting.
17 is a pressure gauge for head press gas, 18 is a pressure gauge for back press gas, 19 is a pressure gauge, and 20 is a leg provided at the bottom of the fractionation device 3.

Two manifolds 22 and 23 capable of branching a plurality of flow paths are provided in the high-temperature oven 12, and the manifold 22 is configured as a 14-way manifold, and the manifold 23 is configured as a 7-way manifold.
The manifold 22 includes seven component outlet ports P _{1 to} P ₇ communicating with the transfer line 2 and seven gas injection ports Pa to Pg communicating with the manifold 23. The pairs are arranged in close proximity to the peripheral surface of the manifold 22 and are in communication with each other.

Also, the manifold 23 head pressing gas source as a carrier gas, in the embodiment helium gas or nitrogen gas (cylinder) communicates six Gasupo an inert gas - has DOO Pg ₁ ~Pg _6, each of these Press gas distribution pipes 24 to 30 are connected between the ports Pg ₁ to Pg ₆ and the gas injection ports Pa to Pg.
In the figure, 31 is a head press gas conduit having one end connected to a manifold 23 and the other end connected to a head press gas source. A pressure regulator 32 and a pressure gauge 33 are inserted into the pipe 31.

One end of the connecting pipes 34 to 40 is connected to the component outlet ports P _{1 to} P ₇ , and the other end is connected to the connection joint 41, and a transparent glass tube is used as a sorting container for the connection joint 41. The collection pipes 42-48 made from are connected. In this case, the connection joint 41 can be constituted by a three-way valve, and the head gas can be introduced from one port to the other.
The collecting tubes 42 to 48 are accommodated in the medium / low temperature oven 11, which is formed in the same abbreviation or U shape, and the other end is bent into a substantially U shape. A discharge pipe 49 is connected to the ends of the portions 42a to 48a.

A slot portion 50 as a liquefying portion is formed inside the collecting tubes 42 to 48 positioned at the upper part of the see-through window 10, and the through holes 51 in the tubes 42 to 48 are locally reduced in diameter. A substantially white liquefaction detection piece 52 is attached to the reduced diameter portion 51a.
The liquefaction detection piece 52 is formed in a substantially truncated cone shape by a monolithic quartz glass material, and a large number of through-holes 53 of several μm to 40 μm are formed in the inside thereof.

  Three-way solenoid valves 55 to 61, which are on-off valves, are connected to the downstream side of the respective discharge pipes 49 through filters 54, and connecting pipes 64 communicating with the back press gas pipes 63 are connected to the respective normally open ports 62. Helium gas or nitrogen gas, which is connected and is the same carrier gas as the head press gas, can be pumped to the downstream ends of the collection tubes 42 to 48.

  The solenoid valves 55 to 61 are automatically and manually operable via the fraction changeover switch 16. In the embodiment, the solenoid valves 55 to 61 are set to be manually operable, and the target vaporized components are guided to the collection tubes 42 to 48. After passing through the slot 50, the state of adiabatic expansion and liquefaction is visually observed, and after completion of the liquefaction, the solenoid valves 55 to 61 corresponding to the flow path of the next component to be collected are opened. I have to.

  Then, the predetermined solenoid valves 55 to 61 are opened, the downstream side of the corresponding discharge pipe 49 is opened, the predetermined collection pipes 42 to 48 connected to the discharge pipe 49, and the corresponding connection pipes 34 to 40. And the next component to be collected introduced into the manifold 22 is led from the connecting pipes 34 to 40 to the collecting pipes 42 to 48, and the liquid component 65 liquefied through the slot 50. Can be collected in the collection tubes 42 to 48.

In the figure, reference numeral 66 denotes a normally closed port of the electromagnetic valves 55 to 61. An outlet pipe 67 is connected to the normally closed port 67, and the pipe 67 is connected to a discharge pipe 69 having a mass flow sensor 68 interposed therebetween. The head and the back press gas and the carrier gas introduced from the GC 1 can be discharged to the outside through the discharge pipe 69.
The back press gas conduit 63 communicates with the gas source of the head press conduit 31, and a pressure regulator 70, a pressure gauge 71, and a three-way electromagnetic valve 72 as a relief valve are inserted in the conduit 63.

  In addition, 73 in the figure is a line heater in which the outside of the transfer line 2 piped between the GC 1 and the sorting device 3 is covered with a heat insulating material, etc., 74 is a collection pipe 42 to 48 and a discharge pipe 49. A trap made of activated carbon or the like interposed between them, 75 is a manifold, 76 is a power source, 77 is a wiring board, and 78 is an operator's eyes.

  The fractionation method, the fractionation device, and the liquefaction determination device configured as described above require a plurality of collection tubes 42 to 48 corresponding to the number of fractionation components as a fractionation container, and the production of the collection tubes 42 to 48 is performed. A transparent glass tube is formed in an abbreviated letter shape or U shape, a slot portion 50 is formed at a predetermined position on the straight tube side, and a liquefaction detection piece 52 is attached to the reduced diameter portion 51a. The liquefaction detection piece 52 has a monolithic structure and is formed of a substantially white quartz glass material in the shape of a truncated cone, and is fitted to the reduced diameter portion 51a.

