JP6260379B2 - Gas spray type liquid injection device and injection container used therefor - Google Patents

Description

  The present invention relates to a gas spraying type liquid injecting apparatus that atomizes the liquid by injecting the liquid containing the target component into the injecting container and sprays the gas to the liquid and promotes evaporation of the solvent, and an injecting container used therefor . The injection container and the gas spray type liquid sample injection device are suitable for, for example, 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 be used.

  For example, in the pharmaceutical field, a preparative purification device using a liquid chromatograph for the purpose of collecting samples for storing various compounds obtained by chemical synthesis as a library or for detailed analysis. Is used. As such a preparative purification apparatus, apparatuses described in Patent Document 1, Patent Document 2, and the like are known.

  In these apparatuses, target components (compounds) in a sample solution are temporally separated by liquid chromatography, and each separated target component is introduced into different trap columns and once collected. Thereafter, a solvent is passed through each trap column to elute the components collected in the column, and a solution containing the target component at a high concentration is collected in a container. Thereafter, the solvent is removed from each of the collected solutions, and an evaporation / drying process for recovering the target component as a solid is performed.

  The evaporation / drying process is generally performed by a method such as heating the collected solution or vacuum centrifuging. However, such a method alone requires a time of several hours to one day. In the pharmaceutical field, in order to search for medicinal compounds from a large number of synthetic compounds, various efficiency improvements such as shortening the analysis time by increasing the speed of analytical instruments and optimizing analytical methods have been attempted. Since the evaporation / drying process takes the longest time among all processes, it is important to shorten this time.

  In order to solve the above problems, in Patent Documents 3 to 5, a solvent at the time of heating is formed by spraying a gas such as air or nitrogen while dropping a solution containing a target component onto a collection container to make the solution mist. Shows how to promote the evaporation of.

  The general procedure of the evaporation / drying step (hereinafter referred to as “gas spraying evaporation / drying step”) by the methods of Patent Documents 3 to 5 will be described with reference to FIG. As shown in FIG. 5, the preparative purification apparatus includes a needle 50 having a double tube structure of an inner tube 50A and an outer tube 50B covering the outer periphery of the inner tube 50A. Note that the lower end of the inner tube 50A protrudes from the lower end of the outer tube. Furthermore, a recovery container 53 accommodated in a temperature control block 54 is disposed under the needle 50. The collection container 53 has a collection container main body 51 and a cap 52 attached to the upper opening of the collection container main body 51. A hole is provided at the center of the cap 52, and a donut-shaped cushion 52 </ b> A is placed on the top of the cap 52. An exhaust duct 55 for exhausting the gas introduced into the recovery container 53 and the sample evaporated in the recovery container 53 so as not to leak out of the apparatus is provided at the upper part of the outer periphery of the needle 50.

  In the gas blowing type evaporation / drying process, the needle 50 descends, passes through the central hole of the cushion 52A and the cap 52, and is inserted into the recovery container 53. As the needle 50 is lowered, the exhaust duct 55 is lowered, and the tip thereof is in close contact with the cushion 52A. Thereby, the space between the collection container 53 and the exhaust duct 55 is hermetically sealed. Thereafter, the solution and the gas are respectively introduced into the collection container 53 through the inner tube 50A and the outer tube 50B.

  At the tip of the needle 50 inserted into the collection container 53, the solution that has passed through the inner tube 50A is dropped, and gas is blown out from an outer tube 50B provided on the outer periphery thereof. The solution dropped from the inner tube 50A is sheared by the gas flow from the outer tube 50B, and becomes a fine droplet (mist) and adheres to the inner wall of the collection container 53. The recovery container 53 is preheated by a temperature control block 54 surrounding the container, and the solvent of the fine droplets adhering to the inner wall evaporates, leaving only the solute as a powder.

  In this way, by dropping the solution containing the target component to the collection container while blowing the gas, the evaporation of the solvent can be promoted, and the time required for the evaporation / drying process can be shortened. However, when performing the gas spraying evaporation / drying process using the needle having the double pipe structure as described above, the solution dripped from the inner pipe is excessively sheared by the gas flow from the outer pipe, In some cases, the particles of the target component remaining as powder on the inner wall of the collection container become too fine. 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 remove it from the collection container.

