JP2015099122A - Sample introduction device and analyzer including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sample introduction device capable of preventing a sample component from remaining in a flow channel after sample introduction, and an analyzer including the same.SOLUTION: A carrier gas flow channel 42 at least from a trap 17 to an analysis unit 2 is shared between a state where a sample component is captured in the trap 17 and a state where the sample component is not captured in the trap 17. In this case, there is a period at which a carrier gas flows in the carrier gas flow channel 42 even after a sample is introduced to the analysis unit 2 via the carrier gas flow channel 42. Though the sample component is present in the carrier gas flow channel 42 when the sample is introduced, the sample component can be discharged from in the flow channel by the carrier gas flowing in the carrier gas flow channel thereafter, so that the sample component can be prevented from remaining in the flow channel after sample introduction.

Description

  The present invention relates to a sample introduction apparatus for introducing a sample into an analysis unit and an analysis apparatus including the same.

  For example, a heat desorption type sample introduction device may be used when introducing an extremely small amount of sample components into the analysis unit, such as when analyzing environmental pollutants in the air (for example, Patent Document 1 below). reference). In this type of sample introduction device, the sample components filled in the sample tube are heated and desorbed to collect the sample components once in the trap, and then the sample components in the trap are heated. It can be desorbed and introduced into the analyzer.

  2A to 2D are diagrams illustrating a configuration example of a conventional heat desorption type sample introduction apparatus 100. FIG. In this sample introduction apparatus 100, by introducing the internal standard sample into the analysis unit 200, the measurement result of the measurement target sample can be corrected using the measurement result of the internal standard sample.

  The sample introduction apparatus 100 includes an internal standard sample supply unit 101, a carrier gas supply unit 102, a sample loop 103, a sample tube 104, a trap 105, an eight-way valve 106, a four-way valve 107, a three-way valve 108, and a plurality of two-way valves 111 to 111. 116 and a plurality of flow control units 121 to 123 are provided. These parts are connected to each other through piping.

  FIG. 2A shows a sample loop supply state in which an internal standard sample is supplied into the sample loop 103. FIG. 2B shows a sample tube supply state in which the internal standard sample in the sample loop 103 is supplied into the sample tube 104. FIG. 2C shows a trap supply state in which the sample component desorbed from the sample tube 104 is supplied into the trap 105. FIG. 2D shows an analysis unit supply state in which the sample component desorbed from the trap 105 is supplied to the analysis unit 200.

  In this sample introduction device 100, first, as shown in FIG. 2A, the two-way valve 111 is opened in a state where the internal standard sample supply unit 101 and the sample loop 103 are communicated by the eight-way valve 106. 2A, the internal standard sample flows from the internal standard sample supply unit 101 side to the two-way valve 111 side by the pressure, and is filled in the sample loop 103.

  Thereafter, as shown in FIG. 2B, the carrier gas supply unit 102, the sample loop 103, the sample tube 104, and the flow rate control unit 121 are in communication with each other by switching the eight-way valve 106. At this time, the two-way valve 112 is closed and the two-way valve 113 is opened. 2B, the carrier gas supplied from the carrier gas supply unit 102 sequentially passes through the sample loop 103 and the sample tube 104 and flows to the flow rate control unit 121 side.

  In the state shown in FIG. 2B, the sample component of the internal standard sample in the sample loop 103 is collected in the sample tube 104, and the sample tube 104 is filled with the sample component. The flow rate of the carrier gas from the carrier gas supply unit 102 to the sample loop 103 and the sample tube 104 can be controlled by the flow rate control unit 121.

  Next, as shown in FIG. 2C, the eight-way valve 106 and the four-way valve 107 are switched, the two-way valves 112 and 114 are opened, and the two-way valve 113 is closed. As a result, as shown by a broken line in FIG. 2C, the carrier gas supply unit 102, the sample tube 104, the trap 105, and the flow rate control unit 122 communicate with each other, and the sample component desorbed from the sample tube 104 enters the trap 105. It is collected.