The produced collection tubes 42 to 48 are installed in the medium / low temperature oven 11 with the door 10 opened, the straight tube side end portion is inserted into the connection joint 41, and the upper end portion thereof is insulated. The slot 50 is positioned so that the slot 50 can be seen through the see-through window 10, and a discharge pipe 49 is connected to one end of the collecting pipes 42 to 48 on the folding side, and the other end of the discharge pipe 49 is connected. The solenoid valves 55 to 61 are connected to the.
The solenoid valves 55 to 61 have one end of a connecting pipe 64 connected to the normally open port 62, the other end of the connecting pipe 64 connected to a back press gas conduit 63, and each normally closed port 66. One end of the outlet pipe 67 is connected, and the other end is connected to the discharge pipe 69.

On the other hand, the manifolds 22 and 23 are installed in the high-temperature oven 12, the transfer line 2 derived from the GC 1 is connected to the manifold 22, and the head press gas conduit 31 is connected to the manifold 23.
One end of the connecting pipes 34 to 40 is connected to the component outlet ports P _{1 to} P ₇ of the manifold 22, the other end is connected to the connecting joint 41, and the connecting pipe 24 is connected to the gas injection ports Pa to Pg. ˜30 are connected to one end and the other end is connected to the gas ports Pg ₁ to Pg ₆ of the manifold 23.

The sorting device 3 manufactured in this way is formed in a vertically long box shape, and this is placed on the work table 4 installed in the proximity of the GC 1 and used.
In addition, a personal computer 5 is installed in the vicinity of the sorting device 3, and the same chromatogram 7 is monitored on the display 6 together with the chromatogram displayed on the recorder of GC1.

In use, the sorting device 3 sets the high temperature oven 12 and the medium / low temperature oven 11 to a predetermined temperature according to the sample to be collected, and also collects the collecting tubes 42 to 48 for the components to be sorted. Is prepared and attached to a predetermined position of the medium / low temperature oven 11.
Thereafter, the head press and the back press gas, in the embodiment, helium gas, are fed into the head press gas conduit 31 and the back press gas conduit 63 from a common gas source.

Of these, the head press gas is fed into the manifold 23 from the head press gas conduit 31 and is divided into gas pipes Pg ₁ to Pg ₆ into connecting pipes 24 to 30, and gas injection ports Pa to the manifold 22. It is led to Pg, merges with each component passage from the ports Pa to Pg, is sent out from the component outlet ports P _{1 to} P ₇ to the connecting pipes 34 to 40, and is connected to the collecting pipe 42 through the connection joint 41. Move to one end of ~ 48.

On the other hand, the back press gas is led from the back press gas conduit 63 through the connecting pipe 64 to the electromagnetic valves 55 to 61, sent from the electromagnetic valves 55 to 61 to the discharge pipe 49, and collected in the collecting pipes 42 to 48. Move to the other end.
Therefore, the collection pipes 42 to 48 receive a pressure of the head press gas and the back press gas at both ends or the entire area thereof and are placed in a kind of plugged state.

Under such circumstances, the carrier gas is fed into the GC 1 and, for example, a perfume or food gas or liquid sample is injected into the carrier gas from the sample introduction portion as a preparative sample, and this is separated into the separation column together with the carrier gas. To introduce.
The sample components are separated for each component by a separation column, and this is vaporized and moved through a carrier gas, guided to a detector, detected by the detector, and a chromatogram is displayed on a recorder by the detection signal, This chromatogram is monitored on the display 6 of the personal computer 5.

The vaporized sample components are transferred to the manifold 22 of the sorting device 3 while moving through the transfer line 2 while being separated from the GC 1 for each component.
Among these, when the peak of the component having the shortest retention time among the components to be collected is confirmed in the chromatogram, it is set in advance corresponding to the sorting route of the low boiling point component at the time of confirmation. A solenoid valve such as the solenoid valve 55 is manually opened.

In this way, the discharge pipe 49 and solenoid valve 55, connecting tube 34 and the outlet port and the collection tube 42 - only path DOO P ₁ is opened, the carrier gas from GC1 is, the head pressing gas and the back press Gas At the same time, it is introduced into the collecting tube 42. Therefore, since the low boiling point component cannot flow into another sorting path, so-called contamination in which the component flows into another sorting path is prevented in advance.

Therefore, a short component of the retention time transfer - to move the line 2 and is guided to the manifold 22, the component outlet port together with a carrier gas - fed from preparative P ₁ to the connecting pipe 34, which is connected joint It moves to the upper end part of the collection pipe 42 through 41.

