Fluid chromatograph

Abstract

A fluid chromatograph includes a flow path switching part configured to switch to one of states including a sampling state in which the measuring pump is connected to a proximal end side of the sampling flow path, a total volume introduction state in which the mobile phase sending part is connected to a proximal end side of the sampling flow path and the needle port and the analysis flow path are connected to each other, an injection state in which the measuring pump is connected to the proximal end side of the sampling flow path and the needle port and the second sample loop are connected to each other, and a loop introduction state in which the mobile phase sending part is connected to one end side of the sample loop and the analysis flow path is connected to the other end side of the sample loop.

Claims

1. A fluid chromatograph comprising: a measuring pump; a mobile phase sending part for sending a mobile phase; a sampling flow path having a needle at a distal end thereof and having a first sample loop, the sample loop configured to retain a liquid sucked from a distal end of the needle that is received from a proximal end of the needle; a needle port communicating with the sampling flow path by inserting the distal end of the needle; a second sample loop provided separately from the first sample loop; an analysis flow path including an analytical column for separating a sample into individual components and a detector for detecting the components separated by the analytical column; and a flow path switching part configured to switch to either a sampling state, a total volume introduction state, an injection state, or a loop introduction state, wherein, in the sampling state, the measuring pump is connected to a proximal end side of the sampling flow path, in the total volume introduction state, the mobile phase sending part is connected to the proximal end side of the sampling flow path and the needle port and the analysis flow path are connected to each other, in the injection state, the measuring pump is connected to the proximal end side of the sampling flow path and the needle port and the second sample loop are connected to each other, in the loop introduction state, the mobile phase sending part is connected to one end side of the second sample loop and the analysis flow path is connected to the other end side of the second sample loop.

2. The fluid chromatograph according to claim 1, wherein the flow path switching part includes at least a first multi-port valve and a second multi-port valve, each having a plurality of connection ports and configured to switch connection between the connection ports, the first multi-port valve includes connection ports to which the needle port, the mobile phase sending part, one end of the second sample loop, the other end of the second sample loop, and a connecting flow path connected to one connection port of the second multi-port valve are respectively connected, the first multi-port valve is configured to switch between a first state and a second state, in the first state, one end of the second sample loop and the needle port are connected to each other and the mobile phase sending part and the connecting flow path are connected to each other, in the second state, one end of the sample loop and the mobile phase sending part are connected to each other and the other end of the sample loop and the bypass flow path are connected to each other, and the second multi-port valve includes connection ports to which the measuring pump, the sampling flow path, the analysis flow path, and the connecting flow path are respectively connected, the second multi-port valve is configured to switch between a first state and a second state, in the first state, the measuring pump and the sampling flow path are connected to each other and the analysis flow path and the connecting flow path are connected to each other, in the second state, the sampling flow path and the connecting flow path are connected to each other.

3. The fluid chromatograph according to claim 1, further comprising: a needle driving mechanism configured to drive the needle; and a control part configured to control operations of at least the measuring pump, the flow path switching part, and the needle driving mechanism, wherein the control part comprises: an injection mode selection part configured to prompt a user for an input to select one of a total volume injection mode and a loop injection mode, a total volume injection operation part configured to execute a total volume injection operation of setting the flow path switching part in the sampling state, upon selection of the total volume injection mode, to suck a sample to be analyzed through the needle, and then inserting the distal end of the needle into the injection port and switching the flow path switching part to the total volume introduction state to introduce a sample into the analysis flow path by using a mobile phase from the mobile phase sending part, and a loop injection operation part configured to execute a loop injection operation of setting the flow path switching part in the sampling state, upon selection of the loop injection mode, to suck a sample to be analyzed through the needle, and then inserting the distal end of the needle into the injection port and switching the flow path switching part to the inflow state, injecting the sucked sample into the second sample loop, and then switching the flow path switching part to the loop introduction state to introduce a sample into the analysis flow path by using a mobile phase from the mobile phase sending part.