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

  Therefore, the present inventor has proposed a device as shown in FIG. 6 as a gas spraying type liquid injection device capable of atomizing a solution (liquid sample) containing a target component to an appropriate particle size.

  This apparatus includes a multiple tube 60 including an inner tube 60A, an outer tube 60B covering the outer periphery of the inner tube 60A, and an exhaust tube 60C covering the outer periphery. In the multiple pipe 60, the lower end of the outer pipe 60B protrudes from the lower end of the exhaust pipe 60C, and the lower end of the inner pipe 60A protrudes therefrom. Further, the injection container 61 used in this apparatus includes an injection port 64 in the center of the lid 63, and the injection port 64 has a concave portion 64A opened upward, a liquid passage 64B, and an atomizing gas passage. 64C. One end of each of the liquid passage 64 </ b> B and the atomizing gas passage 64 </ b> C communicates with the internal space of the recess 64 </ b> A, and the other end opens on the lower surface of the injection port 64. A guide member 65 for guiding the inner tube 60A into the injection port 64 is attached to the center of the recess 64A. When the multiple tube 60 is lowered toward the injection container 61, the lower end of the inner tube 60A is It is inserted into the liquid passage 64B in the injection port 64 through a conduit 66 comprising a tapered portion 66A formed at the upper part of the guide member 65 and a straight pipe portion 66B below the tapered portion 66A. Further, at this time, the lower end of the outer tube 60B is inserted between the inner peripheral surface of the concave portion 64A and the outer peripheral surface of the guide member 65, and the outer peripheral surface of the outer tube 60B and the inner peripheral surface of the concave portion 64A are in airtight contact. The lower end of the exhaust pipe 60C is in airtight contact with a cushion 63A disposed around the guide member 65. In this state, when the solution containing the target component is supplied to the inner tube 60A, the solution flowing out from the lower end of the solution is dropped into the injection container main body 62 through the liquid passage 64B and the cuff portion 67 connected to the lower end. Is done. Further, the atomized gas supplied from the outer tube 60B first enters the recess 64A of the injection port 64 and flows into the atomized gas passage 64C from there, and then the atomized gas provided at the lower end of the channel 64C. It ejects from the blowing pipe 68. Since the tip of the atomizing gas blowing pipe 68 is directed below the outlet of the cuff 67, the atomizing gas ejected from the atomizing gas blowing pipe 68 strikes the solution dripped from the cuff 67 from an oblique direction. It will be.

  In the structure as shown in FIG. 5 described above, since the solution and the atomized gas that have come out of the needle 50 flow coaxially, the distance that the solution is exposed to the atomized gas flow is long, and the diameter of the mist is small. On the other hand, in the structure as shown in FIG. 6, since the atomized gas hits the solution dropped in the injection container 61 from an oblique direction, the distance that the solution 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 by the position and orientation of the tip of the atomizing gas blowing pipe 68 (more specifically, the distance from the tip of the atomizing gas blowing pipe 68 to the liquid sample), the atomizing gas blowing pipe By appropriately changing the position and orientation of the tip of 68, the solution containing the target component can be atomized with an appropriate particle size. The atomized gas introduced into the injection container 61 is discharged out of the injection container 61 by flowing into the exhaust pipe 60C through a gap between the inner periphery of the lid 63 and the cushion 63A and the outer periphery of the injection port 64. .

  Further, in the injection container 61 shown in FIG. 6, a resin O-ring 69 is disposed between the guide member 65 and the bottom surface of the recess 64 </ b> A of the injection port 64. The O-ring 69 is in close contact with the outer periphery of the inner tube 60A when the inner tube 60A is inserted into the injection port 64. Thereby, the effect of preventing the atomized gas supplied from the outer tube 60B from passing between the inner periphery of the pipe 66 and the outer periphery of the inner tube 60A and entering the liquid passage 64B is obtained.

