Liquid chromatography system cleaning method and liquid chromatography system

Abstract

The present invention provides a liquid chromatography system and a cleaning method thereof that can properly clean a flow path including a switching valve. The liquid chromatography system includes: a first cleaning pump that supplies a cleaning liquid to a first valve; a switching valve that is connected to a first column and a second column and switches a connection object to a detector between the first column and the second column, wherein the detector analyzes a separated sample; and a control device. The control device drives the first cleaning pump so that the cleaning liquid flowing through the first analysis flow path can be used to clean the switching valve.

Description

Technical Field

[0001] The present disclosure relates to a cleaning method of a liquid chromatography system and a liquid chromatography system. Background Art

[0002] Liquid chromatography is a technique for separating components contained in a sample by introducing a sample to be analyzed together with an eluent as a mobile phase into a column. The components of the sample separated by liquid chromatography are analyzed by a detector such as a mass spectrometer.

[0003] International Publication No. 2017 / 216934 discloses a chromatography mass analyzer including a plurality of streams for liquid chromatography. The chromatography mass analyzer disclosed in International Publication No. 2017 / 216934 has three streams connected to a column. The chromatography mass analyzer disclosed in International Publication No. 2017 / 216934 connects any one of the three streams to the mass analyzer via a switching valve connected to the mass analyzer. Summary of the invention

[0004] According to the chromatography mass analyzer described in International Publication No. 2017 / 216934, by switching multiple flow paths to continuously analyze, the analysis efficiency can be improved. However, during the period of switching multiple flow paths to analyze the sample, a part of the sample used in the previous analysis will accumulate in the switching valve, etc. as dirt, thereby, it is possible to produce carryover. In the case of carryover, it is possible not to obtain appropriate analysis results.

[0005] An object of the present disclosure is to provide a cleaning method for a liquid chromatography system and a liquid chromatography system that can reduce the generation of carryover or eliminate carryover when carryover is generated.

[0006] A method according to one aspect of the present disclosure is a method for cleaning a liquid chromatography system. The liquid chromatography system includes: a first column and a second column for separating samples; a needle for extracting samples for injection into the first column and the second column; and an injection valve portion connecting the first column and the second column, the injection valve portion including a first injection valve connected to the first column and a second injection valve connected to the second column, the liquid chromatography system also includes: a first pump for supplying an eluent to the first injection valve; a second pump for supplying an eluent to the second injection valve; a first analysis flow path configured to allow the eluent to flow from the first injection valve toward the first column; a second analysis flow path configured to allow the eluent to flow from the second injection valve toward the second column; and a switching valve connected to the first column and the second column to switch a connection object to a detector between the first column and the second column, the cleaning method of the liquid chromatography system includes the following steps: switching a connection object to a detector between the first analysis flow path and the second analysis flow path by controlling the switching valve; and allowing a cleaning solution or a blank sample to flow to the switching valve, thereby using the cleaning solution flowing through the first analysis flow path to clean the switching valve.

[0007] According to one aspect of the present disclosure, a liquid chromatography system includes: a first column and a second column for separating samples; a needle for extracting samples for injection into the first column and the second column; and an injection valve portion connecting the first column and the second column, the injection valve portion including a first injection valve connected to the first column and a second injection valve connected to the second column, the liquid chromatography system also includes: a first pump for supplying an eluent to the first injection valve; a second pump for supplying an eluent to the second injection valve; a first analysis flow path configured to direct the eluent from the first injection valve toward the first column; a second analysis flow path configured to direct the eluent from the second injection valve toward the second column; a switching valve connected to the first column and the second column for switching a connection object to a detector between the first analysis flow path and the second analysis flow path; and a control device, which enables the switching valve to be cleaned using the cleaning liquid flowing through the first analysis flow path by allowing a cleaning liquid or a blank sample to flow to the switching valve.

[0008] [Effects of the Invention]

[0009] According to the present disclosure, it is possible to provide a liquid chromatography system cleaning method and a liquid chromatography system that can reduce the generation of carry-over or eliminate carry-over when it is generated.

[0010] The above and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 This is a schematic diagram of the structure of a liquid chromatography system.

[0012] Figure 2 It is a diagram showing the structure of a liquid chromatography system.

[0013] Figure 3 It is a diagram showing the structure of a liquid chromatography system.

[0014] Figure 4 is a block diagram showing the structure of a liquid chromatography system.

[0015] Figure 5 This is a diagram illustrating a state where a sample is sucked through a needle.

[0016] Figure 6 This is a diagram illustrating a state in which a sample sucked by a needle is injected into the injection port.

[0017] Figure 7 This is a diagram illustrating a state in which, after a sample is introduced into a column, an eluent is injected into the column.

[0018] Figure 8 This is a diagram illustrating a state in which a flow path to be analyzed is switched from a first flow path to a second flow path.

[0019] Fig. 9 It is a diagram showing a comparative example with respect to the liquid chromatography system according to the present embodiment.

[0020] Fig.10 It is a diagram for explaining the outline of the first cleaning mode to the fifth cleaning mode.

[0021] Fig.11 It is a diagram showing a specific configuration example of the first cleaning mode.

[0022] Fig.12 It is a diagram showing a specific configuration example of the second cleaning mode.

[0023] Fig.13 It is a diagram showing a specific configuration example of the third cleaning mode.

[0024] Fig.14 It is a diagram showing a specific configuration example of the fourth cleaning mode.

[0025] Fig.15 It is a diagram showing a specific configuration example of the fifth cleaning mode.

[0026] Fig.16 This is a diagram showing an example in which the flow channel is cleaned by the third cleaning mode and the fourth cleaning mode during the suction of the sample.

[0027] Fig.17 FIG. 1 is a diagram showing an example in which the flow channel is cleaned in the fourth cleaning mode during injection of a sample.

[0028] Fig.18This is a diagram showing an example of cleaning the flow channel in the second cleaning mode during sample analysis.

[0029] Fig.19 This is a diagram showing an example of cleaning the flow channel by the fourth cleaning mode and the fifth cleaning mode during the analysis of the sample.

[0030] Fig. 20 It is a diagram showing the cleaning modes selectable in the first to fourth analysis flow paths.

[0031] Fig.21 This is a timing chart showing an example of the setting of the cleaning mode.

[0032] Fig. 22 2 is a timing chart showing an example of a driving pattern of the washer pump and the high-pressure pump.

[0033] Fig.23 It means that the control device is based on Fig.21 The flowchart shown is a setting of the contents of the processing to be executed.

[0034] Fig.24 This is a flowchart showing the content of the processing related to the setting of the cleaning mode.

[0035] Fig.25 It is a figure which shows an example of the setting screen for automatic cleaning.

[0036] Fig.26 This is a flowchart showing the contents of the process of cleaning the analytical flow path according to the generation status of carry-over. DETAILED DESCRIPTION

[0037] Hereinafter, the embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. In addition, the same or corresponding parts in the drawings are denoted by the same reference numerals, and their description will not be repeated.

[0038] <General structure>

[0039] Figure 1 1 is a schematic diagram of the liquid chromatography system 10. In the liquid chromatography system 10, flow paths 291A to 291D used for sample analysis are configured. The flow paths 291A to 291D are configured to include high pressure valves 180A to 180D, respectively. The flow paths 291A to 291D are connected to a flow path 292 toward a detector 500.

[0040] A divert valve 90 is disposed between the flow paths 291A to 291D and the flow path 292 .

[0041] The flow paths 291A to 291D are respectively switched to a first flow path that goes to the diverter valve 90 via the sample injection device 100 and a second flow path that goes to the diverter valve 90 without going through the sample injection device 100. The sample injection device 100 includes a needle for injecting a sample.

[0042] The diverter valve 90 includes ports 91 to 97. Port 91 is connected to a flow path 291A. Port 92 is connected to a flow path 291B. Port 93 is connected to a flow path 291C. Port 94 is connected to a flow path 291D. Port 95 is connected to a detector 500. Ports 96 and 97 are connected to a drain pipe (not shown). Port 95 is equivalent to a main port. Ports 96 and 97 are equivalent to drain pipe ports.

[0043] The flow dividing valve 90 constitutes a switching valve that switches the connection destination of the port 95 to any one of the ports 91 to 94. The flow dividing valve 90 connects any one of the flow paths 291A to 291D to the flow path 292 that leads to the detector 500.

[0044] The structure of flow path 291A will be described in detail.