4. The fluid chromatograph according to claim 3, wherein the mobile phase sending part includes a liquid sending pump configured to send a liquid chromatograph mobile phase and a liquid sending pump configured to send a supercritical fluid chromatograph mobile phase, the analysis flow path includes a back pressure control mechanism configured to control a pressure in the analysis flow path on an outlet side of the detector, and the control part is configured to also control operations of the mobile phase sending part and the back pressure control mechanism, further includes an analysis mode selection part configured to make a user select one of modes including a liquid chromatograph mode and a supercritical fluid chromatograph mode, and is configured to select the loop injection mode when the supercritical fluid chromatograph mode is selected.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a block diagram schematically showing an embodiment of a fluid chromatograph.

(2) FIG. 2 is a schematic flow path configuration diagram showing a flow path configuration according to the same embodiment.

(3) FIG. 3 is a schematic flow path configuration diagram showing a flow path configuration at the time of sample suction in the same embodiment.

(4) FIG. 4 is a schematic flow path configuration diagram showing a flow path configuration at the time of sample introduction in the total volume injection mode according to the same embodiment.

(5) FIG. 5 is a schematic flow path configuration diagram showing a flow path configuration at the time of sample injection in the loop injection mode according to the same embodiment.

(6) FIG. 6 is a schematic flow path configuration diagram showing a flow path configuration at the time of sample introduction in the loop injection mode according to the same embodiment.

EMBODIMENT OF THE INVENTION

(7) One embodiment of a fluid chromatograph according to the present invention will be described below with reference to the accompanying drawings.

(8) The schematic configuration of the fluid chromatograph will be described with reference to the block diagram of FIG. 1.

(9) The fluid chromatograph according to this embodiment mainly includes a measuring pump 2, a mobile phase sending part 4, a sampling flow path 6, a needle port 14, a second sample loop 16, an analysis flow path 18, a flow path switching part 20, and a control part 22.

(10) The mobile phase sending part 4 is provided with a pump for sending an LC or SFC mobile phase. As will be described later, this fluid chromatograph can operate in the LC mode and the SFC mode. As shown in FIGS. 2 to 6, the mobile phase sending part 4 is configured to select either the LC mode or the SFC mode and configured to be able to send both an LC mobile phase and an SFC mobile phase. The mobile phase sending part 4 sends an LC mobile phase in the LC mode and sends an SFC mobile phase in the SFC mode.

(11) The sampling flow path 6 has a sampling needle 8 at its distal end and a first sample loop 10 at the proximal end side of the needle 8. The first sample loop 10 retains the liquid sucked through the needle 8. The needle 8 is driven by the needle driving mechanism 12. The driving directions of the needle 8 include, for example, a horizontal plane direction and a vertical direction.

(12) The needle port 14 communicates with the sampling flow path 6 by inserting the distal end of the needle 8.

(13) The second sample loop 16 is provided separately from the first sample loop 10 of the sampling flow channel 6 and is used to temporarily retain the sample injected through the needle 14.

(14) Although not shown in FIG. 1, the analysis flow path 18 includes an analytical column configured to separate a sample into individual components, a detector for detecting the sample components separated by the analytical column, and a back pressure control mechanism (hereinafter referred to as BPR) for controlling the pressure in the analysis flow path 18. When the LC mode is selected, the BPR of the analysis flow path 18 is unnecessary and does not operate. In contrast to this, when the SFC mode is selected, the BPR of the analysis flow path 18 operates to set the pressure in the analysis flow path 18 to a predetermined pressure. The predetermined pressure is a pressure at which the mobile phase flowing through the analysis channel 18 is maintained in the supercritical state.

(15) The flow path switching part 20 is used to change the flow path configuration incorporating the measuring pump 2, the mobile phase sending part 4, the sampling flow path 6, the needle port 14, the second sample loop 16, and the analysis flow path 18. The flow path switching part 20 can switch to one of at least four states.

(16) The four states to which the flow path switching part is switched include a suction state in which the measuring pump 2 and the sampling flow path 6 are connected, a total volume introduction state in which the mobile phase sending part 4 and the sampling flow path 6 are connected and the needle port 14 and the second sample loop 16 are connected, an injection state in which the measuring pump 2 and the sampling flow path 6 are connected and the needle port 14 and the second sample loop 16 are connected, and a loop introduction state in which the mobile phase sending part 4 and one end of the second sample loop 16 are connected and the other end of the second sample loop 16 and the analysis flow path 18 are connected. The flow path configuration in each state will be described later with reference to FIGS. 3 to 6.