  The flow rate of the carrier gas from the carrier gas supply unit 102 to the sample tube 104 and the trap 105 can be controlled by the flow rate control unit 122. At this time, the three-way valve 108 is in a state where the carrier gas supply unit 102 and the analysis unit 200 are in communication with each other, whereby the carrier gas from the carrier gas supply unit 102 is supplied to the analysis unit 200.

  After collecting the sample components in the trap 105 in this way, as shown in FIG. 2D, the four-way valve 107 is switched, the two-way valve 113 is opened, and the two-way valves 112 and 114 are closed. At this time, the three-way valve 108 is switched to a state in which the carrier gas supply unit 102 and the trap 105 are communicated.

  2D, the carrier gas supply unit 102 and the trap 105 communicate with each other, the trap 105 communicates with the analysis unit 200 via the four-way valve 107, and the trap 105 communicates with the four-way valve 107. The sample tube 104 and the flow rate control unit 121 are communicated with each other. In this state, a part of the sample component desorbed from the trap 105 is introduced into the analysis unit 200 and the remaining sample component is collected again in the sample tube 104.

  The flow rate of the carrier gas from the carrier gas supply unit 102 to the trap 105 and the sample tube 104 can be controlled by the flow rate control unit 121. Further, when the two-way valve 115 is opened, a part of the sample component supplied to the analysis unit 200 side is guided from the branch unit 130 to the flow rate control unit 123 side. At this time, the flow path from the branch unit 130 to the flow rate control unit 123 forms a split flow channel 131, and the flow rate of the carrier gas in the split flow channel 131 can be controlled by the flow rate control unit 123.

JP 2007-212325 A

  However, in the conventional configuration as described above, there is a problem that the flow path 132 between the four-way valve 107 and the branch portion 130 becomes a dead volume. That is, in the state of FIG. 2D, a part of the sample component desorbed from the trap 105 is introduced into the analysis unit 200 via the flow path 132, but in the other states of FIGS. 2A to 2C, Gas does not flow through the flow path 132.

  Therefore, the sample component remaining in the flow path 132 at the time of analysis is carried over at the time of the next analysis, and the sample component at the time of the previous analysis is included in the gas introduced into the analysis unit 200 via the flow path 132 at the time of the next analysis. There is a problem of mixing. In this case, there is a possibility that an accurate measurement result cannot be obtained, for example, a peak of a sample component that does not exist originally appears in the measurement result. In particular, sample components that have a high boiling point and are difficult to evaporate are likely to remain in the flow path 132, and the above-described problems are likely to occur.

  On the other hand, from the viewpoint of reducing the manufacturing cost of the apparatus and improving the maintainability, there is a demand for a more simplified configuration with fewer parts.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a sample introduction device that can prevent a sample component from remaining in a flow path after sample introduction and an analyzer equipped with the sample introduction device. And It is another object of the present invention to provide a sample introduction device having a more simplified configuration and an analysis apparatus including the sample introduction device.

  A sample introduction device according to the present invention is for introducing a sample into an analysis unit, and includes a sample tube, a first heating unit, a trap, a second heating unit, a carrier gas channel, And a flow path switching mechanism.

  The sample tube is filled with sample components. The first heating unit heats and desorbs the sample component filled in the sample tube. The trap collects sample components detached from the sample tube. The second heating unit heats and desorbs the sample component in the trap. The carrier gas flow path guides the sample component desorbed from the inside of the trap to the analysis unit by the carrier gas. The first flow path switching mechanism switches the carrier gas flow path between a state in which the sample component is collected in the trap and a state in which the sample component is not collected in the trap. At least the carrier gas flow path from the trap to the analysis unit is shared between a state in which sample components are collected in the trap and a state in which sample components are not collected in the trap.

  According to such a configuration, at least the carrier gas flow path from the trap to the analysis unit is shared between the state in which the sample component is collected in the trap and the state in which the sample component is not collected in the trap. Therefore, even after the sample is introduced into the analysis unit via the carrier gas channel, there is a period during which the carrier gas flows in the carrier gas channel. Thus, even if the sample component is present in the carrier gas flow channel at the time of sample introduction, the sample component can be excluded from the flow channel by the carrier gas flowing in the carrier gas flow channel thereafter. It is possible to prevent the component from remaining in the flow path.