[0045] The flow path 291A includes the high pressure valve 180A and extends from the high pressure valve 180A toward the column 230A. The flow path 291A is switched by the high pressure valve 180A to a first flow path toward the column 230A via the sample injection device 100 and a second flow path toward the column 230A without passing through the sample injection device 100.

[0046] In the flow path 291A, at least a high pressure pump 220A, a cleaning pump 143A, a cleaning valve 18A, a high pressure valve 180A, and a column 230A are arranged. The high pressure valve 180A is connected to the column 230A. The column 230A is filled with a stationary phase for separating components of a sample.

[0047] The high-pressure valve 180A is connected to the high-pressure pump 220A and the cleaning pump 143A via the cleaning valve 18A. The high-pressure pump 220A supplies the eluent loaded in the container 210A to the high-pressure valve 180A. The cleaning pump 143A supplies the rinse liquid loaded in the container 250A to the high-pressure valve 180A. The cleaning valve 18A connects either the high-pressure pump 220A or the cleaning pump 143A to the high-pressure valve 180A. As a result, the eluent or the rinse liquid is supplied to the high-pressure valve 180A.

[0048] When the flow path 291A is set as the first flow path through the sample injection device 100, the eluent supplied from the high pressure pump 220A to the high pressure valve 180A flows to the column 230A through the sample injection device 100. The sample held by the sample injection device 100 is sent to the column 230A via the eluent.

[0049] When the flow path 291A is set as the second flow path that does not pass through the sample injection device 100, the eluent supplied from the high-pressure pump 220A to the high-pressure valve 180A flows to the column 230A without passing through the sample injection device 100. When the injection of the sample into the column 230A is completed, the eluent is sent from the high-pressure valve 180A to the column 230A through the second flow path. Thus, the sample is separated in the column 230A.

[0050] The column 230A is connected to the port 91 of the diverter valve 90. When the diverter valve 90 connects the port 91 and the port 95, the components of the sample separated in the column 230A flow to the detector 500 through the diverter valve 90. As a result, the components of the sample separated in the column 230A are analyzed by the detector 500 including a mass analyzer and the like.

[0051] When the cleaning pump 143A and the high-pressure valve 180A are connected via the cleaning valve 18A, the cleaning liquid is supplied to the high-pressure valve 180A. The high-pressure valve 180A allows the cleaning liquid to flow to the column 230A via the sample injection device 100 or without passing through the sample injection device 100. Thus, both the first flow path to the column 230A via the sample injection device 100 and the second flow path to the column 230A without passing through the sample injection device 100 can be cleaned.

[0052] When the port 91 of the diverter valve 90 is connected to the port 95, the flushing liquid flows from the column 230A through the port 91 and the port 95 of the diverter valve 90 toward the detector 500. As a result, the flow path 292 from the diverter valve 90 to the detector 500 is also cleaned. When the port 91 of the diverter valve 90 is connected to the port 96 and the port 97, the port 91 of the diverter valve and the ports 96 and the port 97 are cleaned.

[0053] The structure of the flow path 291A has been described in detail above. Next, the structures of the flow paths 291B to 291D will be described.

[0054] The flow path 291B includes the high pressure valve 180B and extends from the high pressure valve 180B to the column 230B. The flow path 291B is switched by the high pressure valve 180B to a first flow path extending to the column 230B via the sample injection device 100 and a second flow path extending to the column 230B without passing through the sample injection device 100.

[0055] In the flow path 291B, at least a high-pressure pump 220B for sucking an eluent from the container 210B, a cleaning pump 143B for sucking a rinse liquid from the container 250B, a cleaning valve 18B, a high-pressure valve 180B, and a column 230B are arranged.

[0056] The flow path 291C includes the high pressure valve 180C and extends from the high pressure valve 180C toward the column 230C. The flow path 291C is switched by the high pressure valve 180C into a first flow path toward the column 230C via the sample injection device 100 and a second flow path toward the column 230C without passing through the sample injection device 100.

[0057] In the flow path 291C, at least a high-pressure pump 220C for sucking up an eluent from the container 210C, a cleaning pump 143C for sucking up a rinse liquid from the container 250C, a cleaning valve 18C, a high-pressure valve 180C, and a column 230C are arranged.

[0058] The flow path 291D includes the high pressure valve 180D and extends from the high pressure valve 180D toward the column 230D. The flow path 291D is switched by the high pressure valve 180D into a first flow path toward the column 230D via the sample injection device 100 and a second flow path toward the column 230D without passing through the sample injection device 100.

[0059] In the flow path 291D, at least a high-pressure pump 220D for sucking an eluent from the container 210D, a cleaning pump 143D for sucking a rinse liquid from the container 250D, a cleaning valve 18D, a high-pressure valve 180D, and a column 230D are arranged.

[0060] Thus, the configurations of the flow paths 291B to 291D are the same as that of the flow path 291A. Therefore, the detailed description of the flow path 291A will be used as the detailed description of the flow paths 291B to 291D.

[0061] Hereinafter, the flow path 291A, the flow path 291B, the flow path 291C, and the flow path 291D are also referred to as the first analysis flow path 291A, the second analysis flow path 291B, the third analysis flow path 291C, and the fourth analysis flow path 291D, respectively. The first analysis flow path 291A, the second analysis flow path 291B, the third analysis flow path 291C, and the fourth analysis flow path 291D are respectively switched to a first flow path toward the diverter valve 90 via the sample injection device 100 and a second flow path toward the diverter valve 90 without passing through the sample injection device 100.

[0062] The liquid chromatography system 10 can switch the flow path used for analysis between the first analysis flow path 291A, the second analysis flow path 291B, the third analysis flow path 291C, and the fourth analysis flow path 291D. Therefore, according to the liquid chromatography system 10, various samples can be continuously analyzed in the detector 500. As a result, according to the liquid chromatography system 10, the analysis efficiency can be improved.

[0063] Furthermore, the liquid chromatography system 10 includes a cleaning pump 143A corresponding to the first analysis channel 291A, a cleaning pump 143B corresponding to the second analysis channel 291B, a cleaning pump 143C corresponding to the third analysis channel 291C, and a cleaning pump 143D corresponding to the fourth analysis channel 291D. These structures can clean the channels in various modes in the liquid chromatography system 10.

[0064] For example, when the first analysis channel 291A is used for sample analysis, a desired channel among the second analysis channel 291B, the third analysis channel 291C, and the fourth analysis channel 291D can be cleaned.

[0065] <Structure of liquid chromatography system 10>

[0066] Figure 2 as well as Figure 3 is a diagram showing the structure of the liquid chromatography system 10. In particular, Figure 3 2 shows the structure of the diverter valve 90 included in the liquid chromatography system 10.

[0067] If used Figure 1 As illustrated, the liquid chromatography system 10 includes four high pressure valves 180A-180D. Figure 2 In the Figure 1 A diagram showing the structure associated with the high-pressure valve 180C among the four high-pressure valves 180A to 180D shown.

[0068] The high-pressure valves 180A to 180D are connected to the first switching valve 150 and the second switching valve 160. The first switching valve 150 and the second switching valve 160 have a function of selecting a high-pressure valve related to the suction and injection of the sample among the high-pressure valves 180A to 180D. The first switching valve 150 and the second switching valve 160 include, for example, multi-way switching valves.

[0069] The first switching valve 150 is connected to a needle valve 260. The needle valve 260 is connected to a needle 191 via a sample loop 192. The needle 191 is a needle-shaped part for sucking a sample. The sample loop 192 holds the sample sucked by the needle 191. The needle moving mechanism 190 moves the needle 191 in three orthogonal axial directions.

[0070] The liquid chromatography system 10 includes injection ports 198A to 198D. The injection port 198A is provided corresponding to the high pressure valve 180A. The injection port 198B is provided corresponding to the high pressure valve 180B. The injection port 198C is provided corresponding to the high pressure valve 180C. The injection port 198D is provided corresponding to the high pressure valve 180D.

[0071] Containers 302A to 302C containing samples are placed on the sample stage 300. The needle moving mechanism 190 moves the needle 191 to suck the sample from any one of the containers 302A to 302C. The needle moving mechanism 190 moves the needle 191 to inject the sucked sample into any one of the injection ports 198A to 198D.

[0072] The needle valve 260 is further connected to the needle cleaning pump 20 .

[0073] The second switching valve 160 is connected to the low pressure valve 170. The low pressure valve 170 is connected to the metering pump 130. The metering pump 130 is used to draw a predetermined amount of a sample using the needle 191.

