JP2015178967A - Gas spraying type liquid sample injection device and injection container used for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas spraying type liquid sample injection device capable of shearing a liquid sample at a proper diameter in the gas spraying type liquid sample injection device in which the liquid sample is injected into an injection container while atomizing the liquid sample by spraying the liquid sample with gas.SOLUTION: A gas spraying type liquid sample injection device comprises: a sample introduction pipe including an outer pipe for atomization gas and an inner pipe for liquid which has a protruding part downward than a bottom edge of the outer pipe for atomization gas; a branch pipe arranged in an injection container, including a main pipe line into which the sample introduction pipe is inserted, and which has an internal diameter larger than an external diameter of the inner pipe for liquid, and a sub pipe line branching from the middle of the main pipe line; an inlet part arranged at top edge of the main pipe which has a structure in airtight contact with the bottom edge of the outer pipe for atomization gas; an outlet part arranged at the bottom edge of the main pipe which has a structure in airtight contact with an outer periphery of the inner pipe for liquid; and a blowoff pipe which is downwardly extended from the bottom edge of the sub pipe line to the outlet part of the main pipe line.

Description

  The present invention relates to a gas spray type sample injection device for injecting a liquid sample into an injection container while spraying a gas on the liquid sample, and an injection container used therefor. The injection container and the gas spray type liquid sample injection device are preferably used for a preparative purification device that uses a liquid chromatograph to separate one or more components contained in a solution and then purifies and recovers each component. Can do.

  For example, in the pharmaceutical field or the like, a sample to be stored as a library is collected by a preparative purification apparatus using a liquid chromatograph. In the apparatus described in Patent Document 1, target components (compounds) in a sample solution are temporally separated by liquid chromatography, introduced into different trap columns for each target component, and once collected. Thereafter, a solvent is passed through each trap column to elute components collected in the column, and a solution containing the target component is collected in a container. Thereafter, the solvent is removed, and a solidification process for recovering the target component as a solid is performed.

  The drying process is generally performed by heating the collected solution. However, in this method, the temperature cannot be raised too much in order to avoid alteration of the target component, and depending on the component, it takes a time of several hours to about one day. Since this drying process takes the longest time in the preparative purification process, it is important to reduce the time of the drying process in order to shorten the time of all processes.

  In order to solve the above problems, in Patent Documents 2 to 5, evaporation of the solvent is performed by spraying a gas such as air or nitrogen while dropping a solution containing the target component onto the recovery container, and by atomizing the solution. A method of promoting is disclosed.

  A general procedure of a drying process (hereinafter referred to as “gas spraying evaporation / drying process”) according to the methods of Patent Documents 2 to 5 will be described with reference to FIG. 8 is a temperature control block 54 for heating the recovery container 53 to a predetermined temperature, and a solution introduction tube for introducing a solution into the recovery container 53 accommodated in the temperature control block 54. 50, and a seal tube 55 for exhausting the gas introduced into the recovery container 53 and the solvent evaporated in the recovery container 53 so as not to leak out of the apparatus. The solution introduction tube 50 and the seal tube 55 are integrated, and the solution introduction tube 50 has a double tube structure of an inner tube 50A through which the solution flows and an outer tube 50B through which the atomized gas flows. The collection container 53 includes a collection container main body 51 and a lid 52 that is attached to the upper opening of the collection container 53 and has a hole in the center. A donut-shaped cushion 52 </ b> A is placed on the top of the lid 52.

  In the gas blowing type evaporation / drying process, the solution introduction pipe 50 is lowered and inserted into the collection container 53 through the hole at the center of the lid 52 and the cushion 52A. Along with this, the seal tube 55 is also lowered, and its tip presses the cushion 52A. Thereby, the tip of the seal portion 55 is in close contact with the cushion 52A, and the space between the collection container 53 and the seal tube 55 is hermetically sealed. Thereafter, the solution is sent to the inner tube 50A and the atomized gas is sent to the outer tube 50B. As a result, the solution dropped from the tip of the inner tube 50A is sheared by the atomized gas flow from the outer tube 50B, and becomes microdroplets (mist) and adheres to the inner wall of the collection container 53. Since the recovery container 53 is preheated by the temperature control block 54, the solvent of the fine droplets adhering to the inner wall evaporates, and only the target component (solute) remains as a powder. The atomized gas introduced into the recovery container 53 and the solvent evaporated in the recovery container 53 are discharged through the seal tube 55.