(17) The control part 22 controls operations of the measuring pump 2, the mobile phase sending part 4, the needle driving mechanism 12, and the flow path switching part 20. The control part 22 is provided with an analysis mode selection part 24, an injection mode selection part 26, a total volume injection operation part 28, and a loop injection operation part 30.

(18) The analysis mode selection part 24 is configured to make the user select either the LC mode or the SFC mode as an analysis mode. When the LC mode is selected, an LC mobile phase is sent from the mobile phase sending part 4, and the BPR of the analysis flow path 18 is stopped, thereby forming this fluid chromatograph as an LC. In contrast to this, when the SFC mode is selected, an SFC mobile phase is sent from the mobile phase sending part 4, and the BPR of the analysis flow path 18 is operated to adjust the pressure inside the analysis flow path 18 to a predetermined pressure, thereby forming this fluid chromatograph as an SFC.

(19) The injection mode selection part 26 is configured to make the user select either the total volume injection mode or the loop injection mode as an injection mode.

(20) The total volume injection operation part 28 is configured to control the operations of the measuring pump 2, the mobile phase feeding part 4, the needle driving mechanism 12, and the flow path switching part 20 so as to execute a total volume injection operation when the total volume injection mode is selected. The total volume injection operation is an operation in which after the flow path switching part 20 is set in the injection state and a sample is sucked through the needle 8 and retained in the first sample loop 10, the distal end of the needle 8 is inserted into the needle port 14, and the switching part 20 is switched to the total volume introduction mode to guide the whole sample retained in the first sample loop 10 to the analysis flow path 18 by using a mobile phase from the mobile phase sending part.

(21) The loop injection operation part 30 is configured to control the operations of the measuring pump 2, the mobile phase feeding part 4, the needle driving mechanism 12, and the flow path switching part 20 so as to execute a loop injection operation when the loop injection mode is selected. The loop injection operation is an operation in which after the flow path switching part 20 is set in the injection state and a sample is sucked through the needle 8 and retained in the first sample loop 10, the distal end of the needle 8 is inserted into the needle port 14, the flow path switching part 20 is switched to the injection state to inject a predetermined amount of sample of the sample retained in the first sample loop 10 into the second sample loop 16 through the needle port 14, and then flow path switching part 20 is switched to the loop introduction state to guide the sample retained in the second sample loop 16 to the analysis flow path 18 by using a mobile phase from the mobile phase sending part 4.

(22) When the SFC mode is selected as an analysis mode, the loop injection mode is always selected as an injection mode. In order to “always select the loop injection mode”, the loop injection mode may be automatically selected when the SFC mode is selected regardless of user's selection, or an error may be issued when the total volume injection mode is selected in spite of the selection of the SFC mode, or the selection of the total volume injection mode may be inhibited when the SFC mode is selected.

(23) One embodiment of the detailed flow path configuration of the above fluid chromatograph will be described next with reference to FIG. 2.

(24) In this embodiment, the flow path switching part 20 in FIG. 1 includes three switching valves including a switching valve 32 (first multi-port valve), a switching valve 34 (second multi-port valve), and a switching valve 36. Each of the switching valves 32 and 34 is a 6-port valve having six connection ports a to f arranged evenly and counterclockwise on the same circumference and configured to switch connection between the adjacent connection ports. The switching valve 36 is a 7-port valve having six connection ports a to f arranged evenly and counterclockwise on the same circumference and a central port g arranged at the center of the connection ports a to f.

(25) The connection ports a of the switching valves 32 and 34 are connected to each other by a connecting flow path 38 and the connection ports e of the switching valves 32 and 34 are connected to each other by a bypass flow path 40. The connection port c of the switching valve 34 and the connection port a of the switching valve 36 are connected to each other by a pump connecting flow path 42.