After the opening operation of the electromagnetic valve 55, the operator visually observes the upper end portion and the middle / high portion of the heat insulating space 21 and the collection tube 42 located inside the see-through window 10.
In this case, since the low boiling point component is still in a vaporized state and there is no sign of liquefaction at the upper end portion of the collection tube 42 after passing through the high-temperature oven 12, the middle and high portions where the slot portion 50 is located are visually observed. Observe.

When the low boiling point component in the vaporized state moves downward from the upper end portion of the collection tube 42 and moves to the medium / low temperature oven 11, it gradually cools, and further passes through the reduced diameter portion 51a of the slot portion 50. Boiling components are liquefied by adiabatic expansion. This liquefaction state is confirmed by observing the presence or absence of liquid droplets around the slot 50.
For example, when the component has a medium boiling point, the droplets gather and appear at a position directly above the slot 50, and when the component has a low boiling point, the droplet appears immediately below the slot 50. In this case, visual observation can be performed easily and clearly.

  In addition, in this embodiment, since the milky white or gray liquefaction detection piece 52 having a monolith structure is attached to the slot portion 50, when the low boiling point component in the vaporized state moves through the portion, the component becomes fine. The through-hole 53 is moved, the adiabatic expansion is enhanced, and liquefaction is promoted.

  And when the droplet contacts the liquefaction detection piece 52 by the liquefaction, the liquefaction detection piece 52 changes from milky white to gray to translucent or transparent. Therefore, the operator can observe the liquefaction state more easily and more accurately than by observing the presence or absence of liquid droplets in the above-described slot portion 50 by visually observing and confirming the change of the liquefaction detection piece 52.

The low-boiling component liquid droplets thus liquefied flow down along the inner wall of the collection tube 42 and stay at the bottom of the bent portion 42a, and the liquefied component 65 is collected. This situation is as shown in FIG.
In this way, the liquefaction state of the low-boiling component was observed, and after the start of liquefaction, the generation of the liquid droplets stopped, or the transparent or translucent color of the liquefaction detection piece 52 disappeared, and the original milky white color was observed instead. By the way, the end or stop of the liquefied state is confirmed, and the switch 16 corresponding to the solenoid valve, for example, the solenoid valve 56 corresponding to the sorting path of the next low-boiling component or the high-boiling component, which is the next sorting component, is operated. Open the valve.

In this way, the path of the outlet port P ₁ is blocked, and instead, only the paths of the electromagnetic valve 56 and the discharge pipe 49, the collection pipe 43 and the connecting pipe 35, and the outlet port P ₂ are opened. Carrier gas from GC1 is introduced into the collection tube 43 together with the head press gas and the back press gas. Therefore, since the low boiling point component cannot flow into another sorting path, so-called contamination in which the component flows into another sorting path is prevented in advance.

Therefore, the next low-boiling components transfer - to move the line 2 and is guided to the manifold 22, the next low-boiling component outlet port together with a carrier gas - fed to the connecting pipe 35 from the preparative P _2, which is It moves to the upper end of the collection tube 43 via the connection joint 41.

After opening the solenoid valve 56, the operator visually observes the middle and high portions of the collection tube 43 located inside the fluoroscopic window 10 to determine the liquefaction state of the next component in the presence or absence of liquid droplets around the slot 50. Confirm by observing.
In the case of the embodiment, the confirmation is made easy and accurate by observing a transparent or translucent change of the liquefaction detection piece 52.

The liquid droplet of the next component thus liquefied flows down along the inner wall of the collection tube 43 and stays at the bottom of the bent portion 43a, and the liquid component 65 is collected.
Thereafter, the liquefaction state of the next component was observed, and after the start of liquefaction, the generation of the droplets stopped, or the transparent or translucent color of the liquefaction detection piece 52 disappeared, and instead the original milky white was observed instead. After confirming the end or stop of the liquefied state, an electromagnetic valve, for example, an electromagnetic valve 57 corresponding to a fractionation path of the next fractionation component, for example, a high boiling point component, is manually opened.

In this way, the solenoid valve 57 and the discharge pipe 49, connecting pipe 36 and the outlet port and the collection tube 44 - only path DOO P ₃ is opened, the carrier gas from GC1 is, the head pressing gas and the back press Gas At the same time, it is introduced into the collecting tube 44. Therefore, since the low boiling point component cannot flow into another sorting path, so-called contamination in which the component flows into another sorting path is prevented in advance.

Therefore, the high-boiling components transfer - to move the line 2 and is guided to the manifold 22, the high-boiling components exit port along with a carrier gas - fed to the connecting pipe 36 from the preparative P _3, which is connected joint It moves to the upper end part of the collection tube 44 through 41.

After the opening operation of the electromagnetic valve 57, the operator visually observes the upper end portion of the collecting tube 44 located inside the heat insulating space 21, and confirms the liquefied state of the high boiling point component.
In this case, since the high boiling point component generally liquefies immediately at a temperature below the boiling point, it is already liquefied in the slot portion 50 located in the medium / low temperature oven 11, and observation in the slot portion 50 is unnecessary. Become.