JP 2003-149217 A International Publication WO2009 / 044445 International Publication WO2009 / 044426 International Publication No. WO2009 / 044427 International Publication WO2009 / 044428

  Although the conventional preparative purification apparatus having a double-pipe structure as shown in FIG. 8 has high drying and solidification performance, the solution dripped from the inner pipe is excessively sheared by the gas flow from the outer pipe, and the recovery container The target component remaining as a powder on the inner wall of the resin sometimes became very small particles. When such fine particulate powder adheres thinly to the inner wall of the collection container, it becomes difficult to remove the powder from the wall surface and take it out of the collection container.

  The problem to be solved by the present invention is that a liquid sample is sprayed into a predetermined container (hereinafter referred to as “injection container” while gas is sprayed and atomized as in the gas spraying evaporation / drying process described above. Gas injection type liquid sample injection device for injecting the liquid sample into a gas injection type liquid sample injection device capable of atomizing the liquid sample to an appropriate particle size and a gas spray type liquid sample injection device using the injection vessel That is.

The present invention made to solve the above problems
The sample introduction used in a liquid sample injection device comprising a sample introduction tube comprising an outer tube for atomized gas and a liquid inner tube having a protruding portion protruding below the lower end of the outer tube for atomized gas An injection container in which a liquid sample from a tube is supplied by atomization,
An injection container body having an opening at the top;
A lid attached to the opening;
A main pipe having a larger inner diameter than the outer diameter of the liquid inner pipe into which the sample introduction pipe is inserted, and a branch from the middle of the main pipe. A branch pipe provided with a secondary pipe line,
An inlet portion provided at an upper end of the main pipe line and having a structure in airtight contact with a lower end of the outer tube for atomized gas;
An outlet portion provided at the lower end of the main pipe line and having a structure in airtight contact with the outer periphery of the liquid inner pipe;
And a blow-out pipe extending from the lower end of the sub-pipe to the lower side of the outlet of the main pipe.

  In the injection container for the gas spray type liquid sample injection device according to the present invention, the lid portion includes the branch pipe. When the liquid sample is introduced into the injection container, the outer tube for the atomized gas is in airtight contact with the inlet provided at the upper end of the main pipe of the branch pipe. At this time, the protruding portion of the liquid inner pipe is in airtight contact with the outlet provided at the lower end of the main pipe path of the branch pipe. Therefore, the atomizing gas supplied from the outer pipe for atomizing gas first enters the main pipe of the branch pipe, flows from the main pipe toward the sub pipe, and blows out from the blow-out pipe provided at the lower end of the sub pipe. .

  Since the blowing pipe is directed below the outlet portion of the main pipeline, the atomized gas blown from the blowing pipe strikes the dropped liquid sample from an oblique direction. In the conventional double tube structure, since the liquid sample and the atomizing gas flow on the same axis, the distance that the liquid sample is exposed to the atomizing gas flow is long and the diameter of the mist is small. In the structure, since the atomized gas hits the liquid sample obliquely, the distance that the liquid sample is exposed to the atomized gas flow is short, and the diameter of the mist is large. Since the size of this mist is determined mainly by the position and orientation of the tip of the blowing tube (more specifically, the distance from the tip of the blowing tube to the liquid sample) as described in the embodiment, the tip of the blowing tube By appropriately changing the position and orientation of the liquid sample, the liquid sample can be atomized to an appropriate particle size.

In addition, a gas sprayed liquid sample injection device according to the present invention, which has been made to solve the above problems,
A sample comprising an outer tube for atomized gas for atomizing and supplying a liquid sample into the injection container, and an inner tube for liquid having a protrusion protruding below the lower end of the outer tube for atomized gas. An introduction tube;
A main pipe having an inner diameter larger than the outer diameter of the liquid inner pipe into which the sample introduction pipe is inserted, and a sub pipe branched from the middle of the main pipe. A branch pipe comprising:
An inlet portion provided at an upper end of the main pipe line and having a structure in airtight contact with a lower end of the outer tube for atomized gas;
An outlet portion provided at the lower end of the main pipe line and having a structure in airtight contact with the outer periphery of the liquid inner pipe;
And a blow-out pipe extending from the lower end of the sub-pipe toward the bottom of the outlet of the main pipe.