(26) Concerning the switching valve 32, a mobile phase sending flow path 44 from the mobile phase sending part 4 is connected to the connection port b, one end of the second sample loop 16 is connected to the connection port c, the needle port 14 is connected to the port d, and the other end of the second sample loop 16 is connected to the port f. The switching valve 32 can be switched to either a first state (the state of the switching valve 32 in FIG. 5) in which the connection ports a and b, c and d, and e and f communicate with each other or a second state (the state of the switching valve 32 in FIG. 2) in which the connection ports a and f, b and c, and d and e communication with each other.

(27) Concerning the switching valve 34, the proximal end of the sampling flow path 6 is connected to the connection port b, the connection port d communicates with the drain, and the analysis flow path 18 is connected to the connection port f. The switching valve 34 can be switched to either the second state (the state of the switching valve 34 in FIG. 2) in which the connection ports a and b, c and d, and e and f communicate with each other or the first state (the state of the switching valve 34 in FIG. 3) in which the connection ports a and f, b and c, and d and e communication with each other.

(28) Concerning the switching valve 36, a first pump flow path 54 communicating with the first suction/discharge port of the measuring pump 2 is connected to the connection port b, cleaning liquid flow paths 60, 62, and 64 communicating with the cleaning liquid container are respectively connected to the connection ports c, d and e, a cleaning flow path 68 communicating with a cleaning port 70 is connected to the connection port f, and a second pump flow path 56 communicating with the second suction/discharge port of the measuring pump 2 is connected to the central port g. A manual prime valve 58 is provided on the second pump flow path 56. The switching valve 36 can connect a pair of adjacent connection ports out of the connection ports a to f or connect the central port g to any one of the connection ports a to f.

(29) In this embodiment, the mobile phase sending part 4 includes liquid sending pumps 46, 48 and 50 for sending three types of solvents as mobile phases. The liquid sending pumps 46 and 48 are used to send an SFC mobile phase, and the liquid sending pumps 48 and 50 are used to send an LC mobile phase. For example, the liquid sending pump 46 sends liquefied carbon dioxide, the liquid sending pump 48 sends ethanol or methanol, and the liquid sending pump 50 sends water. When the LC mode is selected as an analysis mode, an organic solvent such as ethanol or methanol and water are sent to a mixer 52 by the liquid sending pumps 48 and 50, and the mixture of them is supplied as a mobile phase through the liquid sending flow path 44. When the SFC mode is selected as an analysis mode, a modifier such as ethanol or methanol and liquefied carbon dioxide are sent to a mixer 52 by the liquid sending pumps 46 and 48, and the mixture of them is supplied as a mobile phase through the liquid sending flow path 44.

(30) Cleaning ports 70 and 72 are provided on the movement path of the needle 8 to clean the outer and inner surfaces of the needle 8. A flow path 74 for supplying a cleaning liquid is connected to the cleaning port 72. On the flow path 74, a liquid sending pump 76 and an electromagnetic valve 78 are provided.

(31) The analysis flow path 18 includes an analytical column 82, a detector 84, and a BPR 86 from the upstream side. As described above, the BPR 86 operates only when the SFC mode is selected as an analysis mode, and does not operate when the LC mode is selected.

(32) The operation of sample introduction into the analysis flow path 18 in the total volume injection mode according to this embodiment and the operation of sample introduction into the analysis flow path 18 in the loop injection mode will be described with reference to FIGS. 3 to 6.

(33) First, the case in which the total volume injection mode is selected will be described. When the total volume injection mode is selected, a sample is collected from a sample container 80 containing the sample to be analyzed using the needle 8. As shown in FIG. 3, the switching valve 32 is set in the second state, the switching valve 34 is set in the first state, and the switching valve 36 is set in a state in which the ports a and g are connected. As a result, as indicated by the thick line in FIG. 3, the second suction/discharge port of the measuring pump 2 and the sampling flow path 6 communicate with each other. This state is the “suction state”. In this suction state, the distal end of the needle 8 is immersed in the sample in the sample container 80, and the measuring pump 2 is driven to suck the sample from the distal end of the needle 8. The sample sucked from the distal end of the needle 8 stays in the first sample loop 10 on the proximal end side of the needle 8.