[0074] The high pressure valve 180A includes ports 181A to 186A. Port 181A is connected to a drain pipe not shown. That is, port 181A is a drain pipe port. Port 182A is connected to the injection port 198A. Port 183A is connected to the column 230A. Port 184A is connected to the high pressure pump 220A and the cleaning pump 143A via the cleaning valve 18A. Port 185A is connected to the first switching valve 150. Port 186A is connected to the second switching valve 160.

[0075] The high pressure valve 180A includes connecting portions 187A to 189A. The connecting portions 187A to 189A switch the connection state of the ports 181A to 186A between the first state and the second state.

[0076] The first state is Figure 2 That is, the first state is a state in which the port 181A is connected to the port 182A, the port 183A is connected to the port 184A, and the port 185A is connected to the port 186A.

[0077] In the first state, the first switching valve 150 and the second switching valve 160 are connected via the high pressure valve 180A. In the first state, the column 230A and the high pressure pump 220A or the cleaning pump 143A are connected via the high pressure valve 180A. In the first state, the injection port 198A is connected to the port 181A which is the discharge port of the high pressure valve 180A.

[0078] The second state is Figure 1 The connection parts 187A to 189A shown in the figure are rotated 30 degrees with the center of the high pressure valve 180A as the axis. That is, the second state is a state in which the port 182A is connected to the port 183A, the port 184A is connected to the port 185A, and the port 186A is connected to the port 181A. The second state is, for example, Figure 6 shown.

[0079] The high pressure valves 180B to 180D each include the same structure as the high pressure valve 180A. The high pressure valves 180B to 180D each switch between the first state and the second state in the same manner as the high pressure valve 180A. Further descriptions related to the high pressure valves 180B to 180D will substantially repeat the structural description of the high pressure valve 180A. Therefore, further descriptions of the high pressure valves 180A to 180D will not be repeated here.

[0080] The first switching valve 150 includes ports 151 to 155 . A high pressure valve 180A is connected to the port 151 . A high pressure valve 180B is connected to the port 152 . A high pressure valve 180C is connected to the port 153 . A high pressure valve 180D is connected to the port 154 . A needle valve 260 is connected to the port 155 .

[0081] The first switching valve 150 includes a connection portion 158. The connection portion 158 switches a connection destination to the port 155 among the ports 151 to 154.

[0082] The needle valve 260 includes ports 261 to 266 and connecting portions 267 to 269. The first switching valve 150 is connected to the port 261. The sample loop 192 is connected to the port 262. The needle cleaning pump 20 is connected to the port 263.

[0083] The needle valve 260 switches the state of the connection parts 267 to 269 to Figure 2 The state shown, and the connection parts 267 to 269 from Figure 2 The state shown is a state in which the needle valve 260 is rotated 30 degrees about the center of the needle valve 260.

[0084] Figure 2 In the state shown, the needle 191 is connected to the needle valve 260 via the sample loop 192, the needle valve 260 is connected to the first switching valve 150, and the first switching valve 150 is connected to the high-pressure valve 180A. Furthermore, the high-pressure valve 180A is connected to the second switching valve 160, and the second switching valve 160 is connected to the metering pump 130 via the low-pressure valve 170. Therefore, after the needle 191 is moved to any one of the containers 302A to 302C, the metering pump 130 is driven, thereby sucking the sample through the needle 191.

[0085] like Figure 3 As shown, the pipe columns 230A to 230D are connected to the diverter valve 90 . Figure 3 9 shows a state where port 95 formed in the center of diverter valve 90 is connected to port 91 corresponding to column 230A. At this time, ports 92 to 94 of diverter valve 90 are connected to ports 96 and 97 which are drain ports of diverter valve 90.

[0086] In this state, the flow path including the column 230A is connected to the detector 500. The sample of the column 230A can be analyzed in the detector 500. The flow path including the column 230B passes through the ports 96 and 97 of the diverter valve 90 and is directed to a drain pipe (not shown). The flow path including the column 230C and the flow path including the column 230D also pass through the ports 96 and 97 of the diverter valve 90 and are directed to a drain pipe (not shown).

[0087] As described above, the liquid chromatography system 10 includes a plurality of valves. In relation to the first switching valve 150 and the second switching valve 160, the diverter valve 90 may also be referred to as a third switching valve, and the needle valve 260 may also be referred to as a fourth switching valve.

[0088] <Block Diagram of Liquid Chromatography System 10>

[0089] Figure 4 2 is a block diagram showing the configuration of the liquid chromatography system 10. As described so far, the liquid chromatography system 10 includes a plurality of valves and a plurality of pumps.

[0090] The valves included in the liquid chromatography system 10 include a low-pressure valve 170 , high-pressure valves 180A to 180D, cleaning valves 18A to 18D, a needle valve 260 , a first switching valve 150 , a second switching valve 160 , and a diverter valve 90 .

[0091] Regarding the specific structure of these valves, Figure 1 to Figure 3 has been explained, so the description will not be repeated here.

[0092] The pumps included in the liquid chromatography system 10 include high pressure pumps 220A to 220D, cleaning pumps 143A to 143D, a needle cleaning pump 20, and a metering pump 130. The high pressure pumps 220A to 220D pump eluents from containers 210A to 210D, respectively. The cleaning pumps 143A to 143D pump flushing liquids from containers 250A to 250D, respectively.

[0093] The containers 210A to 210D may be filled with the same eluent or different eluents. The containers 250A to 250D may be filled with the same rinse solution or different rinse solutions.

[0094] The needle cleaning pump 20 draws the washing liquid from the container 200. The container 200 may contain the same washing liquid as the washing liquid contained in the containers 250A to 250D, or a washing liquid of a different type from the washing liquid contained in the containers 250A to 250D.

[0095] The sample injection device 100 includes a first switching valve 150 , a needle valve 260 , a needle 191 , and a sample loop 192 .

[0096] The liquid chromatography system 10 further includes a control device 110, an input device 120, a display device 125, and a needle moving mechanism 190. The needle moving mechanism 190 is described in detail. Figure 2 has been explained, so the description will not be repeated here.

[0097] The control device 110 includes a processor 111 and a memory 112. Typically, the processor 111 is a computing unit such as a central processing unit (CPU) or a multi-processing unit (MPU). The processor 111 reads out a program stored in the memory 112 and executes it, thereby realizing the processing of the liquid chromatography system 10.

[0098] The memory 112 is implemented by a non-volatile memory such as a random access memory (RAM), a read only memory (ROM), and a flash memory. As long as the memory 112 can non-temporarily record a program in a format readable by the processor 111, it may include a compact disc-read only memory (CD-ROM), a digital versatile disc-read only memory (DVD-ROM), a universal serial bus (USB) memory, a memory card, a flexible disk (FD), a hard disk, a solid state drive (SSD), a magnetic tape, a cassette tape, a magnetic optical disc (MO), a mini disc (MD), an integrated circuit (IC) card (except a memory card), an optical card, a mask ROM, or an electrical programmable read only memory (EPROM).

[0099] The input device 120 includes, for example, a keyboard and a mouse. The user can input various instructions to the control device 110 by operating the input device 120. The display device 125 displays an image corresponding to a video signal output by the control device 110.

[0100] The display device 125 displays the first to fourth analysis channels 291A to 291D (see FIG. 1 ) provided in the liquid chromatography system 10. Figure 1 ) setting information. The user can set the analysis schedule using the first analysis flow path 291A to the fourth analysis flow path 291D while viewing the screen of the display device 125. The control device 110 performs the analysis based on the input schedule and cleans the first analysis flow path 291A to the fourth analysis flow path 291D.

[0101] <Suction of sample>

[0102] Figure 5 1 and 2 are diagrams illustrating a state in which a sample is sucked by the needle 191. Here, an example in which the needle 191 sucks the sample injected into the injection port 198A from the container 302A will be described.

[0103] The injection port 198A corresponds to the high pressure valve 180A among the high pressure valves 180A to 180D. Therefore, the first switching valve 150 and the second switching valve 160 are connected to the high pressure valve 180A. As shown in the figure, the first switching valve 150 is connected to the needle 191 via the needle valve 260 and the sample loop 192. The needle moving mechanism 190 guides the needle 191 to the container 302A. The second switching valve 160 is connected to the metering pump 130 via the low pressure valve 170.

[0104] The metering pump 130 applies a predetermined negative pressure to the needle 191 via the low pressure valve 170, the second switching valve 160, the first switching valve 150 and the needle valve 260. Thus, the needle 191 draws a predetermined amount of sample from the container 302A. The sample drawn by the needle 191 is held near the sample loop 192, for example.

