Liquid sample valve, gas chromatograph device, cleaning method, and cleaning program

Abstract

To obtain a liquid sample valve capable of preventing deterioration of analysis accuracy by reducing a residual liquid sample in a flow path.SOLUTION: A liquid sample valve includes: a structure 21 in which a sample chamber 211 inside which a liquid sample passes is formed, and an inflow port 212, an outflow port 213, a first opening 214 and a second opening 215 formed at positions facing each other are formed; a primary side flow path 22 connected to the inflow port 212; a secondary side flow path 23 connected to the outflow port 213; a rod-shaped stem 26 penetrating the first opening 214 and the second opening 215; a first seal material 24 closing a gap between the first opening 214 and the stem 26; a second seal material 25 closing a gap between the second opening 215 and the stem 26; and an ultrasonic vibrator 7 applying ultrasonic vibration to at least one of the structure 21, the primary side flow path 22, the secondary side flow path 23, and the stem 26.SELECTED DRAWING: Figure 5

Description

[Technical Field]

[0001] The present invention relates to a liquid sample valve, a gas chromatograph device, a cleaning method, and a cleaning program. [Background technology]

[0002] Gas chromatographs equipped with detectors that perform component analysis of multi-component mixed samples are known. The detectors perform component analysis of gases. When the multi-component mixed sample to be analyzed is a liquid, the multi-component mixed sample is vaporized from the liquid and sent to the detector. In the following description, the multi-component mixed sample analyzed by the gas chromatograph will simply be referred to as a sample. When the sample is a liquid, it will be referred to as a liquid sample.

[0003] A device that vaporizes a liquid sample and sends it to a detector is, for example, a liquid sample valve disclosed in Patent Document 1. In the liquid sample valve, a portion of the liquid sample is extracted from a flow path through which the liquid sample passes and vaporized. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 5-87705 Summary of the Invention [Problem to be solved by the invention]

[0005] In gas chromatographs, the liquid sample to be analyzed may be switched by switching the liquid sample passed through the liquid sample valve. If the liquid sample before the switch remains in the flow path of the liquid sample valve, it will mix with the liquid sample after the switch, reducing the accuracy of the analysis.

[0006] For example, to prevent the liquid sample from remaining in the flow path, the liquid sample after switching is allowed to flow through the flow path for a certain period of time, thereby removing the liquid sample from the flow path before switching. However, a small amount of remaining liquid sample may lead to a decrease in the analytical accuracy of the liquid sample after switching, and therefore it is desirable to further reduce the amount of remaining liquid sample.

[0007] An object of the present invention is to provide a liquid sample valve that can reduce the amount of liquid sample remaining in a flow path and prevent a decrease in analytical accuracy. [Means for solving the problem]

[0008] The liquid sample valve of the present invention comprises a structure having a sample chamber formed therein through which the liquid sample passes, an inlet for allowing the liquid sample to flow into the sample chamber, an outlet for allowing the liquid sample to flow out of the sample chamber, and first and second openings formed at opposing positions to connect the sample chamber to the outside, a primary side flow path connected to the inlet, a secondary side flow path connected to the outlet, a rod-shaped stem that penetrates the first and second openings, a first sealing material that seals the gap between the first opening and the stem, a second sealing material that seals the gap between the second opening and the stem, and an ultrasonic vibrator that applies ultrasonic vibrations to at least one of the structure, the primary side flow path, the secondary side flow path, and the stem. [Effects of the Invention]

[0009] According to the present invention, it is possible to obtain a liquid sample valve that can reduce the amount of liquid sample remaining in the flow channel and prevent a decrease in analytical accuracy. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a diagram showing a schematic configuration of a gas chromatograph according to a first embodiment. [Figure 2] FIG. 1 is a perspective view of a liquid sample valve according to a first embodiment. [Figure 3]FIG. 1 is a side view of a liquid sample valve according to a first embodiment. [Figure 4] 4 is a cross-sectional view of the liquid sample valve taken along line IV-IV shown in FIG. 3. FIG. [Figure 5] FIG. 5 is a partially enlarged cross-sectional view of a portion A shown in FIG. 4. [Figure 6] 5 is a cross-sectional view of the liquid sample valve according to FIG. 4, showing the stem in a second position. [Figure 7] 10 is a flowchart showing the procedure of ultrasonic cleaning and component analysis executed by the control unit. [Figure 8] FIG. 10 is a cross-sectional view showing a first modified example of the position where an ultrasonic transducer is installed. [Figure 9] FIG. 10 is a cross-sectional view showing a second modified example of the position where the ultrasonic transducer is installed. DETAILED DESCRIPTION OF THE INVENTION

[0011] A liquid sample valve, a gas chromatograph device, a cleaning method, and a cleaning program according to an embodiment of the present invention will be described in detail below with reference to the drawings. Note that the present invention is not limited to the embodiment described below.