  However, in such a device, as shown in FIG. 7, the height of the outlet of the pipe 66 is equal to the height of the upper end of the O-ring 69, so that the inner pipe 60 </ b> A is inserted into the pipe 66 in an inclined state. In some cases, the tip of the inner tube 60A contacts the O-ring 69 at a position close to the upper end of the O-ring 69. In this case, the angle formed by the tangent line of the O-ring 69 and the axial direction of the inner tube 60A (β in the figure) at the contact location is large (that is, the tangent line and the axial direction are close to perpendicular). There is a risk that the tip of the ring may catch on the O-ring 69 or damage the surface of the O-ring 69.

  The present invention has been made in view of the above points, and an object thereof is to have the above-described multiple pipe and injection port, and an inner pipe for supplying liquid at the inlet of the injection port. A gas spraying device comprising a guide member for guiding the gas pipe, and an O-ring that is in close contact with the outer periphery of the inner pipe is disposed between a pipe passage formed in the guide member and a passage located downstream of the pipe passage. In the type liquid injection device, the contact between the O-ring and the tip of the inner tube prevents the inner tube from being inserted and prevents the O-ring from being damaged.

An injection container according to the present invention, which has been made to solve the above problems,
Used in a gas spraying liquid sample injection device comprising a multiple tube having an outer tube to which atomized gas is supplied and an inner tube that protrudes below the lower end of the outer tube and to which a liquid containing a target component is supplied; An injection container in which the liquid from the multiple tube is atomized and supplied, and has an injection container body having an opening in the upper part, and an injection port provided in the opening,
The injection port is
a) a recess provided on the top surface of the injection port;
b) a liquid passage having an inlet end that opens to the bottom surface of the recess, and an outlet end that reaches the internal space of the injection container body;
c) a guide member fitted in the recess;
d) a pipe line formed inside the guide member and having an inlet end into which the inner pipe is inserted and an outlet end facing the inlet end of the liquid passage;
e) It is disposed between the guide member and the bottom surface of the recess, and contacts the outer periphery of the inner tube at the inner periphery when the inner tube is inserted into the liquid passage through the conduit. O-ring,
Have
The guide member protrudes in the axial direction of the pipe line at the periphery of the outlet end of the pipe line.

Moreover, the gas spraying type liquid injection device according to the present invention, which has been made to solve the above problems,
An outer tube that is supplied with an atomizing gas, and an inner tube that protrudes below the lower end of the outer tube and is supplied with a liquid containing a target component, for atomizing and supplying the liquid into an injection container A gas spraying liquid injection device having a multiple tube and an injection port provided at the inlet of the injection container,
The injection port is
a) a recess provided on the top surface of the injection port;
b) a liquid passage having an inlet end that opens to the bottom surface of the recess, and an outlet end that reaches the internal space of the injection container;
c) a guide member fitted in the recess;
d) a pipe line formed inside the guide member and having an inlet end into which the inner pipe is inserted and an outlet end facing the inlet end of the liquid passage;
e) It is disposed between the guide member and the bottom surface of the recess, and contacts the outer periphery of the inner tube at the inner periphery when the inner tube is inserted into the liquid passage through the conduit. O-ring,
Have
The guide member protrudes in the axial direction of the pipe line at the periphery of the outlet end of the pipe line.

  As described above, in the injection container and the gas spraying type liquid injection device according to the present invention, the peripheral edge of the outlet end of the pipe line through which the inner pipe passes projects in the axial direction of the pipe line. For this reason, the said pipe line is extended below by this protrusion part, and when inserting an inner pipe | tube into an injection | pouring port, the front-end | tip of an inner pipe | tube is an O-ring in a position lower than before (namely, a position near a liquid channel) It will come into contact. As a result, the angle formed by the tangent line of the O-ring and the axial direction of the inner tube at this contact portion can be made smaller than before (that is, the tangent line of the O-ring can be made parallel to the axial direction). It is possible to prevent the tip of the inner tube from being caught by the O-ring or damaging the surface of the O-ring.