[0105] Figure 5 , an example of sucking a sample through the high pressure valve 180A is shown. By switching the connection destinations of the first switching valve 150 and the second switching valve 160 between the high pressure valves 180B to 180D, the sample is sucked through each of the high pressure valves 180B to 180D.

[0106] The first switching valve 150 and the second switching valve 160 constitute a switching device that switches the high-pressure valves passing through the flow path from the metering pump 130 to the needle 191 among the high-pressure valves 180A to 180D.

[0107] <Injection of sample>

[0108] Figure 6 This is a diagram illustrating a state in which a sample sucked by the needle 191 is injected into the injection port 198A.

[0109] When the sample is injected into the injection port 198A, the connection parts 187A to 189A are connected from Figure 5 The state shown starts with a 30 degree rotation about the center of the high pressure valve 180A. The cleaning valve 18A connects the high pressure valve 180A and the high pressure pump 220A. Furthermore, the needle moving mechanism 190 moves the needle 191 to the injection port 198A.

[0110] As a result, a flow path is formed from the high pressure pump 220A to the column 230A via the high pressure valve 180A, the first switching valve 150, the needle 191, the injection port 198A, and the high pressure valve 180A. Figure 1 As described above, it corresponds to the first flow path in the first analysis flow path 291A, which passes through the sample injection device 100. At this time, the column 230A is connected to the detector 500 via the diverter valve 90. Figure 6 In the figure, the connection state between the column 230A and the diverter valve 90 is omitted. The connection state is, for example, Figure 3 shown.

[0111] By driving the high-pressure pump 220A in the state where the flow path is formed as described above, the eluent is supplied to the high-pressure valve 180A. The eluent supplied to the high-pressure valve 180A flows toward the needle 191 via the first switching valve 150 and the like. Thus, the sample held near the sample loop 192 is injected into the injection port 198A from the front end of the needle 191 together with the eluent. The injected sample is directed toward the column 230A together with the eluent.

[0112] Figure 6 , an example of injecting a sample into the injection port 198A corresponding to the high pressure valve 180A is shown. By switching the connection destination of the first switching valve 150 between the high pressure valves 180B to 180D, the sample is injected into the injection ports 198B to 198D corresponding to the high pressure valves 180B to 180D, respectively.

[0113] <Injection of eluent>

[0114] Figure 7 This is a diagram illustrating a state in which, after the sample is introduced into the column 230A, an eluent is injected into the column 230A.

[0115] After the sample is introduced into the column 230A, the connection parts 187A to 189A are connected from Figure 6 The state shown starts with a 30 degree rotation about the center of the high pressure valve 180A. As a result, the high pressure pump 220A is connected to the column 230A via the port 184A and the port 183A of the high pressure valve 180A.

[0116] If this flow path is used Figure 1As described above, it corresponds to the second flow path in the first analysis flow path 291A that does not pass through the sample injection device 100. At this time, the column 230A is connected to the detector 500 via the diverter valve 90. This connection state is, for example, Figure 3 By supplying the eluent from the high pressure pump 220A to the high pressure valve 180A, the sample is separated in the column 230A.

[0117] At this time, the injection port 198A is connected to the port 181A which is the discharge port of the high pressure valve 180A. Figure 6 In the state shown, the needle valve 260 is rotated 30 degrees with the center thereof as the axis. As a result, the needle cleaning pump 20 is connected to the needle 191 via the needle valve 260 and the sample loop 192 .

[0118] Figure 7 , an example of injecting the eluent into the column 230A is shown. By driving the high-pressure pumps 220B to 220D corresponding to the high-pressure valves 180B to 180D, respectively, the eluent is similarly injected into the columns 230B to 230D.

[0119] <Switching the analysis flow path>

[0120] Figure 8 291A is a diagram illustrating a state in which the flow path used for analyzing a sample is switched from the first analysis flow path 291A to the second analysis flow path 291B. The concepts of the first analysis flow path 291A and the second analysis flow path 291B are as described using Figure 1 As described.

[0121] When the flow path used for analyzing the sample is switched from the first analysis flow path 291A to the second analysis flow path 291B, the states of the first switching valve 150 and the second switching valve 160 are changed. That is, the connection portion 158 of the first switching valve 150 switches the connection destination of the port 155 from the port 151 to the port 152. The connection portion 168 of the second switching valve 160 switches the connection destination of the port 167 from the port 161 to the port 162.

[0122] Thus, the first switching valve 150 and the second switching valve 160 are connected to the high pressure valve 180B. As shown in the figure, the first switching valve 150 is connected to the needle 191 via the needle valve 260 and the sample loop 192. The second switching valve 160 is connected to the metering pump 130 via the low pressure valve 170.

[0123] For example, after the needle 191 is moved to any one of the containers 302A to 302C containing the sample, the control device 110 drives the metering pump 130. Thus, the sample can be sucked through the high-pressure valve 180B by the needle 191. The injection port 198B corresponds to the high-pressure valve 180B among the high-pressure valves 180A to 180D. Therefore, by injecting the sample sucked by the needle 191 into the injection port 198B, the sample can be guided to the column 230B corresponding to the second analysis flow path 291B.

[0124] <Structure of Comparative Example>

[0125] Fig. 9 1 is a diagram showing a comparative example with respect to the liquid chromatography system 10 according to the present embodiment. The comparative example includes a plurality of high-pressure valves 1800A to 1800F, a first switching valve 1500 , a second switching valve 1600 , and a low-pressure valve 1700 .

[0126] The first switching valve 1500 and the second switching valve 1600 are linked to one of the high pressure valves 1800A to 1800F. The low pressure valve 1700 is connected to one of the high pressure valves 1800A to 1800F via the second switching valve 1600.

[0127] In the comparative example, the cleaning pumps corresponding to the high-pressure valves 1800A to 1800F are not provided, but the cleaning pump 1400 is provided corresponding to the low-pressure valve 1700. By driving the cleaning pump 1400, the flushing liquid is supplied to the second switching valve 1600 via the low-pressure valve 1700. In the comparative example, when the first switching valve 1500 and the second switching valve 1600 are connected to the high-pressure valve 1800A, the flow path formed by the high-pressure valve 1800A can be cleaned by driving the cleaning pump 1400.

[0128] However, when the first switching valve 1500 and the second switching valve 1600 are connected to the high-pressure valve 1800A, the flow path formed by the high-pressure valve 1800B cannot be cleaned. Similarly, when the first switching valve 1500 and the second switching valve 1600 are connected to the high-pressure valve 1800A, the flow paths formed by the high-pressure valves 1800C to 1800F cannot be cleaned.

[0129] When the first switching valve 1500 and the second switching valve 1600 are connected to the high-pressure valve 1800A, the flow path formed by the high-pressure valve 1800A may be used to analyze the sample. At this time, the various flow paths formed by the high-pressure valves 1800B to 1800F are not used for the analysis of the sample. However, in the comparative example, the supply target of the flushing liquid from the cleaning pump 1400 is limited to the connection target of the second switching valve 1600. Therefore, in the comparative example, when the second switching valve 1600 is connected to the high-pressure valve 1800A, the various flow paths formed by the high-pressure valves 1800B to 1800F cannot be cleaned.

[0130] In contrast, the liquid chromatography system 10 according to the present embodiment includes the cleaning pumps 143A to 143D corresponding to the high-pressure valves 180A to 180D, respectively. Therefore, according to the liquid chromatography system 10, regardless of which of the high-pressure valves 180A to 180D the second switching valve 160 is connected to, any flow path formed by including the high-pressure valves 180A to 180D can be cleaned with the flushing liquid.

[0131] <Overview of the First to Fifth Cleaning Modes>

[0132] Fig.10 1 is a diagram for explaining the outline of the first cleaning mode to the fifth cleaning mode. Fig.10 The cleaning mode will be described with reference to the flow path including the high pressure valve 180A. Fig.10 The first to fifth cleaning modes shown are used to clean the flow path including the high-pressure valve 180A.

[0133] In the first cleaning mode and the second cleaning mode, the flow path including the high pressure valve 180A is set as in the upper left frame. In addition, the solid arrow in the diverter valve 90 is the flow path set in the first cleaning mode, and the dotted arrow in the diverter valve 90 is the flow path set in the second cleaning mode.

[0134] In the first cleaning mode and the second cleaning mode, the flushing liquid supplied from the cleaning pump 143A to the high-pressure valve 180A flows in the order of the high-pressure valve 180A, the first switching valve 150, the needle valve 260, the sample loop 192, the needle 191, the high-pressure valve 180A, the column 230A and the diverter valve 90.