  Therefore, when the high boiling point component in the vaporized state moves from the connecting pipe 36 to the upper end portion of the collecting pipe 44 through the connection joint 41, the collecting pipe 44 comes into contact with the air in the heat insulating space 21 and is cooled and liquefied. To do. This liquefied state is confirmed by observing the presence or absence of droplets in the collection tube 44.

  The liquid droplets of the high boiling point component thus liquefied flow down along the inner wall of the collection tube 44, pass through the liquefaction detection piece 52 and the slot portion 50, and stay at the bottom of the bent portion 42a to stay in the liquid component 65. To collect.

  Thus, the liquefaction state of the high-boiling component is observed, and after the start of liquefaction, when the generation of the liquid droplets is stopped, the end or stop of the liquefaction state is confirmed, and the next high-boiling component, which is the next fractionation component, is separated. The solenoid valve corresponding to the intake path, for example, the solenoid valve 57 is opened by operating the switch 16.

  Hereinafter, when the predetermined sample components are liquefied and collected in the collection tubes 42 to 48 in the order of separation, and the sample components of the GC 1 are separated, the sorting is finished, the door 10 is opened, and the collection tube 42 is opened. -48 are taken out and each collected liquid sample 65 is collected.

In this way, the present invention visually observes the liquefied state of the preparative component, confirms the end of the liquefied state, operates the solenoid valve, ends the preparative of the component, and instead separates the next preparative component. Therefore, the fractionated components can be sorted without waste, and the mixing of different components can be prevented, so that accurate fractionation without contamination can be performed.
In addition, the actual liquefaction state of the preparative components was visually observed from the start to the end of the liquefaction, and the sample was collected for confirmation. Can be done.
Accordingly, it is possible to eliminate the unreasonableness caused by the determination of the sorting time based only on the chromatogram information as in the prior art, and to perform the sorting with reasonable and high reliability. In particular, this effect is effective for fractionation of high-boiling components in which the liquefaction time of the fractionated components is delayed as the boiling point increases.

In addition, if the time for introducing the next preparative component is close to the time of introduction of the current preparative component, there is a time when both preparative components are mixed. Without confirming the end of the collection, the collection flow path can be switched, opened, and introduced only for the time mixed in the predetermined waste liquid collection pipe.
Then, after the mixing time is over, the collection flow path for the next fractionation component is opened, so that contamination of both components can be prevented.

On the other hand, at the time of fractionation, the medium / low temperature oven 11 is cooled to about 0 ° C., moisture in the air condenses on the surface of the viewing window 10 and condensation occurs, and it is difficult to see the collection tubes 42 to 48 housed inside. Therefore, it may be difficult to observe the liquefied state.
In such a case, the defroster fan 15 is driven, and indoor air (warm air) is blown onto the fluoroscopic window 10 to heat the fluoroscopic window 10 to eliminate condensation and restore the intended transparent state. Observation of the period becomes possible.

FIG. 10 shows the experimental results of the present invention and shows the contamination prevention effect of the present invention.
That is, FIG. 10 shows a comparison of chromatograms in which 21 μL of the stock solution was introduced into the preparative device 3, each of the collection tubes 42 to 48 was desorbed with 5 mL of acetone, reconcentrated to 1 mL, and individually injected with 1 μL. The figure (a) shows the chromatogram of stock solution, and the figure (b) shows each chromatogram after fractionation.
Comparing these chromatograms, FIG. 5B shows that each peak is sharply and neatly dispersed, there is no mixing or overlapping of different components, and there is no contamination.

11 to 21 show other embodiments of the present invention, and the same reference numerals are used for the components corresponding to those of the above-described embodiments.
Among these, FIG.11 and FIG.12 shows the 2nd Embodiment of this invention, This embodiment is behind the slot part 50 and the upper end part of the collection pipes 42-48 installed in the fractionation apparatus 3. Light sources 79 and 80 such as green, yellow or blue LEDs are attached, and the light sources 79 and 80 of the corresponding collecting tubes are turned on in conjunction with the ON operation of the electromagnetic valves 55 to 61. The change state of the droplet or the liquefaction detection piece 52 is made easy to see and the liquefaction state can be easily visually observed.

  For example, when a green LED is turned on as the light sources 79 and 80, the droplet becomes transparent in the low boiling point side slot portion 50, so that it is easy to confirm, and the liquefaction detection piece 52 is always white, When contacted, the green light of the LED is transmitted and becomes like a melon sherbet, making it easy to check. The same applies to the light source 80 on the high boiling point side, and the confirmation of the droplets becomes easy.

FIGS. 13 to 16 show a third embodiment of the present invention, in which the liquefaction detection piece 52 is implemented as a liquefaction detection sensor.
That is, the liquefaction detection piece 52 has a monolithic structure made of quartz glass, usually exhibits a white color, and changes to transparent or translucent when it contacts (holds) the liquid.
Therefore, by detecting the transmitted light or reflected light, or the transmittance or reflectance, the presence / absence of liquid retention or the physical property of the member through which the reflected light is transmitted is detected.