The principal part block diagram of the fractionation refinement | purification apparatus using the gas spraying type liquid injection apparatus which concerns on one Example of this invention. It is a schematic longitudinal cross-sectional view which shows the structure of the injection container in the gas spraying type liquid injection apparatus of the Example, (a) shows the state before inserting a multiple tube in an injection container, (b) shows a multiple tube. The state after insertion is shown. The figure which shows an example of the dimension of each part of the injection | pouring container in the gas spraying type liquid injection apparatus of the Example. The enlarged view of an O-ring periphery at the time of insertion of the multiple tube to the said injection | pouring container. It is a schematic longitudinal cross-sectional view which shows an example of a structure of the injection | pouring container used for the conventional gas spraying-type liquid injection | pouring apparatus, (a) is the whole figure of the injection | pouring container before inserting a multiple tube, (b) is a multiple tube. FIG. 4 is an overall view of the injection container after insertion, (c) is a view showing a configuration of the multiple tube, and (d) is a view showing a configuration of a lid portion of the injection container. It is a schematic longitudinal cross-sectional view which shows another example of the structure of the injection container used for the conventional gas spraying type liquid injection apparatus, (a) shows the state before inserting a sample introduction tube in an injection container, (b ) Shows the state after inserting the sample introduction tube. FIG. 7 is an enlarged view around an O-ring when a multiple tube is inserted into the injection container of FIG. 6.

  An embodiment of a gas spraying type liquid injection device and an injection container according to the present invention will be described with reference to the drawings. FIG. 1 is a block diagram of a main part of a preparative purification apparatus to which a gas spraying liquid injection apparatus and an injection container according to this embodiment are 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.

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 multiple pipe 17 having an inner pipe 17A, an outer pipe 17B integrally provided on the outer side thereof, and an exhaust seal pipe 17C integrally provided on the outer side thereof. Up and down movement and horizontal movement are possible by an XYZ drive mechanism 29 composed of such a motor. The inner pipe 17A is connected to the flow path 14, and the outer pipe 17B is connected to the flow path 22 (note that the multiple pipe 17 and the injection container 21 in FIG. 1 are schematic views, and the specific configuration is shown in FIG. (Shown in FIG. 4). As will be described later, a solution (sample) containing a target component is sent to the inner pipe 17A through the flow path 14, and atomized gas is sent to the outer pipe 17B through the flow path 22. The lower end portion of the inner tube 17A protrudes below the lower end of the outer tube 17B.

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

  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 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, an injection port 32 into which the inner tube 17 </ b> A and the outer tube 17 </ b> B are inserted is provided at the center of the upper surface of the lid portion 20. A recess 32A having an inner diameter substantially the same as the outer diameter of the outer tube 17B is formed at the center of the upper surface of the injection port 32. The recess 32A has an outer diameter smaller than the inner diameter of the recess 32A. A guide member 33 is attached. In the center of the guide member 33, a pipe line 34 into which the inner pipe 17A is inserted is provided, and the inlet side is a tapered portion 34A for guiding the tip of the inner pipe 17A, and the outlet side is The straight pipe portion 34B has an inner diameter slightly larger than the outer diameter of the inner pipe 17A. Further, two passages of a liquid passage 32B and an atomizing gas passage 32C are formed inside the injection port 32, and the outlet ends of these passages 32B and 32C are both open to the bottom surface of the injection port 32. doing. The inlet end of the liquid passage 32B is opened at a position facing the outlet end of the conduit 34 of the guide member 33, and a cuff 36 is attached to the outlet end of the liquid passage 32B. On the other hand, the inlet end of the atomizing gas passage 32C is opened between the inner periphery of the recess 32A and the outer periphery of the guide member 33, and the atomizing gas blowing pipe 37 is provided at the outlet end of the atomizing gas passage 32C. Is attached below the outlet end of the cuff 36 and toward the center line of the cuff 36.

  Between the bottom surface of the recess 32A and the bottom surface of the guide member 33, an O-ring 35 made of an elastic resin having an inner diameter substantially the same as the outer diameter of the inner tube 17A is disposed coaxially with the conduit 34 and the liquid passage 32B. Has been. On the bottom surface of the guide member 33, the peripheral edge of the outlet end of the conduit 34 protrudes in the axial direction of the conduit 34, that is, downward, and this projecting portion 33A plays a characteristic role in the present invention (details will be described later). To do). The inner diameter of the projecting portion 33A is substantially the same as the inner diameter of the pipe line, and the outer diameter of the projecting portion 33A is smaller than a value obtained by adding the inner diameter to a half of the difference between the outer diameter and the inner diameter of the O-ring 35 ( That is, it is desirable that the protruding portion 33A be positioned inside the circle formed by connecting the upper ends of the O-rings 35). An example of the dimensions of each part is shown in FIG.