[0012] [Embodiment 1] <Overall configuration of gas chromatograph equipment> 1 is a diagram showing a schematic configuration of a gas chromatograph according to embodiment 1. The gas chromatograph 1 is an apparatus for analyzing the components of a multi-component mixed sample (sample). In embodiment 1, the gas chromatograph 1 is illustrated as being configured to vaporize a liquid sample using a liquid sample valve 2 for analysis.

[0013] The gas chromatograph 1 comprises a liquid sample valve 2, a column 3, a detector 4, a constant temperature oven 5, and a control unit 6. The liquid sample valve 2 is a device for vaporizing a liquid sample to be analyzed and sending it to the column 3 provided downstream.

[0014] <Liquid sample valve> Fig. 2 is a perspective view of the liquid sample valve according to embodiment 1. Fig. 3 is a side view of the liquid sample valve according to embodiment 1. Fig. 4 is a cross-sectional view of the liquid sample valve taken along line IV-IV shown in Fig. 3.

[0015] The liquid sample valve 2 comprises a structure 21, a primary side flow path 22, a secondary side flow path 23, a first sealing material 24, a second sealing material 25, a stem 26, an ultrasonic vibrator 7, a driving mechanism part 27, and a vaporization part 28.

[0016] <Structure> 4, a sample chamber 211 through which a liquid sample passes is formed inside the structure 21. An inlet 212 that connects the sample chamber 211 to the outside is formed in the structure 21. An outlet 213 that connects the sample chamber 211 to the outside is formed in the structure 21. In the first embodiment, the inlet 212 and the outlet 213 are formed at positions facing each other.

[0017] Here, the Z axis is set to be parallel to the penetration direction of the inlet 212 and the outlet 213. The X axis is set to be perpendicular to the Z axis and parallel to the direction in which the rod-shaped stem 26 described below extends. The Y axis is set to be perpendicular to the X axis and the Z axis. In the following description, the positive direction along the X axis is defined as the right, and the negative direction is defined as the left. The positive direction along the Z axis is defined as the up, and the negative direction is defined as the down. Note that the up, down, left, and right defined here are for convenience and do not limit the orientation of the liquid sample valve 2 during use.

[0018] The structure 21 is provided inside the cylindrical outer shell 9. The structure 21 is formed with a first opening 214 and a second opening 215 that communicate between the sample chamber 211 and the outside, and that face each other along the left-right direction.

[0019] <Primary side flow path / Secondary side flow path> 5 is a partially enlarged cross-sectional view of portion A shown in FIG. 4. The primary-side flow path 22 is formed in a cylindrical shape and allows a liquid sample to pass through. The primary-side flow path 22 is connected to the inlet 212 of the structure 21. For example, one end of the primary-side flow path 22 is inserted into the inlet 212 and fixed to the structure 21 by brazing. When the primary-side flow path 22 is inserted and fixed in this manner, an abutment surface 212a against which the end of the primary-side flow path 22 abuts may be formed on the inner circumferential surface of the inlet 212. The primary-side flow path 22 may be formed integrally with the structure 21.

[0020] The secondary-side flow path 23 is formed in a cylindrical shape and allows a liquid sample to pass through. The secondary-side flow path 23 is connected to the outlet 213 of the structure 21. For example, one end of the secondary-side flow path 23 is inserted into the outlet 213 and fixed to the structure 21 by brazing. When the secondary-side flow path 23 is inserted and fixed in this manner, an abutment surface 213a against which the end of the secondary-side flow path 23 abuts may be formed on the inner circumferential surface of the outlet 213. The secondary-side flow path 23 may be formed integrally with the structure 21.

[0021] In the liquid sample valve 2, the liquid sample flows into the sample chamber 211 through the primary flow path 22, and the liquid sample that has flowed into the sample chamber 211 flows out through the secondary flow path 23. That is, in the liquid sample valve 2, the flow paths through which the liquid sample passes include the sample chamber 211, the primary flow path 22, and the secondary flow path 23.

[0022] <First sealant and second sealant> The first sealant 24 closes the first opening 214 formed in the structure 21. The first sealant 24 has a through-hole 241 formed therein, which connects the sample chamber 211 to the outside. The second sealant 25 closes the second opening 215 formed in the structure 21. The second sealant 25 has a through-hole 251 formed therein, which connects the sample chamber 211 to the outside.

[0023] The through holes 241 and 251 face each other, and the central axes of the through holes 241 and 251 are coaxial. The directions in which the central axes of the through holes 241 and 251 extend are parallel to the X-axis.