  The gas spraying liquid sample injection device preferably further includes a heating means for heating the injection container. As a result, the solvent in the mist droplets evaporates and the powder remains in the injection container. In the gas spray type liquid sample injection device according to the present invention, since a mist having a larger diameter than that of the conventional one is obtained, the diameter of the powder remaining after the solvent evaporates also increases. As described above, by appropriately changing the position and orientation of the tip of the blowing tube, for example, a powder having an appropriate particle size can be obtained for each liquid sample.

  An injection container for a gas spray type liquid sample injection device according to the present invention is such that gas is sprayed obliquely against a dropped liquid sample by means of a branch pipe and a blow pipe provided in the lid. As a result, the distance over which the liquid sample is exposed to the gas flow is shortened, so that a mist having a large diameter is obtained. Furthermore, by appropriately changing the position and orientation of the tip of the blow-out tube, for example, each liquid sample can be atomized to an appropriate particle size.

The principal part block diagram of the preparative refinement | purification apparatus using the gas spraying-type liquid sample injection device which concerns on one Example of this invention. It is a schematic longitudinal cross-sectional view which shows the structure of the injection container used for the liquid sample introduction apparatus of a present Example, (a) is the whole figure, (b) is a figure which shows each part which comprises an injection container. The schematic longitudinal cross-sectional view which shows the relationship between the sample introduction pipe (a) of the gas spraying-type liquid sample injection device of a present Example, and the branch pipe (b) of an injection container corresponding to it. In the gas sprayed liquid sample injection device of the present embodiment, a schematic longitudinal sectional view (a) showing a state before inserting a sample introduction tube into an injection container, and a schematic longitudinal sectional view showing a state after insertion (b) ). FIGS. 4A and 4B show examples of dimensions of each part of the injection container in the gas spray type liquid sample injection apparatus of the present embodiment.The calculation results of the Reynolds number when the atomized gas is flowed using the injection container of FIG. Table (b) shown. In the gas spray type liquid sample injection device of the modification, a schematic longitudinal sectional view (a) showing a state before inserting the sample introduction tube into the injection container, and a schematic longitudinal sectional view (b) showing the state after insertion . In a gas spray type liquid sample injection device of another modification, a schematic longitudinal sectional view showing a state before inserting a sample introduction tube into an injection container (a), and a schematic longitudinal sectional view showing a state after insertion ( b). Explanatory drawing of the powdering process by the conventional fractionation refinement | purification apparatus.

An embodiment of a gas spraying type liquid sample injection device according to the present invention will be described with reference to FIGS. FIG. 1 is a block diagram of a main part of a preparative purification apparatus to which a gas spraying type liquid sample injection device of this embodiment is applied. In this preparative purification apparatus, as described later, a preparative liquid chromatograph (not shown) preliminarily collects a solution containing a target component. It is also possible to change to a configuration in which the solution separated by the preparative liquid chromatograph is directly introduced into the preparative purification apparatus.
FIG. 2 is a schematic longitudinal sectional view of an injection container used in the gas spraying liquid sample injection device of the present embodiment. FIG. 3 shows a sample introduction tube of the gas spraying liquid sample injection device of the present embodiment. FIG. 4 is a schematic longitudinal sectional view showing the relationship of the branch pipe of the injection container corresponding thereto, and FIG. 4 shows a state before and after inserting the sample introduction pipe into the injection container in the gas sprayed liquid sample injection apparatus of this embodiment. It is a schematic longitudinal cross-sectional view which shows this.

In FIG. 1, a solution container 1 contains a solution containing a target component, which is preliminarily collected and uses a mobile phase used in a preparative liquid chromatograph as a main solvent. The pure water container 2 contains pure water (H ₂ O), and the elution solvent container 3 contains dichloromethane (DCM). The switching valve 4 switches the flow path so that any one of the liquids stored in these three containers 1, 2, 3 is selectively flowed to the flow path 5. Further, a liquid feed pump 6 is provided on the flow path 5 for sucking and sending the liquid at a predetermined flow rate.