  A donut-shaped cushion 20A is provided on the upper surface of the lid portion 20 to enhance the adhesion to the exhaust seal pipe 17C. Further, between the inner periphery of the cushion 20A and the outer periphery of the injection port 32, An exhaust port 38 for discharging the atomized gas introduced into the injection container 21 and the solvent evaporated in the injection container 21 is provided.

  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 17 </ b> B of the multiple 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.

Then, the procedure at the time of performing a gas spraying type evaporation / drying process with the preparative purification apparatus of FIG. 1 is demonstrated. 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 moves the sorting head 16 above the injection port 32 of a predetermined injection container 21 specified by the XYZ drive mechanism 29, and lowers the sorting head 16. When the sorting head 16 is lowered, the multiple tube 17 is also lowered, and first, the lower end of the inner tube 17A reaches the tapered portion 34A of the conduit 34 opened on the upper surface of the guide member 33. When the sorting head 16 is further lowered, the tip of the inner pipe 17A reaches the straight pipe part 34B of the pipe line 34 via the taper part 34A, and further protrudes downward from the outlet end of the pipe line 34 to the inner periphery of the O-ring 35. Contact with.

  At this time, in the conventional gas spraying type liquid injection device shown in FIGS. 6 and 7, since the height of the outlet of the conduit 66 and the height of the upper end of the O-ring 69 are equal, the tip of the inner tube 60A is the O-ring. In some cases, the O-ring 69 may be contacted at a position close to the upper end of the 69. Therefore, the angle (β in the figure) formed by the tangent line of the O-ring 69 and the axial direction of the inner pipe 60A at this contact point increases (that is, the tangent line and the axial direction become nearly perpendicular), and the inner pipe 60A There is a possibility that the tip may be caught by the O-ring 69 or the surface of the O-ring 69 may be damaged.

  On the other hand, in the injection container of this embodiment, as shown in FIG. 4, the pipe 34 is extended downward by providing the protrusion 33 </ b> A on the bottom surface of the guide member 33, and the height of the outlet is O-ring. It becomes lower than the height of the upper end of 35. For this reason, the tip of the inner tube 17A comes into contact with the inner periphery of the O-ring 35 at a position lower than the conventional one. As a result, the angle (α in the figure) formed by the tangent line of the O-ring 35 and the axial direction of the inner tube 17A at this contact point can be made smaller than before (that is, the tangent line of the O-ring and the axial direction). Therefore, it is possible to prevent the tip of the inner tube 17A from being caught by the O-ring 35 or from damaging the surface of the O-ring 35.

  When the sorting head 16 further descends from the above state, the tip of the inner tube 17A passes through the central hole of the O-ring 35 and reaches the middle of the liquid passage 32B. At this time, the outer periphery of the inner tube 17A is sealed by the O-ring 35. As the sorting head 16 is lowered, the outer tube 17B is also lowered and inserted into the recess 32A on the upper surface of the injection port 32 (FIG. 2B). Since the inner diameter of the recess 32A is substantially equal to the outer diameter of the outer tube 17B, the space between the outer tube 17B and the recess 32A is hermetically sealed. Further, the exhaust seal pipe 17 </ b> C is lowered together with the sorting head 16 and presses the cushion 20 </ b> A provided on the lid 20. Thereby, the space between the exhaust seal tube 17C and the injection container 21 is hermetically sealed. Note that the container rack 24 may move instead of the sorting head 16 moving.