[0024] <Stem> The stem 26 is formed in a rod shape. The stem 26 passes through a through-hole 241 formed in the first sealant 24 and a through-hole 251 formed in the second sealant 25. The stem 26 is movable in the left-right direction, but is in close contact with the inner circumferential surfaces of the through-holes 241 and 251, so that the liquid sample passing through the sample chamber 211 does not leak from the gap between the stem 26 and the through-holes 241 and 251.

[0025] Stem 26 has a recess 261 formed in its outer circumferential surface. Fig. 6 is a cross-sectional view of the liquid sample valve corresponding to Fig. 4, showing the stem in a second position. Stem 26 is movable between a first position where recess 261 is located in sample chamber 211 as shown in Fig. 4, and a second position where recess 261 is moved to the outside of sample chamber 211 through through-hole 251 of second sealing material 25 as shown in Fig. 6.

[0026] <Ultrasonic vibrator> Returning to FIG. 5 , the ultrasonic vibrator 7 is formed in a ring shape that penetrates the structure 21 to the inside. The ultrasonic vibrator 7 is provided between the outer shell body 9 and the structure 21. In the first embodiment, two ultrasonic vibrators 7 are provided to sandwich the primary flow path 22 and the secondary flow path 23. Note that the configuration is not limited to providing two ultrasonic vibrators 7, and a configuration in which only one of the ultrasonic vibrators 7 is provided may also be used. Furthermore, the ultrasonic vibrator 7 may be provided so as to protrude from the outer shell body 9 in the left-right direction. Furthermore, the ultrasonic vibrator 7 may also be provided on the outside of the outer shell body 9.

[0027] The ultrasonic vibrator 7 is in contact with the structure 21, the primary-side flow path 22, and the secondary-side flow path 23. When driven, the ultrasonic vibrator 7 applies ultrasonic vibrations to the structure 21, the primary-side flow path 22, and the secondary-side flow path 23, generating ultrasonic waves in the liquid sample therein. Note that the liquid sample valve 2 is not limited to a configuration in which the ultrasonic vibrator 7 is in contact with all of the structure 21, the primary-side flow path 22, and the secondary-side flow path 23. As long as the ultrasonic vibrator 7 is in contact with at least one of the structure 21, the primary-side flow path 22, and the secondary-side flow path 23, ultrasonic waves can be generated in the liquid sample.

[0028] <Drive mechanism> 4 and 6, the drive mechanism 27 is provided on the opposite side of the structure 21 with the first seal material 24 interposed therebetween. The drive mechanism 27 includes a piston 271 and a cylinder 272.

[0029] The piston 271 is connected to the stem 26. The portion of the stem 26 to which the piston 271 is connected is the end of the portion that protrudes to the outside of the structure 21 through the through-hole 241 of the first sealing material 24. The piston 271 and the stem 26 move in conjunction with each other.

[0030] The cylinder 272 has an internal space formed therein that accommodates the piston 271 and the portion of the stem 26 that protrudes to the outside of the structure 21 through the through-hole 241 of the first seal member 24 .

[0031] A first opening 273 and a second opening 274 that communicate the internal space with the outside are formed in the cylinder 272. The first opening 273 is formed at a position farther from the structure 21 than the piston 271, regardless of the position of the piston 271 in the internal space. That is, the first opening 273 is located to the left of the piston 271 in both the state shown in FIG. 4 and the state shown in FIG. 6.

[0032] The second opening 274 is formed at a position closer to the structure 21 than the piston 271, regardless of the position of the piston 271 in the internal space. That is, the second opening 274 is located to the right of the piston 271 in both the state shown in FIG. 4 and the state shown in FIG.

[0033] By sending air into the internal space of the cylinder 272 through the first opening 273, the piston 271 can be moved to the right, thereby moving the stem 26, which is in the first position as shown in FIG. 4, to the second position as shown in FIG. 6.

[0034] Furthermore, the piston 271 can be moved to the left by sending air into the internal space of the cylinder 272 from the second opening 274. This allows the stem 26, which is in the second position as shown in FIG. 6, to move to the first position as shown in FIG.

[0035] <Vaporization section> The vaporizer 28 is provided on the opposite side of the structure 21 with the second sealant 25 sandwiched therebetween. The vaporizer 28 is connected to the outer shell 9 to form an integrated unit. For example, the vaporizer 28 is screwed into the inside of the outer shell 9 to form an integrated unit. The outer shell 9 integrated with the vaporizer 28 and the drive mechanism 27 are connected with a cap nut 291 provided on the cylinder 272, whereby the first sealant 24 sandwiched between the cylinder 272 and the structure 21 and the second sealant 25 sandwiched between the vaporizer 28 and the structure 21 are compressed. As a result, the first sealant 24 is brought into close contact with the first opening 214 formed in the structure 21, and the second sealant 25 is brought into close contact with the second opening 215 formed in the structure 21, preventing leakage of the liquid sample from the sample chamber 211.