  In addition, the number of parts is reduced by sharing at least the carrier gas flow path from the trap to the analysis section when the sample component is collected in the trap and when the sample component is not collected in the trap. Therefore, the configuration can be further simplified. Thereby, the manufacturing cost of the apparatus can be reduced and the maintainability can be improved.

  The sample introduction device may further include a split channel. The split flow channel guides a part of the carrier gas guided to the analysis unit via the trap into the sample tube in a state where the sample component is collected in the trap.

  According to such a configuration, the sample component contained in the carrier gas guided to the split flow path is collected in the sample tube. Thereby, since a sample component can be recollected in a sample tube using a split flow path, the number of parts can be reduced and the configuration can be further simplified.

  The sample introduction device may further include a first flow rate control unit. The first flow rate control unit controls the flow rate of the carrier gas in the split flow path.

  According to such a configuration, the first flow rate controller can control the flow rate of the carrier gas in the split flow path, thereby adjusting the split flow rate and recollecting the sample components in the sample tube. The flow rate can be adjusted. In this way, by sharing the first flow rate control unit and controlling the split flow rate and the flow rate of the sample component to be collected again, the number of parts can be reduced, so that the configuration can be further simplified. it can.

  The sample introduction device may further include an internal standard sample supply path, a second flow path switching mechanism, and a second flow rate control unit. The internal standard sample supply path supplies an internal standard sample. The second flow path switching mechanism includes: a sample loop supply state for supplying an internal standard sample into the sample loop; and a sample tube supply state for supplying an internal standard sample in the sample loop into the sample tube. Switch the standard sample supply path. The second flow rate controller controls the flow rate of the internal standard sample in the internal standard sample supply path in the sample loop supply state and the sample tube supply state.

  According to such a configuration, the flow rate of the internal standard sample in the internal standard sample supply path in the sample loop supply state and the sample tube supply state can be controlled by sharing the second flow rate control unit. Thereby, since the number of parts can be reduced, the configuration can be further simplified.

  The second flow path switching mechanism may be capable of switching the internal standard sample supply path to a trap supply state in which the sample component desorbed from the sample tube is supplied into the trap. In this case, the second flow path control unit may control the flow rate of the internal standard sample in the internal standard sample supply path in the trap supply state.

  According to such a configuration, in addition to the sample loop supply state and the sample tube supply state, the flow rate of the internal standard sample in the internal standard sample supply path is controlled by sharing the second flow rate control unit also in the trap supply state. can do. Thereby, the number of parts can be further reduced, and the configuration can be further simplified.

  The analyzer according to the present invention includes the sample introduction device and an analysis unit that analyzes a sample introduced from the sample introduction device.

  According to the present invention, since the sample component can be excluded from the flow channel by the carrier gas flowing in the flow channel, the sample component can be prevented from remaining in the flow channel after the sample is introduced. Further, according to the present invention, the number of parts can be reduced, so that the configuration can be further simplified.

It is the figure which showed the structural example of the sample introduction apparatus of the thermal desorption type which concerns on one Embodiment of this invention, and has shown the sample loop supply state. It is the figure which showed the structural example of the sample introduction apparatus of the heat | fever desorption system which concerns on one Embodiment of this invention, and has shown the sample tube supply state. It is the figure which showed the structural example of the sample introduction apparatus of the thermal desorption type which concerns on one Embodiment of this invention, and has shown the trap supply state. It is the figure which showed the structural example of the sample introduction apparatus of the thermal desorption type which concerns on one Embodiment of this invention, and has shown the analysis part supply state. It is the figure which showed the structural example of the sample introduction apparatus of the conventional heat desorption system, and has shown the sample loop supply state. It is the figure which showed the structural example of the sample introduction apparatus of the conventional heat desorption system, and has shown the sample tube supply state. It is the figure which showed the structural example of the sample introduction apparatus of the conventional heat desorption system, and has shown the trap supply state. It is the figure which showed the structural example of the sample introduction apparatus of the conventional heat desorption system, and has shown the analysis part supply state.