  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 recess 32A of the injection port 32 through the flow path 22 and the outer tube 17B, and further passes between the inner periphery of the recess 32A and the outer periphery of the guide member 33. Then, it flows into the atomizing gas passage 32C and starts to be blown out from the atomizing gas blowing pipe 37. The recess 32A is sealed by the lower end of the outer tube 17B, and the outer periphery of the inner tube 17A is in close contact with the inner periphery of the O-ring 35, so that the atomized gas introduced from the outer tube 17B is There is hardly any leakage from the upper end of the recess 32A to the outside or entry into the solution passage 32B along the outer peripheral surface of the inner tube 17A. On the other hand, the solution sent from the trap column 8, that is, dichloromethane containing the target component, is supplied to the liquid passage 32B from the lower end of the inner tube 17A of the multiple tube 17 through the flow channel 12 and the flow channel 14, and the cuff portion. It is dripped from the lower end of 36. As described above, since the atomizing gas blowing pipe 37 is designed to face the center line of the cuff 36, the atomized gas blown from the atomizing gas blowing pipe 37 into the solution dropped from the cuff 36. And the solution is sheared to mist.

  In the injection container 21 of the present embodiment, since the solution and the atomizing gas do not flow on the same axis, the distance that the solution is exposed to the atomizing gas is short, and the diameter of the mist is large. Further, as the distance between the position where the solution is sheared (intersection of the center line of the cuff 36 and the straight line indicating the direction of the atomizing gas blowing pipe 37) and the tip of the atomizing gas blowing pipe 37 increases, the atomization increases. Since the gas diffuses and loses energy, the diameter of the mist similarly increases. Therefore, the size of the diameter of the mist obtained can be changed by appropriately adjusting the distance from the tip of the atomizing gas blowing pipe 37 to the shearing position and the angle formed by the center line and the straight line. For example, the lid 20 may have a structure in which the position and / or angle of the tip of the atomizing gas blowing pipe 37 can be freely changed, or the position and angle of the tip of the atomizing gas blowing pipe 37 can be changed. A plurality of different lids 20 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 above is the procedure of the gas spraying evaporation / drying process of the present embodiment using the preparative purification apparatus of FIG. 1, but at the tip of the cuff 36 during the gas spraying evaporation / drying process. Solute may precipitate and grow along the outer wall of the cuff 36. In order to prevent this, the cuff portion 36 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 cuff 36 due to surface tension on the outer wall of the cuff 36. For the same reason, it is desirable that the injection port 32 is also made of a PTFE resin material. Further, it is desirable that the outlet of the atomizing gas blowing pipe 37 has a wide rectangular shape. Thereby, the atomization gas flow which blows off from the atomization gas blowing pipe 37 becomes a wide thing, and can spray 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 body 19 from an oblique direction, the solution accumulated on the bottom surface of the injection container body 19 is agitated to promote evaporation. be able to. At this time, if the angle and position of the atomizing gas blowing pipe 37 and the height of the injection container 21 are appropriately designed so that the atomizing gas hits the center of the bottom surface, the solution accumulated on the bottom surface can be more efficiently obtained. Can diffuse.

  Further, in the configuration of the present embodiment, the lengths of the injection port 32 and the inner tube 17A are designed so that the tip of the inner tube 17A does not protrude from the outlet end of the liquid passage 32B and is contained in the liquid passage 32B. The solution containing the target component supplied from the inner tube 17A is discharged into the injection container 21 from the cuff 36 through the liquid passage 32B. In the injection port 32 having this structure, since the inner tube 17A is not exposed to the injection container 21, droplets and powder scattered in the injection container 21 are prevented from adhering to the inner tube 17A. Further, since the outer tube 17B is not introduced into the injection container 21, no droplets or powder adhere to the outer tube 17B. Thereby, contamination can be prevented from occurring when a different liquid sample is injected in the next injection container.

  In the above configuration, the inner tube 17A may be made of stainless steel, but the cuff portion 36 is preferably made of PTFE for the reason described above. Further, the cuff 36 may be bent so that the lower end of the cuff 36 is slightly inclined toward the atomizing gas blowing pipe 37 side. According to such a configuration, the retention of the solution at the tip of the cuff 36 is reduced, and the state of the powder obtained in the injection container 21 can be improved. Further, instead of bending the cuff portion 36 or in addition to bending the cuff portion 36, the length of the cuff portion 36 is changed or the tip of the cuff portion 36 is cut obliquely. The state of the powder can be adjusted.