[0036] Vaporizer 28 is formed with vaporized sample flow path 281 and carrier gas flow path 282. Vaporized sample flow path 281 extends linearly rightward from through-hole 251 of second sealant 25 so as to be able to accommodate stem 26 in the second position. Vaporized sample flow path 281 is connected to column 3.

[0037] A cylinder 8 is inserted into vaporized sample flow path 281. Cylinder 8 is, for example, a cylindrical glass tube. Cylinder 8 is inserted to a position where one end is near second sealing material 25. The outer diameter of cylinder 8 is smaller than the inner diameter of vaporized sample flow path 281. A gap is formed between the outer peripheral surface of cylinder 8 and the inner peripheral surface of vaporized sample flow path 281.

[0038] The inner diameter of cylindrical body 8 is larger than the outer diameter of stem 26, and stem 26 in the second position is inserted into cylindrical body 8. As will be described in detail later, the liquid sample transported by stem 26 to the inside of vaporized sample flow path 281, more specifically, to the inside of cylindrical body 8, is vaporized. In the following description, the vaporized liquid sample will be referred to as the vaporized sample.

[0039] The carrier gas flow path 282 is connected to the vaporized sample flow path 281. A carrier gas is sent into the carrier gas flow path 282 from the outside. The carrier gas sent from the outside passes through a gap between the inner circumferential surface of the vaporized sample flow path 281 and the outer circumferential surface of the cylindrical body 8 and flows into the inside of the cylindrical body 8. The carrier gas that has flowed into the inside of the cylindrical body 8 is then transported to the column 3. The vaporized sample vaporized inside the cylindrical body 8 is transported to the column 3 by the flow of the carrier gas. The carrier gas is, for example, hydrogen, nitrogen, or argon.

[0040] Vaporization unit 28 is provided with temperature element 283 and heater 284. Heater 284 makes it easier to vaporize the liquefied sample by increasing the temperature of vaporized sample flow path 281. Temperature element 283 detects the temperature and controls the on / off of heater 284, thereby controlling the temperature of vaporized sample flow path 281.

[0041] <Columns and detectors> Returning to Figure 1, column 3 is formed in a tubular shape that allows the vaporized sample to pass through. As the vaporized sample passes through column 3, the components contained in the vaporized sample are separated by utilizing differences in their movement speeds. Column 3 is connected to detector 4, and the vaporized sample from which the components have been separated is sent to detector 4. Detector 4 outputs an electrical signal to control unit 6 that corresponds to each component of the separated vaporized sample. The carrier gas and vaporized sample are discharged from detector 4 as exhaust gas.

[0042] <Operation when vaporizing a liquid sample> Next, we will explain the operation of the liquid sample valve 2 when transporting the liquid sample passing through the sample chamber 211 to the vaporization sample flow path 281 and vaporizing it. As shown in Figures 4 and 5, when the stem 26 is in the first position, the recess 261 is located in the sample chamber 211.

[0043] 6, when stem 26 moves to the second position, recess 261 moves to vaporized sample channel 281. At this time, the liquid sample inside recess 261 is also transported to vaporized sample channel 281 (inside cylindrical body 8) together with recess 261. The transported liquid sample evaporates inside cylindrical body 8 and is vaporized.

[0044] <Liquid sample switching> In the gas chromatograph 1, a liquid sample to be analyzed is sent to the sample chamber 211 through the primary flow path 22 of the liquid sample valve 2. In the gas chromatograph 1, the liquid sample sent to the sample chamber 211 may be switched to perform component analysis of a liquid sample different from the previous one.

[0045] The liquid sample may be switched by exchanging the connection destination of the primary flow path 22, or may be automatically switched by a switching valve.

[0046] <Constant temperature oven> The constant temperature oven 5 heats the liquid sample valve 2, the column 3, and the detector 4, and maintains the temperature to promote vaporization of the liquefied sample.

[0047] <Control unit> The control unit 6 controls the operation of the gas chromatograph apparatus 1. For example, the control unit 6 displays the detection results (including information indicating the concentrations of each of the multiple components contained in the sample) on a display unit (not shown) based on an electrical signal output from the detector 4. The control unit 6 also controls a valve (not shown) to send air into the cylinder 272 from a first opening 273 of the cylinder 272 to move the stem 26 to the second position. The control unit 6 also sends air into the cylinder 272 from a second opening 274 of the cylinder 272 to move the stem 26 to the first position. The control unit 6 also controls the driving of the ultrasonic vibrator 7. The control unit 6 also controls the heater 284 based on the detection result of the temperature element 283 to control the temperature of the vaporized sample flow path 281.