  The outlet end of the flow path 5 is connected to the a port of the switching valve 7. A flow path 10 leading to a trap column 8 filled with an adsorbent for collecting a target component is connected to the b port of the switching valve 7, and an atomizing gas flow path 22 described later is connected to the c port. The flow paths 11 are connected to each other. The switching valve 7 selectively connects the channel 10 or the channel 11 to the channel 5.

  The trap column 8 is erected and held substantially vertically by the column rack 9 with the inlet end to which the flow path 10 is connected right below and the outlet end to which the flow path 12 described later is connected upward. Although only one trap column 8 is shown in FIG. 1, it is also possible to hold a plurality of trap columns 8 side by side in the column rack 9 as shown by dotted lines in FIG.

  The other end of the flow path 12 whose one end is connected to the outlet end of the trap column 8 is connected to the a port of the switching valve 15 built in the sorting head 16, and the flow path 14 is connected to the b port of the switching valve 15. Connected to the c port is a flow path 13 leading to a waste liquid port. The switching valve 15 alternatively connects the flow path 13 or the flow path 14 to the flow path 12.

  The sorting head 16 includes a sample introduction pipe 17 and an exhaust seal pipe 18 integrally provided outside thereof, and can be moved up and down and horizontally by an XYZ drive mechanism 29 including a plurality of motors. Yes. The sample introduction tube 17 includes an inner tube 40 connected to the flow channel 14 and an outer tube 41 connected to the flow channel 22 (note that the sample introduction tube 17 and the injection container 20 in FIG. Such a configuration is shown in FIGS. As will be described later, a solution containing a target component is sent to the inner pipe 40 through the flow path 14, and atomized gas is sent to the outer pipe 41 through the flow path 22. Further, the inner tube 40 has a protruding portion 40 </ b> A that protrudes below the lower end of the outer tube 41.

  The injection container 21 into which the solution is injected is individually accommodated in a heater 25, a temperature sensor 26 such as a thermistor, and a temperature control block 27 of the container rack 24. The container rack 24 and the temperature control block 27 are made of a material having good thermal conductivity such as aluminum, and the outside is covered with a heat insulating material to prevent heat from escaping to the surroundings (not shown).

  At least the bottom of each injection container 21 is in contact with the temperature control block 27 so that heat from the temperature control block 27 can be easily conducted. As a more preferable form, the side peripheral surface of the injection container 21 may be in contact with the temperature control block 27. The temperature control unit 28 provided separately from the container rack 24 adjusts the heating current supplied to the heater 25 so that the monitor temperature detected by the temperature sensor 26 becomes the target temperature. As a result, the injection container 21 is maintained at an appropriate constant temperature.

  The sorting head 16 moves onto an arbitrary injection container 21 among a plurality of containers accommodated in the container rack 24 by the XYZ drive mechanism 29 (FIG. 4A) and descends.

The injection container 21 includes an injection container main body 19 and a lid portion 20 attached to the upper opening thereof. As shown in FIGS. 2 to 4, the lid 20 has a characteristic structure of the present invention. The main pipe line having an inner diameter φ ₄ larger than the outer diameter φ ₁ of the inner pipe 40 into which the sample introduction pipe 17 is inserted. 42A and a branch pipe 42 having a secondary pipe 42B that branches from the middle of the main pipe 42A. At the upper end of the main pipe line 42A of the branch pipe 42, an inlet portion 43 that guides the sample introduction pipe 17 to the main pipe line 42A is provided. An outlet 46 having an inner diameter equal to the outer diameter φ ₁ of the inner tube 40 is provided at the lower end of the main pipeline 42A. At the lower end of the sub-pipe 42B of the branch pipe 42, a blow-out pipe 47 is provided below the outlet 46 and facing the center line C of the main pipe 42A. In FIGS. 2 to 4, the branch pipe 42, the inlet portion 43, the outlet portion 46, and the blowout pipe 47 are illustrated as separate bodies, but these may be configured integrally. The part may be configured separately.
The lid 20 improves the adhesion between the atomizing gas introduced into the injection container 21 and the exhaust port 44 for discharging the solvent evaporated in the injection container 21, and the lid 20 and the exhaust seal pipe 18. A donut-shaped cushion 45 is provided.