  Among these, FIG. 13 is a conduit into which a sample gas can be introduced. For example, the monolithic liquefaction detection piece 52 having a rod shape or a drum shape is fitted into the slot portion 50 of the collection tube 42, while the collection gas is collected. For example, a light emitter 81 that constitutes a photosensor that is a liquefaction detection sensor capable of emitting red light and a light receiver 82 that can receive the reflected light are disposed at a position close to the tube 42, and a light reception signal of the light receiver 82 is disposed. Can be input to the calculator 83 such as a personal computer incorporated in the GC 1 or the sorting device 3.

  The calculator 83 calculates the reflectance based on information when the carrier gas is introduced or passed on the condition that the received light signal is input, and uses the calculated reflectance signal as a monolith sensor signal. The GC1 recorder or personal computer 5 can be input and used as a detector or monitoring. In this case, when the reflected light passes through a gas such as a carrier gas, the reflectivity is higher than the reference reflectivity when the carrier gas passes through the reflection medium, and the liquid is transmitted. In this case, it was confirmed that the reflectance decreased.

The inventor actually examined the consistency between the monolith sensor signal and the chromatogram (chromatographic data) based on the above findings, and obtained the results shown in FIG.
That is, acetone, hexane, heptane, octane, nonane, and limonene were used as sample components, and 1 μL of each was injected into a packed column of GC1, and the split of the fractionation part was fractionated at 5:30, Components separated by the column were detected by FID, and a chromatogram as shown in FIG. 15 was obtained based on the detection signal.
On the other hand, in the sorting device 3, the red light is irradiated to the slot portions 50 of the corresponding collecting tubes 42 to 48, the reflected light is input to the calculator 83 every moment, the reflectance is calculated, The calculated reflectance was input to the recorder and plotted on the chromatograph as a monolith sensor signal.

Therefore, when FIG. 15 is verified, a clear peak in which the monolith sensor signal protrudes to the + side is formed at a substantially central position of the peak width of each sample.
In this case, since the split ratio was 5:30 in the above experiment and the amount of the sample component was very small, liquefaction was observed only in the limonene peak that was most liable to liquefy, and the protrusion protruded to one side at the central position. It was seen. It was also confirmed that the monolith sensor signal appeared for every component at the peak position of the chromatogram.
Therefore, in this case, since it is suggested and confirmed that a gas sample such as a carrier gas has been introduced into or passed through the slot 50, it is possible to notify the start of analysis such as subsequent fractionation. By operating an analytical instrument or the like based on the monolith sensor signal, it becomes possible to construct rationalization and automation of the analytical system in place of the conventional detector such as FID.

In other words, FIG. 15 suggests that fractionation is possible based on the monolith sensor signal instead of the chromatogram.
That is, if the monolith sensor signal is monitored and the electromagnetic valve is opened at the position of the protrusion, the target component can be sorted in the embodiment described above, and the monolith sensor signal is used as such. This suggests that the monolith sensor signal functions equivalently to a conventional detector and that the detector can be omitted.

On the other hand, FIG. 16 shows the results of an experiment conducted under the same conditions except that the same sample as FIG. 15 was used and the amount of the sample was increased to 10 μL.
In this case, since the amount of the sample is increased as compared with FIG. 15, it is liquefied at the fractionation portion, and this appears to protrude toward the minus side at a substantially central position of the peak width of the chromatogram. Prove the characteristics of the signal. Therefore, instead of the conventional chromatogram information or detector based on the monolith sensor signal, it is possible to determine the fractionation time and to sort.

FIG. 14 shows an application form of FIG. 13 in which a light emitter 81 capable of emitting red light and a light receiver 82 capable of receiving the transmitted light are arranged with the slot 50 of the collection tube 42 interposed therebetween. The received light signal of the light receiver 82 can be input to the computing unit 83 such as a personal computer built in the GC 1 or the sorting device 3.
The computing unit 83 computes the amount of transmitted light based on information stored in advance on the condition that the received light signal is input, and uses the computed light amount signal as a monolith sensor signal to record the GC1 recorder or parameter. -It is possible to input to the sonal computer 5 to determine whether the fractionation component has been liquefied in the fractionation unit, and to accurately confirm whether or not the fractionation has been performed and the liquefaction time.

17 and 18 show a fourth embodiment of the present invention, which shows another embodiment of the collection tube 84. That is, instead of forming the collection tube 84 in the shape of a letter or U as described above, it is formed in a substantially straight tube shape, and the lower end side of the collection tube 84 is accommodated in a large-capacity storage tube 85, A reducing union 86 is attached to the upper end of the storage pipe 85.
Of these, in FIG. 17, three reducing unions 86 are used, the collection pipe 84 is supported by the unions 86, and one end of the discharge pipe 49 is attached to the side.
In FIG. 18, a normal reducing union 86 is used, and one end of the discharge pipe 49 is attached on the same axis of the union 86.
In any case, a large amount of waste liquid can be stored in the storage pipe 85, and can be used for a large capacity packed column.