[0048] The control unit 6 is, for example, an electronic circuit. Examples of the electronic circuit include an integrated circuit such as an ASIC (Application Specific Integrated Circuit) or an FPGA (Field Programmable Gate Array), a CPU (Central Processing Unit), or an MPU (Micro Processing Unit).

[0049] <Cleaning when switching liquid samples> If the liquid sample before switching remains in the flow path of the liquid sample valve 2 when switching liquid samples, it will mix with the liquid sample after switching, reducing the accuracy of the analysis. After switching liquid samples, the liquid sample after switching is passed through the flow path for a certain amount of time to wash away the liquid sample before switching before starting the analysis, thereby preventing a reduction in the accuracy of the analysis. However, there are cases where the liquid sample before switching is not sufficiently removed. In particular, when the component concentrations of the liquid sample before switching and the liquid sample after switching are significantly different, even a small amount of remaining liquid can have a significant impact on the accuracy of the analysis.

[0050] In the gas chromatograph device 1 of the first embodiment, when the liquid sample is switched, the ultrasonic vibrator 7 is driven to remove the liquid sample remaining in the flow path before the switch.

[0051] When the ultrasonic vibrator 7 is driven, ultrasonic waves are generated in the liquid sample passing through the flow path, and the inside of the flow path is ultrasonically cleaned. In ultrasonic cleaning, the ultrasonic waves generated in the liquid sample generate bubbles in the liquid sample, and the liquid sample remaining in the flow path before switching is removed by the cavitation effect, etc.

[0052] Ultrasonic cleaning can reduce the amount of pre-switching liquid sample remaining in the flow path compared to cleaning that simply passes the post-switching liquid sample. Furthermore, ultrasonic cleaning can shorten the cleaning time compared to cleaning that simply passes the post-switching liquid sample. In the flow path, the pre-switching liquid sample is likely to remain in areas where components contact each other. In Figure 5, examples of areas where the liquid sample is likely to remain are shown enclosed by dashed lines. Specifically, these areas include the area where the primary-side flow path 22 and the structure 21 contact, the area where the secondary-side flow path 23 and the structure 21 contact, the area where the first sealant 24 and the structure 21 contact, the area where the second sealant 25 and the structure 21 contact, the area where the first sealant 24 and the stem 26 contact, and the area where the second sealant 25 and the stem 26 contact. Even in these areas, ultrasonic cleaning can more reliably remove the pre-switching liquid sample remaining in the flow path by utilizing the cavitation effect, etc.

[0053] Ultrasonic cleaning when switching liquid samples may be performed by the control unit 6. The ultrasonic cleaning procedure performed by the control unit 6 will be described below. Fig. 7 is a flowchart showing the ultrasonic cleaning and component analysis procedure performed by the control unit.

[0054] First, the liquid sample after switching is passed through the flow path (step S1). Next, the ultrasonic vibrator 7 is driven for a predetermined time to clean the inside of the flow path (step S2). Next, the driving of the ultrasonic vibrator 7 is stopped (step S3). Step S3 completes the ultrasonic cleaning. Next, air is sent into the first opening 273 formed in the cylinder 272 to move the stem 26 to the second position (step S4). This transports the switched liquid sample to the vaporized sample flow path 281, and component analysis begins. Next, air is sent into the second opening 274 formed in the cylinder 272 to move the stem 26 to the first position (step S5). Component analysis of the switched liquid sample is performed in steps S4 and S5. Note that in the above procedure, an example has been shown in which the stem 26 is stopped at the first position during cleaning of the inside of the flow path by driving the ultrasonic vibrator 7 in step S2. Here, the stem 26 may be moved to the second position and stopped there during cleaning of the inside of the flow path by driving the ultrasonic vibrator in step S2. Furthermore, during cleaning of the flow path by driving the ultrasonic vibrator 7 in step S2, the stem 26 may be caused to reciprocate between the first position and the second position. Furthermore, this reciprocating movement of the stem 26 may be repeatedly performed. Furthermore, when the stem 26 is repeatedly reciprocated in step S2, carrier gas may be simultaneously flowed through the carrier gas flow path 282 and the vaporized sample flow path 281. Furthermore, when the stem 26 is repeatedly reciprocated and carrier gas is flowing in step S2, the component concentrations of the liquid sample may be measured even during cleaning of the flow path, thereby making it possible to confirm that cleaning has been performed sufficiently based on the detected component concentration results. Once it has been confirmed that cleaning has been performed sufficiently, the process proceeds to step S3, in which the driving of the ultrasonic vibrator 7 is stopped. The subsequent reciprocating movement of the stem 26 corresponds to the movement of the stem 26 in steps S4 and S5.