[0135] The cleaning flow path set in the first cleaning mode and the second cleaning mode corresponds to the first flow path passing through the needle valve 260, the sample loop 192, and the needle 191. The first flow path is, for example, one form of the first analysis flow path 291A.

[0136] In the first cleaning mode, port 91 of the diverter valve 90 is connected to port 95, so the flushing liquid flowing into the diverter valve 90 flows through ports 91 and 95, and cleans the flow path from the diverter valve 90 to the detector 500. In the second cleaning mode, port 91 of the diverter valve 90 is connected to ports 96 and 97, so the flushing liquid flowing into the diverter valve 90 cleans port 91 and is discharged from ports 96 and 97.

[0137] In the third cleaning mode and the fourth cleaning mode, the flow path including the high pressure valve 180A is set as in the lower left frame. In addition, the solid arrow in the diverter valve 90 is the flow path set in the third cleaning mode, and the dotted arrow in the diverter valve 90 is the flow path set in the fourth cleaning mode.

[0138] In the third cleaning mode and the fourth cleaning mode, the flushing liquid supplied from the cleaning pump 143A to the high-pressure valve 180A flows in the order of the high-pressure valve 180A, the column 230A, and the diverter valve 90 .

[0139] The cleaning flow path set in the third cleaning mode and the fourth cleaning mode corresponds to a second flow path that does not pass through the needle valve 260, the sample loop 192, and the needle 191. The second flow path is, for example, one form of the first analysis flow path 291A.

[0140] In the third cleaning mode, port 91 of the diverter valve 90 is connected to port 95, so the flushing liquid flowing into the diverter valve 90 flows through ports 91 and 95, and cleans the flow path from the diverter valve 90 to the detector 500. In the fourth cleaning mode, port 91 of the diverter valve 90 is connected to ports 96 and 97, so the flushing liquid flowing into the diverter valve 90 cleans port 91 and is discharged from ports 96 and 97.

[0141] In the fifth cleaning mode, the flow path including the high pressure valve 180A is set as shown in the right frame. In the fifth cleaning mode, the flushing liquid supplied from the needle cleaning pump 20 to the needle valve 260 flows in the order of the needle valve 260, the sample loop 192, the needle 191, and the high pressure valve 180A. The flushing liquid flowing into the high pressure valve 180A is discharged from the port 181A of the high pressure valve 180A.

[0142] Next, the specific configurations of the first to fifth cleaning modes will be described. Hereinafter, the configuration of a flow path including the high-pressure valve 180A will be described as a representative example.

[0143] <First cleaning mode and second cleaning mode>

[0144] Fig.11 It is a diagram showing a specific configuration example of the first cleaning mode. Fig.12It is a diagram showing a specific configuration example of the second cleaning mode. Fig.11 as well as Fig.12 In the figure, part of the structure is omitted and the structure related to the diverter valve 90 is surrounded by a frame. Figures 13 to 19 Same here.

[0145] In the first cleaning mode, for example, Fig.11 The flow path shown. That is, the port 151 of the first switching valve 150 is connected to the port 155. The needle 191 is connected to the injection port 198A. In the high pressure valve 180A, the port 182A is connected to the port 183A, the port 184A is connected to the port 185A, and the port 186A is connected to the port 181A. In the diverter valve 90, the port 91 is connected to the port 95.

[0146] When the flushing liquid is supplied from the cleaning pump 143A to the high pressure valve 180A, the flow path including the high pressure valve 180A, the first switching valve 150, the needle valve 260, the sample loop 192, the needle 191, the injection port 198A, the high pressure valve 180A, the column 230A, and the diverter valve 90 is cleaned by the flushing liquid. Furthermore, the flow path toward the detector 500 is cleaned by the flushing liquid. At this time, a container of a blank sample such as a flushing liquid or an eluent may be prepared in advance on the sample stage 300, and the flushing liquid may be sucked by the needle 191 to perform cleaning in the first cleaning mode.

[0147] In the second cleaning mode, for example, Fig.12 In the second cleaning mode, the setting of the flow path of the diverter valve 90 is different from that in the first cleaning mode. That is, in the second cleaning mode, the port 91 of the diverter valve 90 is connected to the port 96 and the port 97. Therefore, in the second cleaning mode, the flow path from the port 91 of the diverter valve 90 toward the port 96 and the port 97 is cleaned. At this time, a container of a blank sample such as a flushing liquid or an eluent may be prepared in advance on the sample table 300, and the sample may be cleaned in the second cleaning mode after being sucked out by the needle 191.

[0148] <Third cleaning mode and fourth cleaning mode>

[0149] Fig.13 It is a diagram showing a specific configuration example of the third cleaning mode. Fig.14 It is a diagram showing a specific configuration example of the fourth cleaning mode.

[0150] In the third cleaning mode, for example, Fig.13 That is, port 181A of high pressure valve 180A is connected to port 182A, port 183A is connected to port 184A, and port 185A is connected to port 186A. In diverter valve 90, port 91 is connected to port 95.

[0151] The flushing liquid supplied from the flushing pump 143A to the high pressure valve 180A flows toward the column 230A instead of the needle 191. As a result, the diverter valve 90 and the flow path from the diverter valve 90 to the detector 500 are cleaned by the flushing liquid.

[0152] In the fourth cleaning mode, for example, Fig.14 In the fourth cleaning mode, the setting of the flow path of the diverter valve 90 is different from that in the third cleaning mode. That is, in the fourth cleaning mode, the port 91 of the diverter valve 90 is connected to the port 96 and the port 97. Therefore, in the fourth cleaning mode, the flow path from the port 91 of the diverter valve 90 to the port 96 and the port 97 is cleaned.

[0153] <Fifth cleaning mode>

[0154] Fig.15 It is a diagram showing a specific configuration example of the fifth cleaning mode.

[0155] In the fifth cleaning mode, for example, Fig.15 That is, port 262 of needle valve 260 is connected to port 263, port 264 is connected to port 265, and port 266 is connected to port 261. Port 181A of high-pressure valve 180A is connected to port 182A, port 183A is connected to port 184A, and port 185A is connected to port 186A.

[0156] When the flushing liquid is supplied from the needle cleaning pump 20 to the needle valve 260, the flow path including the sample loop 192, the needle 191, the injection port 198A and the high pressure valve 180A is cleaned by the flushing liquid. At this time, a container of a blank sample such as a flushing liquid or an eluent may be prepared in advance on the sample stage 300, and the flushing liquid may be sucked by the needle 191 to perform cleaning in the fifth cleaning mode.

[0157] As described above, according to the first cleaning mode and the second cleaning mode, not only the flow path from the column 230A to the diverter valve 90 but also the flow path including the needle 191 and the sample loop 192 can be cleaned.

[0158] In the third cleaning mode and the fourth cleaning mode, the range that can be cleaned is smaller than that in the first cleaning mode and the second cleaning mode. However, the third cleaning mode and the fourth cleaning mode do not include the needle 191 and the sample loop 192, which has the effect of increasing the variation of the cleaning method. That is, by making use of the third cleaning mode and the fourth cleaning mode, the flow path can be cleaned at the time of aspirating the sample using the needle 191 and the sample loop 192.

[0159] According to the first cleaning mode and the third cleaning mode, the flow path toward the detector 500 can be cleaned including the port 95 of the diverter valve 90. This cleaning mode is effective, for example, when a high-concentration sample is used for analysis, or in a structure that can switch multiple analysis flow paths (first analysis flow path 291A to fourth analysis flow path 291D) to continuously analyze, as in the liquid chromatography system 10 involved in this embodiment.

[0160] When multiple analysis channels are switched for continuous analysis, components of the sample may accumulate in the diverter valve 90 for switching the analysis channels. In particular, components of the sample may repeatedly accumulate in the port 95 of the diverter valve 90 connected to the detector 500, thereby generating carryover. Alternatively, since the sample is continuously fed to the interface portion of the detector 500 through the diverter valve 90, carryover may be generated in the interface portion.

[0161] According to the first cleaning mode and the third cleaning mode, the port 95 of the diverter valve 90 and the interface part of the detector 500 can be included in the cleaning, so that efficient analysis using multiple analysis flow paths can be performed and the parts that become the cause of the carryover can be fully cleaned.