  FIGS. 19 to 21 show a fifth embodiment of the present invention, which applies the above-described fourth embodiment, and arranges a substantially straight collecting tube 84 inside the fluoroscopic window 10, A slot 50 is formed on the top of the tube 84, a monolithic liquefaction detection piece 52 is arranged in the slot 50, and a temperature measuring sensor 87 is arranged directly under the detection piece 52. In this case, the liquefaction detection piece 52 can be omitted, and the temperature measuring sensor 87 can be disposed immediately below the slot portion 50. By doing so, the configuration can be simplified. In the embodiment, as the temperature sensor 87, a thermistor element that can detect a change in temperature as an electric change amount, in this case, as a change in electric resistivity, has a large specific resistance, and has a large change is used. Is drawn out from the lower end of the collecting tube 84, is led out from the nut side of the reducing union 86, and the lead wire 88 is fixed by appropriate means at the lead-out portion.

  And the signal of the said temperature measurement sensor 87 is input into the calculator 83, and this calculator 83 judges the presence or absence of the liquefaction state of the preparative component based on the calculation information stored in advance on the condition of the signal input, The determination or detection signal of the liquefied state can be output to the predetermined solenoid valves 55 to 61. The electromagnetic valves 55 to 61 are opened by the signal, and a carrier gas is introduced into a collecting tube inserted in a corresponding sorting path so that a predetermined sorting component can be introduced. Therefore, compared to the visual confirmation of the liquefaction state described above, the liquefaction state can be confirmed automatically and accurately, and the opening and closing of the solenoid valves 55 to 61 is automatically controlled to save labor, reduce analysis costs, and realize remote control. In addition, the light sources 79 and 80 as described above can be omitted, and the manufacturing cost can be reduced accordingly. Further, the computing unit 83 detects the arrival of the sorting component and records the arrival time in the storage circuit. By doing so, for example, when continuously sorting, the fluctuation of the recorded time is detected. By doing so, it becomes an index for judging the credibility of each sorting, and can be used for correcting the fractionation time of the target component based on the arrival time.

In the above-described embodiment, when the low boiling point component in the vaporized state, which is a preparative component, moves to the slot portion 50 and passes through the through-hole 53 of the liquefaction detection piece 52, adiabatic expansion is promoted and liquefied, immediately after liquefaction. In contact with the thermistor element 87. In this case, since the fractionated component generates heat immediately after being liquefied from the gas, the temperature of the thermistor element 87 is increased, and the electrical resistivity of the thermistor element 87 is decreased to form a peak. Thereafter, re-vaporization may occur, and the heat of the surface of the thermistor element 87 is deprived during vaporization, so that the electrical resistivity of the thermistor element is increased and a peak having the opposite polarity to the above is formed. The peak polarity can be switched by an electric circuit that converts the resistivity into a voltage to form a peak. Even when the droplet does not touch directly, the same result is obtained because the same ambient temperature is measured.
Further, in this case, it is considered that the same peak can be obtained even if the thermistor element 87 is attached to the outer surface of the collection tube 84 corresponding to the liquefaction detection piece 52 without touching the droplet directly, although the change width is small. Therefore, the liquefaction state can be detected by the peak.
This liquefaction state can be visually confirmed by an external change of the liquefaction detection piece 52 as described above.

  Therefore, the inventor uses 1 μL of hexane as a sample component, injects it into a packed column, detects the component separated by the column by FID, and monitors the chromatogram (not shown) based on the detection signal. -Created as data. On the other hand, a temperature sensor 87 is arranged in the slot 50 of the collecting tube 84 as shown in FIG. 19 to measure a potential difference accompanying a change in the electrical resistivity of the thermistor element which is the temperature sensor 87. When the change in potential difference was distributed in association with the analysis time, experimental data as shown in FIG. 20 was obtained.

In the experimental data, the potential difference suddenly increases at the peak rising position (a). This is because the electrical resistivity of the thermistor element 87 rapidly decreases and the thermistor element 87 It is thought that the temperature rose rapidly.
As a cause thereof, when the sorting component moves through the slot 50 and the liquefaction detection piece 52 and is adiabatically expanded, and when this component is liquefied and the droplet comes into contact with the thermistor element 87, This is thought to be due to the absorption of the heat released during the liquefaction.
Therefore, since the preparative component is estimated to have been liquefied at the peak rising position (a), it was confirmed that the liquefied state of the preparative component can be detected by the position (a).

  After the liquefaction, re-vaporization occurs, the surface of the thermistor element 87 is deprived of heat and the temperature is lowered, so that the electrical resistivity is increased and the voltage between the terminals of the conductive wire 88 is lowered. Is reversed. This situation is as shown in FIG. 21, and the re-vaporization state is detected at the peak falling position (b) in the figure. It was confirmed that this tendency appears more remarkably as the amount of the preparative component introduced is larger.