The lower end portion of the outer tube 41 (reference numeral 41A in FIG. 3A) and the inner peripheral portion of the inlet portion 43 are both narrowed downward. Specifically, angle of theta ₁ which forms the outer circumferential surface of the lower end portion 41A and the center axis _thereof, the inner peripheral surface of the inlet portion 43 and the corner that forms the central axis and theta _2, these, θ _2> θ ₁ (FIG. 3). Further, the diameter of the thinnest part of the outer periphery of the lower end 41A is φ ₂ , the outer diameter of the thickest part is φ ₃ , the diameter of the thinnest part of the inner periphery of the inlet 43 is φ ₄ , and the diameter of the thickest part is φ When _5, it is dimensioned to satisfy _{φ 2 <φ 4 <φ 3} <φ 5 is designed.
By designing the dimensions and angles of the lower end portion 41A and the inlet portion 43 in this way, the sample introduction tube 17 is guided to the center of the inlet portion 43, and the outer tube 41 and the inlet portion 43 are in airtight contact. Further, since the outer diameter of the inner tube 40 and the inner diameter of the outlet portion 46 are equal, they are in airtight contact (FIG. 4 (b)).

When the sample introduction pipe 17 is lowered, the exhaust seal pipe 18 is also lowered and presses the cushion 45 provided on the lid portion 20. Thereby, the space between the exhaust seal pipe 18 and the injection container 21 is hermetically sealed (FIG. 4B). In this state, the gas spraying evaporation / drying process described later is performed.
Note that the container rack 24 may move instead of the sorting head 16 moving.

  The gas supply unit 23 includes a proportional valve 23 </ b> A, a gas cylinder 23 </ b> B, and the like, and sends atomized gas to the outer tube 41 of the sample introduction tube 17 through the flow path 22.

  The control unit 30 including the CPU or the like performs switching operation of the switching valves 4, 7, 15, operation of the liquid feeding pump 6 and the gas supply unit 23 (flow rate or flow velocity), and target temperature of the temperature control unit 28 according to a preset program. And the control of the movement of the preparative head 16 via the XYZ drive mechanism 29, the preparative purification work is automatically performed. The operation unit 31 is used to input and set conditions for the preparative purification work.

  Next, the procedure of the gas spraying evaporation / drying process by the preparative purification apparatus of FIG. 1 will be described. First, in order to collect the target component contained in the solution in the solution container 1 in the adsorbent in the trap column 8 and discard the solvent (mobile phase) in the solution, the control unit 30 uses the switching valve 4 to Flow through the container 1 (b port) and the flow path 5 (a port), through the switching valve 7 through the flow path 5 (a port) and the flow path 10 (b port), and through the switching valve 15 through the flow path 12 (a port). Each of the passages 13 (c port) is connected, and the liquid feed pump 6 is operated so as to feed the liquid at a predetermined constant flow rate. The liquid feed pump 6 sucks the solution in the solution container 1 and introduces it into the trap column 8 through the flow path 5 and the flow path 12. Then, the target component in the solution is collected by the adsorbent in the trap column 8. The solution (mobile phase) from which the target component has been removed is discarded through the flow path 12 and the flow path 13 to the waste liquid port.

  When the solution in the solution container 1 is supplied to the trap column 8 for a predetermined time or a predetermined amount, the control unit 30 then switches to connect the pure water container 2 (c port) and the flow path 5 (a port). Switch valve 4. Then, the liquid feed pump 6 sucks the pure water in the pure water container 2 and introduces it into the trap column 8. Thereby, undesired water-soluble substances such as salts adhering to the adsorbent during the collection of the target component are removed from the trap column 8. By supplying pure water, the mobile phase accumulated in the trap column 8 immediately before the start of the supply is replaced with water, and the trap column 8 is filled with water. Since the target component collected in the adsorbent hardly elutes in water due to the strong adsorption action, the state of being collected in the trap column 8 is maintained at this point.