[0162] In use Figure 10 to Figure 15 In the description, an example of using a flushing liquid to clean the flow path is described. However, in the first cleaning mode to the fifth cleaning mode, an eluent (blank liquid) can also be used to clean the flow path. For example, in the first cleaning mode to the fourth cleaning mode, by replacing the cleaning pump 143A with the high-pressure pump 220A, cleaning using an eluent can also be achieved, and in the fifth cleaning mode, by connecting the needle cleaning pump 20 to a container filled with an eluent, cleaning using an eluent can also be achieved. Furthermore, in the first cleaning mode to the fifth cleaning mode, cleaning by combining a flushing liquid and an eluent can also be achieved. For example, after the flow path is cleaned with a flushing liquid, the flow path can be cleaned with an eluent.

[0163] Here, the first cleaning mode to the fifth cleaning mode are described by taking the flow path including the high-pressure valve 180A as an example. However, the liquid chromatography system 10 can also perform cleaning based on the first cleaning mode to the fifth cleaning mode for the flow paths including the high-pressure valves 180B to 180D, respectively. The above description is also applicable to the flow paths including the high-pressure valves 180B to 180D, respectively.

[0164] Next, refer to Figure 16 to Figure 19An example will be described in which the flow channels configured in the liquid chromatography system 10 are cleaned in various cleaning modes when a sample is analyzed or prepared for analysis using one of the first to fourth analysis flow channels 291A to 291D.

[0165] <Example of cleaning during sample suction>

[0166] Fig.16 1 is a diagram showing an example of cleaning the flow path by the third cleaning mode and the fourth cleaning mode during the aspiration of the sample. In particular, an example is described here in which the first analysis flow path 291A is cleaned by the third cleaning mode and the second analysis flow path 291B is cleaned by the fourth cleaning mode during the aspiration of the sample.

[0167] Fig.16 In the embodiment, the first switching valve 150 and the second switching valve 160 are connected to the high pressure valve 180A. In the diverter valve 90, the port 91 toward the column 230A is connected to the port 95 toward the detector 500. Therefore, in the first analysis flow path 291A including the high pressure valve 180A, the sample can be analyzed.

[0168] The metering pump 130 is connected to the needle 191 via the low pressure valve 170, the second switching valve 160, the high pressure valve 180A, the first switching valve 150, and the needle valve 260. The needle 191 is guided to the container 302A containing the sample. The needle 191 sucks the sample from the container 302A by the negative pressure given by the metering pump 130.

[0169] In the high-pressure valve 180B, the port 183B and the port 184B are connected.

[0170] In this state, the liquid chromatography system 10 can execute cleaning in the third cleaning mode for the first analysis channel 291A including the high pressure valve 180A and cleaning in the fourth cleaning mode for the second analysis channel 291B including the high pressure valve 180B.

[0171] The rinse liquid supplied from the cleaning pump 143A to the high-pressure valve 180A flows through the high-pressure valve 180A, the column 230A, and the diverter valve 90 to clean these components and the flow path toward the detector 500 (third cleaning mode).

[0172] The flushing liquid supplied from the cleaning pump 143B to the high-pressure valve 180B flows through the high-pressure valve 180B, the column 230B, and the diverter valve 90 to clean the flow path including these components (fourth cleaning mode).

[0173] In this way, the liquid chromatography system 10 can clean the first analysis flow path 291A while continuing the operation of sucking the sample in order to analyze the sample in the first analysis flow path 291A. Furthermore, the liquid chromatography system 10 can clean the second analysis flow path 291B. In addition, the liquid chromatography system 10 can of course clean the third analysis flow path 291C including the high-pressure valve 180C and the fourth analysis flow path 291D including the high-pressure valve 180D at the same time.

[0174] <Example of cleaning during sample injection>

[0175] Fig.17 1 is a diagram showing an example of cleaning the flow path in the fourth cleaning mode during sample injection. In particular, an example is described here in which the second analysis flow path 291B is cleaned in the fourth cleaning mode when the sample is injected into the column 230A of the first analysis flow path 291A.

[0176] Fig.17 In the flow divider 90 , the first switching valve 150 and the second switching valve 160 are connected to the high pressure valve 180A. In the flow divider 90 , the port 91 facing the column 230A and the port 95 facing the detector 500 are connected.

[0177] The high-pressure pump 220A is connected to the needle 191 via the high-pressure valve 180A, the first switching valve 150, and the needle valve 260. The needle 191 is connected to the injection port 198A. The sample loop 192 holds the sample. The needle 191 injects the sample in the sample loop 192 into the injection port 198A together with the eluent supplied from the high-pressure pump 220A. Thus, the sample is injected into the column 230A via the high-pressure valve 180A.

[0178] In the high-pressure valve 180B, the port 183B and the port 184B are connected.

[0179] In this state, the liquid chromatography system 10 can perform cleaning based on the fourth cleaning mode with the second analysis flow path 291B including the high-pressure valve 180B as the object. That is, by supplying a flushing liquid from the cleaning pump 143B to the high-pressure valve 180B, the flow path including the high-pressure valve 180B, the column 230B and the diverter valve 90 can be cleaned (the fourth cleaning mode).

[0180] Thus, the liquid chromatography system 10 can clean the second analysis channel 291B while the sample is continuously injected into the column 230A in the first analysis channel 291A. In addition, the liquid chromatography system 10 can also clean the third analysis channel 291C including the high pressure valve 180C and the fourth analysis channel 291D including the high pressure valve 180D.

[0181] <First example of cleaning during sample analysis>

[0182] Fig.18 2 is a diagram showing an example of cleaning the flow path in the second cleaning mode during sample analysis. In particular, an example is described here in which the second analysis flow path 291B is cleaned in the second cleaning mode when the sample is analyzed using the first analysis flow path 291A.

[0183] Fig.18 In the embodiment, the high pressure pump 220A is connected to the column 230A via the high pressure valve 180A. The column 230A is loaded with a sample. In the diverter valve 90, the port 91 toward the column 230A is connected to the port 95 toward the detector 500. The eluent supplied from the high pressure pump 220A is injected into the column 230A loaded with the sample via the high pressure valve 180A. In the detector 500, the sample is analyzed.

[0184] The first switching valve 150 and the second switching valve 160 are connected to the high pressure valve 180B. The cleaning pump 143B is connected to the needle 191 via the high pressure valve 180B, the first switching valve 150, and the needle valve 260. The needle 191 is guided to the injection port 198B.

[0185] In this state, the liquid chromatography system 10 can perform cleaning in the second cleaning mode with the second analysis flow path 291B including the high pressure valve 180B as the target. That is, by supplying the cleaning liquid from the cleaning pump 143B to the high pressure valve 180B, the cleaning liquid flows in the order of the high pressure valve 180B, the first switching valve 150, the needle valve 260, the sample loop 192, the needle 191, the injection port 198B, the high pressure valve 180B, the column 230B and the diverter valve 90, and the flow path including the above parts is cleaned (second cleaning mode).

[0186] Thus, the liquid chromatography system 10 can clean the second analysis channel 291B in the second cleaning mode when analyzing the sample in the first analysis channel 291A. In addition, the liquid chromatography system 10 can of course clean the third analysis channel 291C including the high pressure valve 180C or the fourth analysis channel 291D including the high pressure valve 180D in the second cleaning mode instead of the second analysis channel 291B.

[0187] Furthermore, the liquid chromatography system 10 can also clean the second analysis channel 291B in the fourth mode when analyzing a sample in the first analysis channel 291A. Furthermore, the liquid chromatography system 10 can also clean the second analysis channel 291B in the second cleaning mode and clean the third analysis channel 291C in the fourth cleaning mode when analyzing a sample in the first analysis channel 291A.

[0188] <Second example of cleaning during sample analysis>

[0189] Fig.19 1 is a diagram showing an example of cleaning the flow path by the fourth cleaning mode and the fifth cleaning mode in the analysis of the sample. In particular, the following example is described here, that is, when the first analysis flow path 291A is used to analyze the sample, the second analysis flow path 291B is cleaned by the fourth cleaning mode, and the flow path including the high-pressure valve 180A is cleaned by the fifth cleaning mode.

[0190] Fig.19 In the detector 500, the first switching valve 150 and the second switching valve 160 are connected to the high pressure valve 180A. In the diverter valve 90, the port 91 toward the column 230A is connected to the port 95 toward the detector 500. The eluent supplied from the high pressure pump 220A is injected into the column 230A loaded with the sample through the high pressure valve 180A. In the detector 500, the sample is analyzed.

[0191] In the needle valve 260, the port 262 is connected to the port 263. In the high-pressure valve 180B, the port 183B is connected to the port 184B.

[0192] In this state, the liquid chromatography system 10 can execute cleaning in the fifth cleaning mode for the channel including the high-pressure valve 180A and cleaning in the fourth cleaning mode for the second analysis channel 291B including the high-pressure valve 180B.