  As described above, in the fifth embodiment, after the monitoring by the FID, the fractionation (fractionation) time is determined, and only the peak and its arrival time are confirmed by the temperature measuring sensor 87 each time. Thus, it is possible to obtain an index that improves the reliability and reliability of the sorting. Therefore, instead of the chromatogram, the temperature sensor signal can be used for sorting, and the construction of an analysis system that omits the FID can be promoted. On the other hand, when performing analysis and fractionation using GC, the sorting time may be shifted for some reason. In particular, when performing automatic fractionation, there is a situation where the target sample cannot be fractionated well. However, by automatically correcting the fractionation time based on the peak arrival time based on the temperature sensor signal, reliable fractionation can be achieved. It becomes possible to draw.

  Note that the temperature measuring sensor 87 of the fifth embodiment uses a sensor that can detect a change in electrical resistivity by using a temperature change as an electrical change amount. It is also possible to use one that can detect electric power.

  As described above, the present invention is suitable for the separation of samples such as foods and fragrances, prevents contamination of the sample separated by the chromatograph, reliably separates the target sample and separates it. The actual liquefaction time of the collected sample is visually confirmed, the timing of the sorting is confirmed accurately and reliably, the delay in sorting due to only the information from the chromatogram is prevented, and a highly reliable sorting is achieved. The accuracy and reliability of the visual confirmation can be improved, and the introduction or liquefaction state of the gas sample can be reasonably detected, which is suitable for a fractionation method, a fractionation device, and a liquefaction determination device.

It is a front view which shows the installation condition of the fractionation apparatus of this invention, and the personal computer for monitoring. It is a right view of the sorting apparatus shown in FIG. It is a front view which expands and shows the piping condition inside the fractionation apparatus shown in FIG. It is the fragmentary sectional view which expands and shows the principal part of FIG. 2, and has shown the arrangement | positioning condition of a defroster fan. It is a piping diagram which expands and shows piping conditions, such as a carrier gas conduit | pipe, a manifold, a collection pipe | tube, etc. which were applied to the fractionation apparatus shown in FIG. It is a piping diagram which shows the principal part of FIG.

It is sectional drawing which expands and shows the principal part of the collection pipe applied to the fractionation apparatus of this invention, and a liquefaction determination apparatus. It is sectional drawing which expands and shows the slot part of the principal part of FIG. It is sectional drawing which follows the AA line of FIG. It is an experiment figure of the contamination prevention effect by the fractionation apparatus of this invention, (a) shows the chromatogram of stock solution, (b) has shown the chromatogram of the sample by this invention apparatus.

It is sectional drawing which expands and shows the principal part of the liquefaction determination apparatus applied to the 2nd Embodiment of this invention. It is sectional drawing which expands and shows the slot part of the principal part of FIG. It is sectional drawing which expands and shows the principal part of the liquefaction determination apparatus applied to the 3rd Embodiment of this invention. It is sectional drawing which expands and shows the principal part of the liquefaction determination apparatus applied to the 3rd Embodiment of this invention.

It is an experimental view of the liquefaction determination apparatus applied to the third embodiment of the present invention, and shows the consistency of timing between the monolith sensor signal and the chromatogram. FIG. 6 is an experimental diagram of a liquefaction determination apparatus applied to the third embodiment of the present invention, showing the consistency of the timing of a monolith sensor signal and a chromatogram, and performing experiments by increasing the amount of the sample as compared with FIG. It is sectional drawing which expands and shows the principal part of the collection pipe | tube applied to the 4th Embodiment of this invention. It is sectional drawing which expands and shows the principal part of the collection pipe | tube applied to the 4th Embodiment of this invention.

It is sectional drawing which shows the principal part of the 5th Embodiment of this invention, arrange | positions the temperature sensor in the slot part of a collection pipe, determines the liquefaction state of a preparative component based on the electrical signal, The solenoid valve inserted in the path of the collection tube can be controlled to open and close by the liquefaction determination signal. It is an experimental data which shows the electric signal (electrical resistivity thru | or detection voltage) by the temperature sensor applied to the 5th Embodiment of this invention. It is another experimental data which shows the electrical signal (electrical resistivity or detection voltage) by the temperature sensor applied to the 5th Embodiment of this invention.