  1A to 1D are diagrams showing a configuration example of a heat desorption type sample introduction apparatus 1 according to an embodiment of the present invention. In the sample introduction apparatus 1, by introducing an internal standard sample into the analysis unit 2, the measurement result of the measurement target sample can be corrected using the measurement result of the internal standard sample. The analysis unit 2 is a gas chromatograph including, for example, a column 3 and analyzes a sample introduced from the sample introduction device 1.

  The sample introduction apparatus 1 includes an internal standard sample supply unit 11, an AFC (Auto Flow Controller) 12, an APC (Auto Pressure Controller) 13, an MFC (Mass Flow Controller) 14, a sample loop 15, a sample tube 16, a trap 17, 2 Three six-way valves 18 and 19, a three-way valve 20, and three two-way valves 21 to 23 are provided. These parts are connected to each other through piping.

  FIG. 1A shows a sample loop supply state in which an internal standard sample is supplied into the sample loop 15. FIG. 1B shows a sample tube supply state in which the internal standard sample in the sample loop 15 is supplied into the sample tube 16. FIG. 1C shows a trap supply state in which the sample component desorbed from the sample tube 16 is supplied into the trap 17. FIG. 1D shows an analysis unit supply state in which the sample component desorbed from the trap 17 is supplied to the analysis unit 2.

  The internal standard sample supply unit 11 is composed of, for example, a cylinder in which the internal standard sample is stored at a high pressure, and can supply the internal standard sample by the internal pressure. The AFC 12 constitutes a carrier gas supply unit, and controls the supply flow rate of the carrier gas for introducing the sample component into the analysis unit 2. The APC 13 constitutes a collection gas supply unit, and controls the supply pressure of the collection gas for collecting the sample components in the sample tube 16 and the trap 17. The MFC 14 controls the flow rate of gas exhausted to the outside of the apparatus via the exhaust path 41.

  In the sample introduction apparatus 1, first, as shown in FIG. 1A, the two-way valve 21 is opened and the two-way valves 22 and 23 are closed. The loop 15 and the MFC 14 are connected. Thereby, as indicated by a broken line in FIG. 1A, the internal standard sample flows from the internal standard sample supply unit 11 side to the MFC 14 side by the pressure, and is filled in the sample loop 15. At this time, a carrier gas is supplied from the AFC 12, and the carrier gas is introduced into the column 3 of the analysis unit 2 via the carrier gas flow path 42 indicated by a two-dot chain line in FIG. 1A.

  Thereafter, as shown in FIG. 1B, the two-way valve 21 is closed and the two-way valve 22 is opened. In this state, the flow path is switched by the six-way valve 19, and the APC 13, the sample loop 15, the sample tube 16, and the MFC 14 are communicated in this order as shown by a broken line in FIG. 1B. As a result, the collection gas supplied from the APC 13 sequentially passes through the sample loop 15 and the sample tube 16 and flows to the MFC 14 side.

  In the state shown in FIG. 1B, the sample component of the internal standard sample in the sample loop 15 is collected in the cooled sample tube 16, and the sample tube 16 is filled with the sample component. The flow rate of the collection gas to the sample tube 16 can be controlled by the MFC 14. Note that the hexagonal valve 18 is in the same state as in FIG. 1A, and the carrier gas from the AFC 12 is introduced into the column 3 of the analysis unit 2 via the carrier gas channel 42 as shown by a two-dot chain line in FIG. 1B. .

  Next, as shown in FIG. 1C, the two-way valve 22 is closed and the two-way valve 23 is opened. In this state, the flow path is switched by the six-way valve 18 and the three-way valve 20, and the APC 13, the sample tube 16, the sample loop 15, the trap 17 and the MFC 14 communicate with each other in this order, as indicated by a broken line in FIG. 1C. Become. The six-way valve 19 is in the same state as in FIG. 1B.

  At this time, the sample tube 16 is heated by the heater (first heating unit) 31 provided adjacent to the sample tube 16, and the sample component filled in the sample tube 16 is desorbed. Thereby, the collection gas supplied from the APC 13 sends the sample component desorbed from the sample tube 16 to the trap 17 side, and the sample component is collected in the cooled trap 17. The flow rate of the collecting gas to the trap 17 can be controlled by the MFC 14.