  However, the present invention is not limited to this configuration, and the cuff portion 36 is not provided at the outlet end of the liquid passage 32B, and the length of the injection port 32 and the inner pipe 17A is such that the tip of the inner pipe 17A protrudes from the outlet end of the liquid passage 32B. You may design. In this case, the solution supplied from the inner tube 17A is directly discharged into the injection container 21 from the tip of the inner tube 17A.

  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. In addition, 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 port 38 and the exhaust seal pipe 17C.

  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.

17 ... Multiple pipes 17A ... Inner pipe 17B ... Outer pipe 17C ... Exhaust seal pipe 19 ... Injection container body 20 ... Lid 20A ... Cushion 21 ... Injection container 32 ... Injection port 32A ... Recess 32B ... Liquid passage 32C ... Atomization Gas passage 33 ... guide member 33A ... protruding portion 34 ... pipe 34A ... tapered portion 34B ... straight pipe portion 35 ... O-ring 36 ... cuff portion 37 ... atomization gas blowing pipe 38 ... exhaust port

Claims (4)

Used in a gas spraying liquid sample injection device comprising a multiple tube having an outer tube to which atomized gas is supplied and an inner tube that protrudes below the lower end of the outer tube and to which a liquid containing a target component is supplied; An injection container in which the liquid from the multiple tube is atomized and supplied, and has an injection container body having an opening in the upper part, and an injection port provided in the opening,
The injection port is
a) a recess provided on the top surface of the injection port;
b) a liquid passage having an inlet end that opens to the bottom surface of the recess, and an outlet end that reaches the internal space of the injection container body;
c) a guide member fitted in the recess;
d) a pipe line formed inside the guide member and having an inlet end into which the inner pipe is inserted and an outlet end facing the inlet end of the liquid passage;
e) It is disposed between the guide member and the bottom surface of the recess, and contacts the outer periphery of the inner tube at the inner periphery when the inner tube is inserted into the liquid passage through the conduit. O-ring,
Have
The injection container, wherein the guide member protrudes in an axial direction of the pipe line at a peripheral edge of an outlet end of the pipe line. The guide member has an outer diameter smaller than the inner diameter of the recess,
When the inner tube is inserted into the conduit, the recess is in airtight contact with the outer peripheral surface of the lower end of the outer tube at the inner peripheral surface of the recess,
The injection port further comprises
f) an atomizing gas passage having an inlet end that opens between the inner periphery of the recess and the outer periphery of the guide member; and an outlet end that reaches the internal space of the injection container;
g) an atomizing gas blowing pipe extending from the outlet end of the atomizing gas passage toward the lower side of the outlet end of the liquid passage;
The injection container according to claim 1, comprising: An outer tube that is supplied with an atomizing gas, and an inner tube that protrudes below the lower end of the outer tube and is supplied with a liquid containing a target component, for atomizing and supplying the liquid into an injection container A gas spraying liquid injection device having a multiple tube and an injection port provided at the inlet of the injection container,
The injection port is
a) a recess provided on the top surface of the injection port;
b) a liquid passage having an inlet end that opens to the bottom surface of the recess, and an outlet end that reaches the internal space of the injection container;
c) a guide member fitted in the recess;
d) a pipe line formed inside the guide member and having an inlet end into which the inner pipe is inserted and an outlet end facing the inlet end of the liquid passage;
e) It is disposed between the guide member and the bottom surface of the recess, and contacts the outer periphery of the inner tube at the inner periphery when the inner tube is inserted into the liquid passage through the conduit. O-ring,
Have
The gas spraying liquid injection device according to claim 1, wherein the guide member protrudes in an axial direction of the pipe line at a peripheral edge of the outlet end of the pipe line. The guide member has an outer diameter smaller than the inner diameter of the recess,
When the inner tube is inserted into the conduit, the recess is in airtight contact with the outer peripheral surface of the lower end of the outer tube at the inner peripheral surface of the recess,
The injection port further comprises
f) an atomizing gas passage having an inlet end that opens between the inner periphery of the recess and the outer periphery of the guide member; and an outlet end that reaches the internal space of the injection container;
g) an atomizing gas blowing pipe extending from the outlet end of the atomizing gas passage toward the lower side of the outlet end of the liquid passage;
The gas spraying type liquid injection device according to claim 3, wherein

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