[0193] The flushing liquid supplied from the needle cleaning pump 20 to the needle valve 260 flows through the needle valve 260, the sample loop 192, the needle 191, and the high-pressure valve 180A, and the flow path including these parts is cleaned (fifth cleaning mode).

[0194] The flushing liquid supplied from the cleaning pump 143B to the high-pressure valve 180B flows through the high-pressure valve 180B, the column 230B, and the diverter valve 90, and the flow path including these parts is cleaned (fourth cleaning mode).

[0195] In this way, while the liquid chromatography system 10 continues to analyze the sample using the first analysis channel 291A, it is possible to perform cleaning based on the fifth cleaning mode for the channel including the high-pressure valve 180A and cleaning based on the fourth cleaning mode for the second analysis channel 291B including the high-pressure valve 180B.

[0196] In addition, the liquid chromatography system 10 can of course clean both the third analysis channel 291C including the high-pressure valve 180C and the fourth analysis channel 291D including the high-pressure valve 180D in the fourth cleaning mode.

[0197] <Selectable cleaning modes>

[0198] Fig. 20It is a diagram showing the cleaning modes selectable in the first to fourth analysis flow paths 291A to 291D. Fig. 20 In FIG. 1 , the types of cleaning modes selectable at each stage of three processes performed using the first analysis channel 291A are shown corresponding to each of the first to fourth analysis channels 291A to 291D.

[0199] If you have used Figure 10 to Figure 19 By organizing the various cleaning modes described above, for example, when the first analysis flow path 291A is used for sample analysis, the types of cleaning modes for cleaning the first analysis flow path 291A to the fourth analysis flow path 291D can be selected as follows: Fig. 20 shown.

[0200] The flow path cleaned by the fifth cleaning mode is a flow path where the cleaning liquid flows toward the drain pipe ports 181A to 184A of the high-pressure valves 180A to 180D. Fig. 20 In FIG. 1 , the fifth cleaning mode is described in association with the first to fourth analysis channels 291A to 291D using the position notation of the cleaning modes associated with the first to fourth analysis channels 291A to 291D.

[0201] Fig. 20 The stages of sample aspiration, sample injection and eluent injection shown respectively refer to: the stage of aspirating the sample through the needle 191, the stage of injecting the aspirated sample from the needle 191 into the column 230A via the injection port 198A and the high-pressure valve 180A, and the stage of injecting the eluent supplied from the high-pressure pump 220A to the high-pressure valve 180A into the column 230A.

[0202] When the sample is sucked through the needle 191, the first to fourth analysis channels 291A to 291D can be cleaned in the third cleaning mode or the fourth cleaning mode. For example, the first analysis channel 291A can be cleaned in the third cleaning mode, and the second to fourth analysis channels 291B to 291D can be cleaned in the third cleaning mode.

[0203] When the sample sucked from the needle 191 is injected into the column 230A via the injection port 198A and the high pressure valve 180A, the second to fourth analysis channels 291B to 291D can be cleaned in the third cleaning mode or the fourth cleaning mode. For example, the second analysis channel 291B can be cleaned in the third cleaning mode, and the third and fourth analysis channels 291C and 291D can be cleaned in the fourth cleaning mode.

[0204] When the eluent supplied from the high pressure pump 220A to the high pressure valve 180A is injected into the column 230A, the first analysis flow path 291A can be cleaned in the fifth cleaning mode. The parts cleaned at this time are the needle valve, the sample loop 192, the needle 191, the injection port 198A, the port 182A of the high pressure valve 180A, and the port 181A of the high pressure valve 180A.

[0205] When the eluent supplied from the high pressure pump 220A to the high pressure valve 180A is injected into the column 230A, the second to fourth analysis flow paths 291B to 291D can be cleaned in any one of the second cleaning mode, the fourth cleaning mode, and the fifth cleaning mode. For example, the second analysis flow path 291B can be cleaned in the second cleaning mode, and the third analysis flow path 291C and the fourth analysis flow path 291D can be cleaned in the fourth cleaning mode.

[0206] In this way, the liquid chromatography system 10 can clean the first to fourth analytical channels 291A to 291D in various cleaning patterns. The liquid chromatography system 10 receives input of a cleaning pattern and a cleaning timing for cleaning each analytical channel.

[0207] The user uses the input device 120 (see Figure 4 ) to set the cleaning mode and cleaning timing for cleaning each analytical flow path. The set contents are displayed on the display device 125 (refer to Figure 4 ). Control device 110 (refer to Figure 4 ) According to user instructions input to the input device 120, the cleaning mode and cleaning timing for cleaning each analysis flow path are set.

[0208] <An example of cleaning mode setting>

[0209] Fig.21 This is a timing chart showing an example of the setting of the cleaning mode. Fig.21 In the example, (1) to (5) represent the first cleaning mode to the fifth cleaning mode, respectively. Fig.21 The flow of processing performed by the liquid chromatography system 10 according to the cleaning mode and cleaning timing set according to the user's instruction will be described.

[0210] The analysis using the sample is performed using the first analysis flow path 291A to the fourth analysis flow path 291D in sequence. First, the first analysis flow path 291A is used as the object for cleaning based on the first cleaning mode. As a result, the flow path including the high-pressure valve 180A, the first switching valve 150, the needle valve 260, the sample loop 192, the needle 191, the injection port 198A, the high-pressure valve 180A, the column 230A and the diverter valve 90 is cleaned by the flushing liquid. Furthermore, the flow path from the diverter valve 90 to the detector 500 is cleaned by the flushing liquid.

[0211] Next, the sample is sucked from the first analysis flow path 291A through the needle 191. While the sample is sucked from the needle 191, cleaning in the fourth cleaning mode is performed on the second to fourth analysis flow paths 291B to 291D. Thus, for example, in the second analysis flow path 291B, the flow path from the high pressure valve 180B to the column 230B and the flow path from the column 230B to the ports 96 and 97 of the diverter valve 90 are cleaned.

[0212] When the aspiration of the sample for the first analysis flow path 291A is completed, the sample is injected into the column 230A together with the eluent. When all the samples are injected from the needle 191, the cleaning based on the fifth cleaning mode is performed. Thus, the flow path including the needle valve 260, the sample loop 192, the needle 191, the injection port 198A and the high pressure valve 180A is cleaned.

[0213] When all the sample is injected from the needle 191 in the first analysis flow path 291A, the connection state of the high pressure valve 180A is switched, and a process of flowing the eluent to the sample injected into the column 230A is started.

[0214] While analysis is being performed in the first analysis channel 291A, cleaning in the second cleaning mode is performed in the order of the second to fourth analysis channels 291B to 291D. When analysis is completed in the first analysis channel 291A, cleaning in the second cleaning mode and cleaning in the third cleaning mode are performed on the first analysis channel 291A.

[0215] Next, the process for analyzing the sample using the second analysis channel 291B is started. That is, the connection destination of the first switching valve 150 and the second switching valve 160 is switched from the high pressure valve 180A to the high pressure valve 180B. Then, cleaning in the first cleaning mode is performed on the second analysis channel 291B.

[0216] The following, such as Fig.21 As shown, the process of analyzing the sample using the second to fourth analysis channels 291B to 291D and the process of cleaning the first to fourth analysis channels 291A to 291D are repeatedly performed according to the same flow.

[0217] <Cleaning using a combination of rinse solution and eluent>

[0218] Fig. 22The timing chart shows an example of the driving pattern of the cleaning pumps 143A to 143D and the high-pressure pumps 220A to 220D. When the liquid chromatography system 10 cleans the flow path in the first to fourth cleaning modes, the flushing liquid and the eluent (blank liquid) can be used as the cleaning liquid.

[0219] For example, when cleaning the first analysis flow path 291A, the cleaning pump 143A is first driven. Thus, the first analysis flow path is cleaned with the flushing liquid. At a time point after a time T1 has passed since the driving of the cleaning pump 143A, the high-pressure pump 220A is driven instead of the cleaning pump 143A. Thus, the first analysis flow path is cleaned with the eluent. At a time point after a time T2 has passed since the driving of the high-pressure pump 220A, the driving of the high-pressure pump 220A is stopped.

[0220] According to this driving mode, after washing with the flushing liquid, the eluent is allowed to flow. Therefore, in the columns 230A to 230D, the mobile phase containing the eluent can be set to a balanced state. This driving mode can also be adopted in all the first washing mode to the fourth washing mode. For example, Fig.21 In the cleaning mode settings shown, you can also Fig. 22 The wash solutions are combined with the eluents as shown.