[0055] The gas chromatograph apparatus 1 may include a storage unit (not shown) that stores a program for causing the control unit 6 to execute the ultrasonic cleaning procedure described above. The storage unit is, for example, a semiconductor memory element such as a random access memory (RAM), a read only memory (ROM), or a flash memory, or a storage device such as a hard disk or an optical disk.

[0056] <First Modification> FIG. 8 is a cross-sectional view showing a first modified example of the position at which the ultrasonic vibrator is installed. In this first modified example, the ultrasonic vibrator 7 is formed in a ring shape with the primary-side flow path 22 penetrating inside. The ultrasonic vibrator 7 abuts against at least one of the structure 21 and the primary-side flow path 22. Even when the ultrasonic vibrator 7 is provided in this manner, ultrasonic waves can be generated in the flow path to remove the liquid sample before switching. When bubbles are generated by ultrasonic waves in the primary-side flow path 22, the bubbles flow downstream with the flow of the liquid sample. Therefore, the bubbles can be introduced into the sample chamber 211 located downstream of the primary-side flow path 22, allowing the sample chamber 211 to be cleaned.

[0057] The ultrasonic vibrator 7 may be formed in a ring shape with the secondary side flow path 23 penetrating inside, or both an ultrasonic vibrator 7 with the primary side flow path 22 penetrating inside and an ultrasonic vibrator 7 with the secondary side flow path 23 penetrating inside may be provided.

[0058] <Second Modification> 9 is a cross-sectional view showing a second modified example of the position where the ultrasonic vibrator is installed. In the second modified example, the ultrasonic vibrator 7 is built into the stem 26. Even when the ultrasonic vibrator 7 is installed in this way, ultrasonic waves can be generated in the flow path to remove the liquid sample before switching. Furthermore, since there is no need for space around the structure 21 to install the ultrasonic vibrator 7, it is possible to prevent the liquid sample valve 2 from becoming larger due to the installation of the ultrasonic vibrator 7.

[0059] <Summary of effects> The liquid sample valve 2 of embodiment 1 includes a structure 21 having a sample chamber 211 formed therein through which the liquid sample passes, an inlet 212 for allowing the liquid sample to flow into the sample chamber 211, an outlet 213 for allowing the liquid sample to flow out of the sample chamber 211, and a first opening 214 and a second opening 215 formed at opposite positions to connect the sample chamber 211 to the outside, a primary side flow path 22 connected to the inlet 212, a secondary side flow path 23 connected to the outlet 213, a rod-shaped stem 26 passing through the first opening 214 and the second opening 215, a first sealing material 24 sealing the gap between the first opening 214 and the stem 26, a second sealing material 25 sealing the gap between the second opening 215 and the stem 26, and an ultrasonic vibrator that applies ultrasonic vibrations to at least one of the structure 21, the primary side flow path 22, the secondary side flow path 23, and the stem 26.

[0060] This makes it possible to reduce the amount of liquid sample remaining before switching in the liquid sample flow paths (primary flow path 22, sample chamber 211, secondary flow path 23) of the liquid sample valve 2. Reducing the amount of liquid sample remaining in the flow paths before switching reduces contamination of the liquid sample after switching, and makes it possible to prevent a decrease in the accuracy of component analysis.

[0061] The ultrasonic vibrator 7 may be formed in a ring shape and provided so as to penetrate the inside of the structure 21. This allows for more reliable removal of the liquid sample before switching by ultrasonic cleaning, which generates ultrasonic waves in the liquid sample inside the flow path.

[0062] The ultrasonic vibrator 7 may be in contact with at least one of the primary flow path 22 and the secondary flow path 23. This allows for more reliable removal of the liquid sample before switching by ultrasonic cleaning, which generates ultrasonic waves in the liquid sample inside the flow path. Furthermore, when the ultrasonic vibrator 7 is in contact with the primary flow path 22, bubbles generated inside the primary flow path 22 are sent downstream to the sample chamber 211 and the secondary flow path 23 by the flow of the liquid sample, so that the inside of the flow path can be efficiently cleaned with a small number of ultrasonic vibrators 7.

[0063] The ultrasonic vibrator 7 may be in contact with the structure 21. By having the ultrasonic vibrator 7 in contact with the structure 21, ultrasonic cleaning is performed by generating ultrasonic waves in the liquid sample in the sample chamber 211, thereby more reliably removing the liquid sample before switching.

[0064] The ultrasonic vibrator 7 may be formed in a ring shape, and may penetrate the primary-side flow path 22 to the inside, with its inner circumferential surface abutting the primary-side flow path 22. By ultrasonic cleaning in which ultrasonic waves are generated in the liquid sample in the primary-side flow path 22, the liquid sample before switching can be more reliably removed.