Explanation of symbols

3 Sorting device 10 Peeping window 11 Medium / low temperature oven 15 Defroster fan 21 Peeping space (insulation space)
42-48 collection tube, conduit

50 Slot part (liquefaction part)
52 Liquefaction detection piece 55-64 Open / close valve (solenoid valve)
79,80 Light source (LED)
81 Photosensor / Liquefaction detection sensor (light emitter)
82 Photosensor / Liquefaction detection sensor (receiver)
83 Calculator 87 Liquefaction detection sensor (temperature sensor)

Claims (26)

  In the fractionation method in which a target fractional component in a sample component separated by a column is introduced into a fractionation device, and the target fractional component is introduced into a predetermined collection tube to be liquefied and fractionated, A sorting method characterized by confirming or detecting a liquefied state of a sorting component introduced into a pipe and sorting.   The fractionation method according to claim 1, wherein the liquefaction state of the fractionation component is visually confirmed or detected by a liquefaction detection sensor.   The fractionation method according to claim 1, wherein the fractionation component introduced into the collection tube is liquefied by adiabatic expansion.   2. After confirming or detecting the end of liquefaction of the preparative component introduced into the collection tube, the collection channel for the next preparative component is opened, and the next preparative component is introduced into the predetermined collection tube. Sorting method.   The sorting method according to claim 1, wherein a carrier gas having a predetermined pressure is introduced from an upstream side of the collection pipe.   The sorting method according to claim 5, wherein a carrier gas having a predetermined pressure is introduced from an upstream side of the collection pipe, and a carrier gas having a predetermined pressure is introduced from a downstream side of the collection pipe.   3. The sensor according to claim 2, wherein the liquefaction detection sensor is a photosensor capable of detecting reflected light in the liquefaction part in the collection tube, or a temperature measurement sensor capable of detecting a temperature change in the liquefaction part in the collection tube as an electrical signal. How to take.   In a fractionation apparatus provided with a collection tube capable of introducing a target fraction component in a sample component separated by a column through a carrier gas, liquefying the fraction component, and collecting the liquefied component, A sorting apparatus comprising a liquefying section having a slot at at least one location of a collecting tube, and a sorting component moving through the slot capable of adiabatic expansion.   The sorting apparatus according to claim 8, wherein the liquefaction portion can be seen through from the outside.   9. The sorting apparatus according to claim 8, wherein a viewing window or a viewing space is provided facing the liquefying section.   9. The sorting apparatus according to claim 8, wherein a liquefaction detection piece having a monolith structure is provided in the slot portion, and the discoloration is enabled when the liquefaction detection piece holds a liquefied fractionation component.   The sorting apparatus according to claim 8, wherein a light source or a liquefaction detection sensor is installed in a proximity position of the liquefaction unit.   13. The component according to claim 12, wherein the liquefaction detection sensor is a photosensor capable of detecting reflected light in the liquefaction part in the collection tube or a temperature measurement sensor capable of detecting a temperature change in the liquefaction part in the collection tube as an electrical signal. Taking device.   The photosensor includes a light emitter capable of irradiating light to the liquefaction detection piece and a light receiver capable of detecting reflected light from the liquefaction detection piece, and liquefaction detection under the preparative component introduced by the detection signal of the light receiver. A reflectance of a piece is calculated, the liquefied state of the sorting component can be detected via the calculated reflectance, and the flow path of the next sorting component is opened via the detection signal, thereby enabling sorting. 13. The sorting apparatus according to 13.   The temperature measuring sensor is provided so that a temperature change of the temperature measuring section can be detected as an electrical signal, and an arithmetic unit capable of inputting the detection signal is provided, and the arithmetic unit detects a liquefied state of the preparative component, and the detection 14. The sorting apparatus according to claim 13, wherein the next sorting component flow path is opened via a signal to enable sorting.   The sorting device according to claim 14 or 15, wherein an on-off valve inserted in the flow path of the sorting component is provided so as to be openable and closable via the liquefaction detection signal.   11. The sorting apparatus according to claim 10, wherein a medium / low temperature oven is provided inside the viewing window, a defroster fan is disposed outside the viewing window, and air can be blown to the outer surface of the viewing window.   The sorting device according to claim 8, wherein the on-off valve can be opened after visually confirming a time when the sorting component is substantially liquefied.   The sorting device according to claim 12, wherein the light source can be turned on when the on-off valve is opened.   The sorting apparatus according to claim 8, wherein a carrier gas having a predetermined pressure can be introduced from an upstream side of the collection pipe.   21. The sorting apparatus according to claim 20, wherein a carrier gas having a predetermined pressure can be introduced from an upstream side of the collection pipe, and a carrier gas having a predetermined pressure can be introduced from a downstream side of the collection pipe.   A conduit capable of introducing a gas sample is arranged vertically, a liquefying portion having a slot portion is provided at at least one location of the conduit, and a gas sample moving through the slot portion is provided so as to be capable of adiabatic expansion. A liquefaction determination device, wherein a liquefaction detection sensor is arranged facing a part.   The liquefaction determination device according to claim 22, wherein a liquefaction detection piece having a monolith structure is provided in the slot portion.   The liquefaction determination device according to claim 22, wherein the liquefaction unit is provided so as to be seen through from the outside. The liquefied detection sensor, detectable photosensor or the liquefied portion liquefaction determining apparatus according to claim 22 Symbol mounting a detectable temperature measuring sensor as an electric signal the temperature change in the reflected light in the liquefaction unit. The liquefaction determination device according to claim 22 or 25, wherein the temperature measuring sensor is arranged immediately below the liquefaction detection piece.

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