  As the flow path is switched by the hexagonal valve 18, the carrier gas flow path 42 from the AFC 12 to the analysis unit 2 does not pass through the trap 17 as indicated by a two-dot chain line in FIG. 1C. In this state, the carrier gas from the AFC 12 is introduced into the column 3 of the analysis unit 2 via the carrier gas channel 42.

  After collecting the sample components in the trap 17 in this way, the flow path is switched by the six-way valves 18 and 19 as shown in FIG. 1D. As a result, as indicated by a two-dot chain line in FIG. 1D, the carrier gas channel 42 communicates with the analysis unit 2 from the AFC 12 via the trap 17. At this time, the trap 17 is heated by the heater (second heating unit) 32 provided adjacent to the trap 17, and the sample component in the trap 17 is desorbed. The sample component desorbed from the trap 17 is guided to the column 3 of the analysis unit 2 by the carrier gas through the carrier gas channel 42.

  As shown in FIGS. 1A to 1D, the hexagonal valve 18 has a carrier gas flow path 42 in a state where the sample component is collected in the trap 17 and in a state where the sample component is not collected in the trap 17. The 1st flow path switching mechanism which switches is comprised. In this embodiment, at least the carrier gas flow path 42 from the trap 17 to the analysis unit 2 is in a state where the sample component is collected in the trap 17 (FIG. 1D), and the sample component is collected in the trap 17. It is shared in a state (FIG. 1A and FIG. 1B) that is not present.

  In this case, even after the sample is introduced into the analysis unit 2 via the carrier gas channel 42 in the state of FIG. 1D, the period during which the carrier gas flows in the carrier gas channel 42 as shown in FIGS. 1A and 1B. There is. Thereby, even if the sample component is in the carrier gas channel 42 at the time of sample introduction, the sample component can be excluded from the channel by the carrier gas flowing in the carrier gas channel 42 after that. It is possible to prevent the sample component from remaining in the channel later.

  Further, by sharing at least the carrier gas flow path 42 from the trap 17 to the analysis unit 2 in a state in which the sample component is collected in the trap 17 and a state in which the sample component is not collected in the trap 17. Since the number of parts can be reduced, the configuration can be further simplified. Thereby, the manufacturing cost of the apparatus can be reduced and the maintainability can be improved.

  In the state of FIG. 1D, a part of the carrier gas guided to the analysis unit 2 via the trap 17 is guided to the sample tube 16 by the split flow path 43 indicated by a one-dot chain line in the drawing. At this time, the sample component contained in the carrier gas guided to the split flow path 43 is collected in the cooled sample tube 16.

  Thereby, since the sample component can be collected again in the sample tube 16 by using the split flow path 43, the number of parts can be reduced and the configuration can be further simplified. In the case where the sample component is not collected again, the hexagonal valve 19 may not be switched when shifting from the state of FIG. 1C to the state of FIG. 1D.

  A downstream side of the sample tube 16 in the split flow path 43 is connected to the AFC 12, and the AFC 12 constitutes a first flow rate control unit that controls the flow rate of the carrier gas in the split flow path 43. Therefore, by controlling the flow rate of the carrier gas in the split flow path 43 with the AFC 12, the split flow rate can be adjusted, and the flow rate of the sample component recollected in the sample tube 16 can be adjusted. . In this way, the number of parts can be reduced by sharing the AFC 12 and controlling the split flow rate and the flow rate of the sample component to be collected again, thereby further simplifying the configuration.

  The internal standard sample supply path 44 for supplying the internal standard sample is supplied by the second flow path switching mechanism constituted by the hexagonal valves 18 and 19, and the sample loop supply state indicated by the broken line in FIG. 1A and the sample indicated by the broken line in FIG. It is possible to switch between a tube supply state and a trap supply state indicated by a broken line in FIG. 1C. The MFC 14 constitutes a second flow rate control unit that controls the flow rate of the internal standard sample in the internal standard sample supply path 44 in the sample loop supply state, the sample tube supply state, and the trap supply state. The pressure in the internal standard sample supply path 44 can be detected by a pressure sensor 45 connected to the internal standard sample supply path 44.