  Next, the control unit 30 causes the XYZ drive mechanism 29 to move the sorting head 16 above the branch pipe 42 of a predetermined injection container 21 specified in advance, and lowers the sorting head 16 (FIG. 4 (b)). . Then, the control unit 30 instructs the target temperature to the temperature control unit 28, starts heating the temperature control block 27, and starts heating the injection container 21. The target temperature may be about the same as or slightly higher than the boiling point of dichloromethane used as an elution solvent for the target component, and may be about 40 to 45 ° C. Thereafter, the control unit 30 switches the switching valve 4 so as to connect the elution solvent container 3 (d port) and the flow path 5 (a port). As a result, the liquid feed pump 6 sucks the dichloromethane in the elution solvent container 3 and starts to introduce it into the trap column 8.

  When dichloromethane is introduced into the trap column 8, the interface between dichloromethane and water gradually rises with little mixing with the water present in the trap column 8. That is, dichloromethane gradually accumulates from the bottom of the trap column 8 while pushing up water. On the other hand, the pushed-up water overflows from the outlet end at the upper end of the trap column 8, passes through the switching valve 15 and reaches the waste liquid port from the flow path 13. On the other hand, since dichloromethane has a strong dissolution power, the target component collected in the trap column 8 dissolves in the dichloromethane accumulated in the trap column 8.

  When the dichloromethane in the elution solvent container 3 is supplied to the trap column 8 for a predetermined time or in a predetermined amount and water is completely removed from the trap column 8, the switching valve 15 is changed from the flow path 13 (c port) to the flow path 14 Switch to (b port) and start sorting the target component. Further, the control unit 30 causes the gas supply unit 23 to start supplying nitrogen gas (or other inert gas). The atomized gas delivered from the gas supply unit 23 is introduced into the main pipeline 42 </ b> A of the branch pipe 42 through the flow path 22 and the outer pipe 41. The inlet 43 provided at the upper end of the main pipe 42A is sealed by the lower end 41A of the outer pipe 41, and the outlet 46 provided at the lower end of the main pipe 42A is sealed by the outer periphery of the inner pipe 40. Therefore, the atomized gas introduced into the main pipeline 42 </ b> A flows toward the secondary pipeline 42 </ b> B and starts to be blown out from the blowout pipe 47. On the other hand, the solution sent from the trap column 8, that is, dichloromethane containing the target component, is dropped from the lower end of the inner pipe 40 of the sample introduction pipe 17 through the flow path 12 and the flow path 14. As described above, since the blowing pipe 47 is designed to face the center line C of the main pipe line 43A, the atomized gas blown from the blowing pipe 47 hits the solution dripped from the inner pipe 40, and the solution is applied to the solution. Shears into mist.

In the injection container 21 of the present embodiment, unlike the conventional case, the solution and the atomized gas do not flow on the same axis, so the distance that the solution is exposed to the atomized gas is short and the diameter of the mist is large. In addition, as the distance between the position E at which the solution is sheared (intersection of the center line C and the straight line D indicating the direction of the blowing tube 47) and the tip of the blowing tube 47 increases, the atomized gas diffuses and the energy is increased. Since it loses, the diameter of mist becomes large similarly. Therefore, the size of the diameter of the mist obtained can be changed by appropriately adjusting the distance d from the tip of the blowing tube 47 to the shearing position E and the angle θ _{3 formed} by the center line C and the straight line D. For example, the lid 20 may have a structure in which the position and / or angle of the tip of the blowing tube 47 can be freely changed, or a plurality of lids 20 having different angles from the position of the tip of the blowing tube 47 may be provided. Kinds may be prepared. Thereby, according to the magnitude | size of the powder to obtain or according to the kind of sample, it becomes possible to perform said gas spraying type evaporation to dryness process with a suitable magnitude | size of mist.

  The injection container 21 is heated to the same temperature as the boiling point of dichloromethane by heat conduction from the temperature control block 27 using the heater 25 as a heat source. Therefore, when a fine droplet of the solution adheres to the inner periphery or inner wall surface of the injection container 21, the solvent (dichloromethane) in the droplet immediately evaporates and the target component remains as a powder. In this way, the powdery target component is deposited on the inner periphery and inner wall surface of the injection container 21. The atomized gas and the evaporated solvent introduced into the injection container 21 are discharged to the outside of the injection container 21 through the exhaust seal pipe 18.