(34) In the above-described suction state, the mobile phase sending flow path 44, the second sample loop 16, the connecting flow path 38, the analysis flow path 18 are sequentially connected, and a mobile phase from the mobile phase sending part 4 is connected to the analysis flow path 18.

(35) After completion of the above sampling operation, as shown in FIG. 4, the needle 8 is moved to connect the distal end of the needle 8 to the needle port 14, and the switching valves 32 and 34 are set in the second state. As a result, the mobile phase sending flow path 44 is connected to the sampling flow path 6 through the second sample loop 16 and the connecting flow path 38, and the sampling flow path 6 is connected to the analysis flow path 18 through the needle port 14 and the bypass flow path 40. This is the “total volume introduction state”. In this total volume introduction state, the sample retained in the first sample loop 10 is transferred to the analysis flow path 18 by the mobile phase from the mobile phase supply section 4, and separated into individual components by the analytical column 82. Each component is detected by the detector 84.

(36) The case in which the loop injection mode is selected will be described next. Even when the loop injection mode is selected, the first sampling operation is the same as the total volume injection operation, and a sample is collected from the sample container 80 in the “suction state” in FIG. 3 to stay in the first sample loop 10.

(37) After completion of the sampling operation, as shown in FIG. 5, the needle 8 is moved to connect the distal end of the needle 8 to the needle port 14, and the switching valves 32 and 34 are both set in the first state. The switching valve 36 is set in a state in which the ports a and g are connected. As a result, the second suction/discharge port of the measuring pump 2 is connected to the sampling flow path 6, and the sampling flow path 6 is connected to the drain through the needle port 14, the second sample loop 16, and the bypass flow path 40. This state is the “injection state”. A predetermined amount of sample is injected into the second sample loop 16 by driving the measuring pump 2 to discharge the sample in this injection state.

(38) After the injection of the sample into the second sample loop 16 is completed, as shown in FIG. 6, the switching valve 32 is set in the second state and the switching valve 34 is set in the first state. As a result, the mobile phase sending flow path 44 is connected to the analysis flow path 18 through the second sample loop 16 and the connecting flow path 38. This state is a “loop introduction state”. In this loop introduction state, the sample in the second sample loop 16 is transferred to the analysis flow path 18 by the mobile phase from the mobile phase supply section 4, and separated into individual components by the analytical column 82. Each component is detected by the detector 84.

(39) In the above-described loop introduction state, by connecting between the ports a and b of the switching valve 36 and driving the measuring pump 2 to perform a discharge operation, the liquid remaining in the system from the measuring pump 2 to the needle 8 can be discharged to the drain.

(40) In the above embodiment, the switching valves 32 and 34, which are 6-port valves, are exemplified as multi-port valves constituting the flow path switching part 20 (see FIG. 1). However, the present invention is not limited to this, and any arrangement that has the same function as that of the flow path switching valve 20 can be used. For example, the switching valves 32 and 34 may be multi-port valves other than 6-port valves, such as 8-port valves, or may be multi-port valves having more ports (for example, 4-port valves).

(41) In the above embodiment, as a fluid chromatograph, a fluid chromatograph capable of switching to either the LC mode or the SFC mode has been exemplified. However, the present invention is not limited to this, and a fluid chromatograph having only the LC function may be provided.

DESCRIPTION OF REFERENCE SIGNS

(42) 2: measuring pump 4: mobile phase sending part 6: sampling flow path 8: needle 10: first sample loop 12: needle driving mechanism 14: needle port 16: second sample loop 18: analysis flow path 20: flow path switching part 22: control part 24: analysis mode selection part 26: injection mode selection part 28: total volume injection operation part 30: loop injection operation part 32: switching valve (first multi-port valve) 34: switching valve (second multi-port valve) 36: switching valve 38: connecting flow path 40: bypass flow path 42: pump connecting flow path 44: mobile phase sending flow path 46 to 50, 76: liquid sending pump 80: sample container 82: analytical column 84: detector 86: back pressure control mechanism (BPR)