  When the internal standard sample supply path 44 is in a sample loop supply state as indicated by a broken line in FIG. 1A, the internal standard sample supplied from the internal standard sample supply unit 11 is supplied into the sample loop 15. Further, when the internal standard sample supply path 44 is in the sample tube supply state as shown by the broken line in FIG. 1B, the internal standard sample in the sample loop 15 is supplied into the sample tube 16.

  In this embodiment, the MFC 14 can be shared to control the flow rate of the internal standard sample in the internal standard sample supply path 44 in the sample loop supply state and the sample tube supply state. Thereby, since the number of parts can be reduced, the configuration can be further simplified.

  When the internal standard sample supply path 44 is in a trap supply state as shown by a broken line in FIG. 1C, the sample component detached from the sample tube 16 is supplied into the trap 17. In the present embodiment, in addition to the sample loop supply state and the sample tube supply state, the MFC 14 can be shared in the trap supply state, and the flow rate of the internal standard sample in the internal standard sample supply path 44 can be controlled. Thereby, the number of parts can be further reduced, and the configuration can be further simplified.

  In the above embodiment, the configuration has been described in which the measurement result of the measurement target sample can be corrected using the internal standard sample. However, the present invention is not limited to such a configuration, but can be applied to a configuration in which an internal standard sample is not used. In this case, after attaching the sample tube 16 filled with the sample component of the sample to be measured to the sample introduction device 1, the operation after FIG. 1C may be performed.

  Moreover, the sample introduction apparatus 1 according to the present invention is not limited to the analysis unit 2 such as a gas chromatograph but can be applied to a configuration in which a sample is introduced into another analysis unit 2.

1 Sample Introduction Device 2 Analysis Unit 3 Column 11 Internal Standard Sample Supply Unit 12 AFC
13 APC
14 MFC
15 Sample loop 16 Sample tube 17 Trap 18, 19 Six-way valve 20 Three-way valve 21-23 Two-way valve 31, 32 Heater 41 Exhaust passage 42 Carrier gas passage 43 Split passage 44 Internal standard sample supply passage 45 Pressure sensor

Claims (6)

A sample introduction device for introducing a sample into an analysis unit,
A sample tube filled with sample components;
A first heating section for heating and desorbing the sample components filled in the sample tube;
A trap for collecting a sample component detached from the sample tube;
A second heating unit that heats and desorbs the sample components in the trap;
A carrier gas flow path for guiding the sample component desorbed from the trap to the analysis unit by a carrier gas;
A first flow path switching mechanism that switches the carrier gas flow path between a state in which the sample component is collected in the trap and a state in which the sample component is not collected in the trap;
At least the carrier gas flow path from the trap to the analysis unit is shared between a state in which sample components are collected in the trap and a state in which sample components are not collected in the trap. Sample introduction device.   2. A split flow path for guiding a part of a carrier gas guided to the analysis section through the trap into the sample tube in a state where a sample component is collected in the trap. Item 2. The sample introduction device according to Item 1.   The sample introduction apparatus according to claim 2, further comprising a first flow rate control unit that controls a flow rate of the carrier gas in the split flow path. An internal standard sample supply path for supplying an internal standard sample;
A second flow for switching the internal standard sample supply path between a sample loop supply state in which an internal standard sample is supplied into the sample loop and a sample tube supply state in which the internal standard sample in the sample loop is supplied into the sample tube. A path switching mechanism;
4. The apparatus according to claim 1, further comprising a second flow rate control unit that controls a flow rate of the internal standard sample in the internal standard sample supply path in the sample loop supply state and the sample tube supply state. A sample introduction device according to claim 1. The second flow path switching mechanism can switch the internal standard sample supply path to a trap supply state in which the sample component desorbed from the sample tube is supplied into the trap.
The sample introduction apparatus according to claim 4, wherein the second flow path control unit controls a flow rate of the internal standard sample in the internal standard sample supply path in the trap supply state. A sample introduction device according to any one of claims 1 to 5;
And an analyzer for analyzing a sample introduced from the sample introduction device.

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