  When the above steps are completed, the sorting head 16 is raised. When powdering another target component continuously, the sorting head 16 is moved to a position where the next injection container 21 is located, and the same processing is performed.

The above is the procedure of the gas spraying evaporation / drying process of the present embodiment using the preparative purification apparatus of FIG. 1, but the inner tube of the sample tube 17 during the gas spraying evaporation / drying process The solute may precipitate at the tip of 40 and grow along the outer wall of the inner tube 40. In order to prevent this, the inner tube 40 is preferably made of a polytetrafluoroethylene (PTFE) resin material such as Teflon (registered trademark). Since the PTFE resin has low wettability, the solution hardly rises from the tip of the inner tube 40 due to surface tension to the outer wall of the inner tube. For the same reason, it is desirable that the branch pipe 42 is also made of a PTFE resin material.
Further, it is desirable that the outlet of the blow-out pipe 47 has a wide rectangular shape. Thereby, the atomization gas flow which blows off from the blowing pipe 47 becomes a wide thing, and can atomize an atomization gas flow in a wide range.

Further, in the configuration of the present embodiment, since the atomizing gas can be applied to the bottom surface of the injection container 19 from an oblique direction, the solution accumulated on the bottom surface of the injection container 19 can be agitated to promote evaporation. it can. At this time, if the angle and position of the blowing tube 47, the height of the injection container 19 and the like are appropriately designed so that the atomized gas hits the center of the bottom surface, the solution accumulated on the bottom surface is more efficiently diffused. be able to. FIG. 5 (a) is an example of the dimensions of each part of the injection container 19 designed so that the atomized gas hits the center of the bottom surface. In this design, the atomized gas is placed at a portion 0.2 mm away from the center of the bottom surface. Incident from an angle.
5A is used to calculate the Reynolds number when the atomized gas is flowed with the gas flow rate, average flow velocity, kinematic viscosity, and inner diameter of the blow pipe shown in the table of FIG. 5B. did. As shown in this table, the Reynolds number Re at this time was 2254572, which was larger than the critical Reynolds number Rec = 2320. As described above, when the Reynolds number Re becomes larger than the critical Reynolds number Rec, the atomized gas blown from the blowing pipe 47 becomes turbulent.

2 to 5, the length of the branch pipe 42 is designed so that the protruding portion 40A protrudes from the outlet portion 46. As shown in FIGS. 6 (a) and 6 (b), the protruding portion The length of the branch pipe 42 may be designed so that 40A is accommodated in the outlet portion 46. In the branch pipe 42 having this structure, since the inner pipe 40 is not exposed to the injection container 21, it is possible to prevent droplets and powder scattered in the injection container 21 from adhering to the inner pipe 40. Further, since the outer tube 41 is not introduced into the injection container 21, no droplets or powder adhere to the outer tube 41. Thereby, contamination can be prevented from occurring when a different liquid sample is injected in the next injection container.
In the above description, the protruding portion 40A is accommodated in the outlet portion 46 by lengthening the branch pipe 42. However, the length of the branch pipe 42 remains the same, and the protruding portion 40A is shortened by shortening the protruding portion 40A. You may make it fit in the exit part 46. FIG.

  When the inner tube 40 is formed from a PTFE-based resin material, if the projection 40A of the inner tube 40 is repeatedly inserted and removed from the outlet 46 of the lid portion 20, the projection 40A of the inner tube 40 may be worn out. . Therefore, as shown in FIG. 7, the lengths of the branch pipe 42 and the inner pipe 40 are designed so that the protruding portion 40A of the inner pipe 40 is accommodated in the main pipe path 42A when the sample introduction pipe 17 is inserted into the branch pipe 42. A cylindrical cuff 46A may be attached to the outlet 46 of the branch pipe 42. The length of the cuff portion 46A is designed so that when the sample introduction tube 17 is inserted into the branch tube 42, the lower end of the protruding portion 40 of the inner tube 40 is close to the upper end of the cuff portion 46A. According to such a configuration, the protrusion 40A does not come into contact with the outlet 46 when the sample introduction tube 17 is inserted into the branch tube 42, so that the wear of the protrusion 40A can be prevented.