[0065] The ultrasonic vibrator 7 may be formed in a ring shape, and may penetrate the secondary-side flow path 23 to the inside, with its inner circumferential surface abutting the secondary-side flow path 23. By ultrasonic cleaning in which ultrasonic waves are generated in the liquid sample in the secondary-side flow path 23, the liquid sample before switching can be more reliably removed.

[0066] The ultrasonic vibrator 7 may be built inside the stem 26. This allows ultrasonic vibrations to be applied to the stem 26. Since the stem 26 is provided so as to penetrate the sample chamber 211, ultrasonic cleaning, which generates ultrasonic waves in the liquid sample in the sample chamber 211, can more reliably remove the liquid sample before switching.

[0067] The gas chromatograph device 1 further includes a liquid sample valve 2 and a control unit 6 that controls the driving of the ultrasonic vibrator 7. This allows ultrasonic cleaning to be performed under the control of the control unit 6.

[0068] A recess 261 is formed on the outer peripheral surface of stem 26, and stem 26 is movable between a first position where recess 261 is in sample chamber 211 and a second position where recess 261 has moved to the outside of sample chamber 211 via second sealant 25. After switching the liquid sample flowing through primary flow path 22, controller 6 drives ultrasonic vibrator 7 for a predetermined time, and while ultrasonic vibrator 7 is being driven, may move the stem back and forth between the first position and the second position, or may stop the stem. This allows ultrasonic cleaning after switching the liquid sample to be performed under the control of controller 6.

[0069] The cleaning method for the gas chromatograph device 1 includes a step of driving the ultrasonic vibrator 7 for a predetermined time after switching the liquid sample flowing through the primary flow path 22. Thereby, ultrasonic cleaning is performed under the control of the control unit 6.

[0070] In the cleaning method for gas chromatograph 1, recess 261 is formed on the outer peripheral surface of stem 26, and stem 26 is movable between a first position where recess 261 is in sample chamber 211 and a second position where recess 261 has moved to the outside of sample chamber 211 through second sealant 25, and the step of driving the ultrasonic vibrator for a predetermined time may be a step of moving the stem back and forth between the first position and the second position or stopping the stem while the ultrasonic vibrator is being driven. Thus, ultrasonic cleaning is performed under the control of control unit 6.

[0071] 〔others〕 Some examples of combinations of the disclosed technical features are set out below.

[0072] (1) A liquid sample valve comprising: a structure having a sample chamber formed therein through which a liquid sample passes, an inlet for introducing the liquid sample into the sample chamber, an outlet for discharging the liquid sample from the sample chamber, and first and second openings formed at opposing positions to connect the sample chamber to the outside; a primary flow path connected to the inlet; a secondary flow path connected to the outlet; a rod-shaped stem penetrating the first opening and the second opening; a first sealing material sealing the gap between the first opening and the stem; a second sealing material sealing the gap between the second opening and the stem; and an ultrasonic vibrator applying ultrasonic vibrations to at least one of the structure, the primary flow path, the secondary flow path, and the stem.

[0073] (2) The liquid sample valve according to (1) above, wherein the ultrasonic vibrator is formed in an annular shape and is provided so as to penetrate the structure to the inside.

[0074] (3) The liquid sample valve according to (2) above, wherein the ultrasonic vibrator is in contact with at least one of the primary flow path and the secondary flow path.

[0075] (4) The liquid sample valve according to (1) or (2) above, wherein the ultrasonic vibrator is in contact with the structure.

[0076] (5) The liquid sample valve according to (1) above, wherein the ultrasonic vibrator is formed in an annular shape, and the primary side flow path is passed through the ultrasonic vibrator inward, with the inner circumferential surface abutting the primary side flow path.

[0077] (6) The liquid sample valve according to (1) above, wherein the ultrasonic vibrator is formed in an annular shape, and the secondary flow path is passed through the ultrasonic vibrator inward, with the inner circumferential surface abutting the secondary flow path.

[0078] (7) The liquid sample valve according to (1) above, wherein the ultrasonic vibrator is built into the stem.

[0079] (8) A gas chromatograph apparatus further comprising the liquid sample valve according to any one of (1) to (7) above, and a control unit that controls the driving of the ultrasonic vibrator.

[0080] (9) A gas chromatograph apparatus according to (8) above, wherein a recess is formed on the outer peripheral surface of the stem, and the stem is movable between a first position where the recess is in the sample chamber and a second position where the recess has moved outside the sample chamber through a second sealing material, and the control unit drives the ultrasonic vibrator for a predetermined time after switching the liquid sample flowing through the primary side flow path, and while the ultrasonic vibrator is being driven, moves the stem back and forth between the first position and the second position, or stops the stem.