In the above configuration, the inner tube 40 may be made of stainless steel, but the cuff portion 46A is preferably made of PTFE for the reason described above. Further, the cuff portion 46A may be bent so that the lower end of the cuff portion 46A is slightly inclined toward the blowing tube 47 side. According to such a configuration, the stagnation of the solution at the tip of the cuff portion 46A is reduced, and the state of the powder obtained in the injection container 21 can be improved.
Further, instead of bending the cuff portion 46A, or in addition to bending the cuff portion 46A, the length of the cuff portion 46A is changed, or the tip of the cuff portion 46A is cut obliquely. The state of the powder can be adjusted.

  As described above, the injection container and the gas spraying type liquid sample injection device according to the present invention have been described using the embodiments. However, it is a matter of course that changes and modifications can be appropriately made within the scope of the present invention.

DESCRIPTION OF SYMBOLS 1 ... Solution container 2 ... Pure water container 3 ... Elution solvent container 4 ... Switching valve 5, 10, 11, 12, 13, 14, 22 ... Flow path 6 ... Liquid feed pump 7 ... Switching valve 8 ... Trap column 9 ... Column rack 15 ... switching valve 16 ... sorting head 17 ... sample introduction tube 40 ... inner tube 41 ... outer tube 41A ... lower end 18 ... exhaust seal tube 19 ... injection vessel body 20 ... lid portion 21 ... injection vessel 23 ... gas Supply unit 23A ... Proportional valve 23B ... Gas cylinder 24 ... Container rack 25 ... Heater 26 ... Temperature sensor 27 ... Temperature control block 28 ... Temperature control unit 29 ... XYZ drive mechanism 30 ... Control unit 31 ... Operation unit 42 ... Branch pipe 42A ... Main pipe Road 42B ... Sub-pipe 43 ... Inlet 44 ... Exhaust 45 ... Cushion 46 ... Outlet 46A ... Cuff 47 ... Blowout pipe

Claims (5)

The sample introduction used in a liquid sample injection device comprising a sample introduction tube comprising an outer tube for atomized gas and a liquid inner tube having a protruding portion protruding below the lower end of the outer tube for atomized gas An injection container in which a liquid sample from a tube is supplied by atomization,
An injection container body having an opening at the top;
A lid attached to the opening;
A main pipe having a larger inner diameter than the outer diameter of the liquid inner pipe into which the sample introduction pipe is inserted, and a branch from the middle of the main pipe. A branch pipe provided with a secondary pipe line,
An inlet portion provided at an upper end of the main pipe line and having a structure in airtight contact with a lower end of the outer tube for atomized gas;
An outlet portion provided at the lower end of the main pipe line and having a structure in airtight contact with the outer periphery of the liquid inner pipe;
An injection container comprising: a blow-out pipe extending from a lower end of the sub pipe line toward a lower portion of an outlet portion of the main pipe line.   The injection container according to claim 1, wherein the position and / or orientation of the tip of the blowing tube is variable. A sample comprising an outer tube for atomized gas for atomizing and supplying a liquid sample into the injection container, and an inner tube for liquid having a protrusion protruding below the lower end of the outer tube for atomized gas. An introduction tube;
A main pipe having an inner diameter larger than the outer diameter of the liquid inner pipe into which the sample introduction pipe is inserted, and a sub pipe branched from the middle of the main pipe. A branch pipe comprising:
An inlet portion provided at an upper end of the main pipe line and having a structure in airtight contact with a lower end of the outer tube for atomized gas;
An outlet portion provided at the lower end of the main pipe line and having a structure in airtight contact with the outer periphery of the liquid inner pipe;
A gas blowing type liquid sample injection device, comprising: a blowing pipe extending from a lower end of the sub pipe line toward a lower portion of an outlet portion of the main pipe line.   The gas spraying liquid sample injection device according to claim 3, wherein the position and / or direction of the tip of the blowing tube is variable.   The gas spraying type liquid sample injection device according to claim 3, further comprising a heating unit that heats the injection container.

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