[0081] (10) A cleaning method for the gas chromatograph apparatus described in (8) above, comprising the step of driving the ultrasonic vibrator for a predetermined time after switching the liquid sample flowing through the primary flow path.

[0082] (11) A cleaning method according to (10) above, wherein a recess is formed on the outer peripheral surface of the stem, and the stem is movable between a first position where the recess is in the sample chamber and a second position where the recess has moved outside the sample chamber through a second sealing material, and the step of driving the ultrasonic vibrator for a predetermined time is a step of moving the stem back and forth between the first position and the second position while the ultrasonic vibrator is being driven, or of stopping the stem.

[0083] (12) A cleaning program that causes the control unit in the gas chromatograph device described in (8) above to perform a step of driving the ultrasonic vibrator for a predetermined time after switching the liquid sample flowing through the primary side flow path. [Explanation of symbols]

[0084] 1. Gas chromatograph 2 Liquid sample valves 21 Structure 211 Sample Room 212 Inlet 212a Abutment surface 213 Outlet 213a Abutment surface 214 First Opening 215 Second Opening 22 Primary flow path 23 Secondary flow path 24 First sealing material 241 Through hole 25 Second sealing material 251 Through hole 26 Stem 261 recess 27 Drive mechanism 271 Piston 272 cylinders 273 First Opening 274 Second Opening 28 Vaporization section 281 Vaporization sample flow path 282 Carrier gas flow path 283 Temperature element 284 Heater 291 Cap nut 3 columns 4. Detector 5 Constant Temperature Oven 6 Control Unit 7 Ultrasonic transducer 8 cylinder

Claims

1. a structure having a sample chamber formed therein through which a liquid sample passes, an inlet for allowing the liquid sample to flow into the sample chamber, an outlet for allowing the liquid sample to flow out of the sample chamber, and a first opening and a second opening formed at positions opposite to each other and connecting the sample chamber to the outside; a primary flow path connected to the inlet; a secondary flow path connected to the outlet; a rod-shaped stem that passes through the first opening and the second opening; a first sealing material that seals a gap between the first opening and the stem; a second sealing material that seals the gap between the second opening and the stem; a liquid sample valve including the structure, the primary flow path, the secondary flow path, and an ultrasonic vibrator that applies ultrasonic vibrations to at least one of the stem.

2. 2. The liquid sample valve according to claim 1, wherein the ultrasonic vibrator is formed in an annular shape and is provided so as to penetrate the structure to the inside.

3. 3. The liquid sample valve according to claim 2, wherein the ultrasonic vibrator is in contact with at least one of the primary flow path and the secondary flow path.

4. 3. The liquid sample valve according to claim 1, wherein the ultrasonic vibrator is in contact with the structure.

5. 2. The liquid sample valve according to claim 1, wherein the ultrasonic vibrator is formed in an annular shape, penetrates the primary flow passage to the inside, and has an inner peripheral surface that abuts against the primary flow passage.

6. 2. The liquid sample valve according to claim 1, wherein the ultrasonic vibrator is formed in an annular shape, penetrates the secondary flow path to the inside, and has an inner circumferential surface that abuts against the secondary flow path.

7. 2. The liquid sample valve according to claim 1, wherein the ultrasonic vibrator is built into the stem.

8. A liquid sample valve according to claim 1; The gas chromatograph apparatus further comprises a control unit that controls driving of the ultrasonic vibrator.

9. A recess is formed on the outer circumferential surface of the stem, the stem is movable between a first position where the recess is in the sample chamber and a second position where the recess is moved to the outside of the sample chamber through a second sealant; the control unit drives the ultrasonic transducer for a predetermined time after switching the liquid sample flowing through the primary flow path; 9. The gas chromatograph apparatus according to claim 8, wherein the stem is reciprocated between the first position and the second position or is stopped while the ultrasonic transducer is being driven.

10. 9. A method for cleaning a gas chromatograph apparatus according to claim 8, comprising: and driving the ultrasonic vibrator for a predetermined time after switching the liquid sample flowing through the primary flow path.

11. A recess is formed on the outer circumferential surface of the stem, the stem is movable between a first position where the recess is in the sample chamber and a second position where the recess is moved to the outside of the sample chamber through a second sealant; 11. The cleaning method according to claim 10, wherein the step of driving the ultrasonic vibrator for a predetermined time comprises a step of moving the stem back and forth between the first position and the second position or stopping the stem while the ultrasonic vibrator is being driven.

12. The control unit of the gas chromatograph according to claim 8 further comprises: and driving the ultrasonic vibrator for a predetermined time after switching the liquid sample flowing through the primary flow path.

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