[0221] Here, the driving of high-pressure pump 220A is stopped at the time point when time T2 has passed since the driving of high-pressure pump 220A. However, the driving of high-pressure pump 220A may be kept constant and may be driven at all times except when the rinse liquid is supplied from washing pump 143A.

[0222] <Flowchart (Cleaning by each cleaning mode)>

[0223] Fig.23 It means that the control device 110 is based on Fig.21 A flowchart showing the contents of the processing to be executed by the settings shown.

[0224] First, the control device 110 sets the variable N to 1 (step S1). Next, the control device 110 switches the Nth analysis channel to the first cleaning position for cleaning (step S2). Thus, first, the first analysis channel 291A is cleaned in the first cleaning mode.

[0225] Next, the control device 110 switches the Nth analysis channel to the suction position, and aspirates the sample with the needle 191 (step S3). Next, the control device 110 switches all analysis channels except the Nth analysis channel to the fourth cleaning position for cleaning (step S4). Thus, for example, the first analysis channel 291A is switched to the suction position, and the second analysis channel 291B to the fourth analysis channel 291D are cleaned by the fourth cleaning mode.

[0226] Next, the control device 110 determines whether the aspiration of the sample has been completed (step S5). More specifically, it determines whether a predetermined time has passed since the processing of step S3. The control device 110 repeatedly performs the determination of step S5 until it is determined that the aspiration of the sample has been completed. When the control device 110 determines that the aspiration of the sample has been completed, the Nth analysis flow path is switched to the injection position and the sample is injected (step S6). Thus, for example, in the first analysis flow path 291A, the sample is injected into the column 230A.

[0227] Next, the control device 110 determines whether the injection of the sample has been completed (step S7). More specifically, it is determined whether a specified time has passed since the processing of step S6. The control device 110 repeatedly performs the determination of step S7 until it is determined that the injection of the sample has been completed. When the control device 110 determines that the injection of the sample has been completed, the Nth analysis flow path is switched to the fifth cleaning position for cleaning (step S8). Thus, for example, the first analysis flow path 291A is cleaned by the fifth cleaning mode. Furthermore, the control device 110 switches the other analysis flow paths other than the Nth analysis flow path to the second cleaning position for cleaning (step S9). Thus, for example, the second analysis flow path 291B to the fourth analysis flow path 291D are cleaned in sequence by the third cleaning mode.

[0228] Next, the control device 110 determines whether a predetermined analysis time has passed (step S10). The control device 110 repeatedly performs the determination of step S10 until it is determined that the analysis time has passed. When the analysis time has passed, the control device 110 switches the Nth analysis flow path to the second cleaning position and the third cleaning position in sequence to clean the Nth analysis flow path (steps S11 and S12). Thus, for example, the first analysis flow path 291A is cleaned in sequence by the second cleaning mode and the third cleaning mode.

[0229] Next, the control device 110 determines whether the analysis method in the method file has been completed (step S13). The control device 110 stores the schedule for analyzing the sample using the first to fourth analysis channels as a method file. The method file also includes a cleaning mode and a cleaning timing.

[0230] When the control device 110 determines that the analysis method of the method file has not been completed, the variable N is updated (step S14). As a result, for example, the analysis channel used for sample analysis is updated from the first analysis channel 291A to the second analysis channel 291B. The control device then returns to the process of step S2. When the control device 110 determines that the analysis method of the method file has been completed, the process based on this flowchart ends.

[0231] <Flowchart (setting of cleaning mode)>

[0232] Fig.24 1 is a flowchart showing the content of the process related to the setting of the cleaning mode. The process based on this flowchart is executed by the control device 110.

[0233] First, the control device 110 determines whether a setting operation is detected (step S21). For example, the control device 110 determines whether an operation for setting using the input device 120 is detected. If a setting operation is not detected, the process based on this flowchart ends.

[0234] When the control device 110 detects the setting operation, it reads the setting items from the memory 112 (step S22). The setting items include the analysis schedule and the cleaning mode of the sample corresponding to the first analysis flow path 291A to the fourth analysis flow path 291D. Next, the control device 110 displays the read setting items on the screen of the display device 125 (step S23).

[0235] Next, the control device 110 updates the settings of the setting items according to the user's operation (step S24). The contents set according to the user's operation also include the cleaning mode and the conditions for cleaning in this cleaning mode. The cleaning conditions include the cleaning time, the number of cleaning times, the type of cleaning liquid, etc. Through the processing of step S24, the analysis schedule and the cleaning mode of the sample are updated respectively corresponding to the first analysis flow path 291A to the fourth analysis flow path 291D.

[0236] As a result, a method file for performing new analysis is generated.

[0237] Next, the control device 110 determines whether the user's completion operation is detected (step S25). If the control device 110 has not detected the user's completion operation, the process returns to step S23. If the control device 110 detects the user's completion operation, the setting of the memory 112 is updated to the content of step S24 (step S26), and the process based on this flowchart ends.

[0238] <Settings screen>

[0239] Fig.25 1 is a diagram showing an example of a setting screen for automatic cleaning. When the control device 110 receives an operation to change the setting for automatic cleaning of the flow path, it displays the setting items on the display device 125 (see Figure 4 As a result, on the display device 125 (refer to Figure 4 ) on the display, a setting screen for automatically cleaning the flow paths including the first analysis flow path 291A to the fourth analysis flow path 291D is displayed.

[0240] Fig.25 400. The user can set the analysis flow path (stream) to be cleaned, the cleaning mode, the type of cleaning liquid, etc. while viewing the setting screen 400. For example, when the user operates any of the plurality of setting items using a mouse, etc., a window of the setting item corresponding to the operation is opened in the setting screen 400. The user can enter the desired setting value in the opened window. For example, in the setting screen 400, a window 404 opened in response to the operation of selecting the target setting item 401 is shown.

[0241] For example, the user can select a sample to be cleaned in the target setting item 401, set a threshold used by the control device 110 to determine whether to clean the flow path, and set a threshold to be used to end cleaning, etc. Furthermore, the user can select the cleaning method of the autosampler and the flow path in the autosampler item 402 and the flow path item 403. Furthermore, the user can also set the number of times to inject blank solution in the setting screen 400.

[0242] As described above, in the present embodiment, various settings related to automatic cleaning can be input from one setting screen, so the convenience for the user is improved.

[0243] <Modification (Cleaning according to the generation of residues>

[0244] Fig.26 1 is a flowchart showing the contents of the process of cleaning the analysis flow path according to the generation status of the carryover. So far, the liquid chromatography system 10 that cleans the first analysis flow path 291A to the fourth analysis flow path 291D based on a predetermined schedule has been described. However, the liquid chromatography system 10 may also detect the generation of carryover and clean the first analysis flow path 291A to the fourth analysis flow path 291D according to the generation status thereof. Here, as a modified example, the liquid chromatography system 10 that cleans the analysis flow path according to the generation status of the carryover is described.

[0245] Fig.26 The process according to this flowchart is executed by the control device 110 .

[0246] First, the control device 110 sets the variable N to 1 (step S31). Next, the control device 110 acquires the MS data of the Nth analysis channel (step S32). Here, the MS data is used to determine whether carryover is generated in the Nth analysis channel.

[0247] For example, before starting a new analysis using the first analysis channel 291A, the detector 500 is used to acquire analysis data based on the eluent in the column 230A flowing into the first analysis channel 291A. If a portion of the sample used until the last time remains in the first analysis channel 291A, the remaining sample will affect the analysis data. The detector 500 sends the acquired analysis data to the control device 110 as MS data.

[0248] The control device 110 determines whether the contamination degree of the Nth analytical channel exceeds a threshold value, that is, whether carry-over is generated, based on the MS data (step S33).

[0249] When no carryover is generated, the control device 110 switches the Nth analysis flow path to the suction position and uses the needle 191 to aspirate the sample (step S34). Next, the control device 110 determines whether the aspiration of the sample has been completed (step S35). More specifically, it is determined whether a specified time has passed since step S34. The control device 110 repeatedly performs the determination of step S35 until it is determined that the aspiration of the sample has been completed. When the control device 110 determines that the aspiration of the sample has been completed, the Nth analysis flow path is switched to the injection position and the sample is injected (step S36). Thus, for example, in the first analysis flow path 291A, the sample is injected into the column 230A.

[0250] Next, the control device 110 determines whether the injection of the sample has been completed (step S37). More specifically, it determines whether a specified time has passed since step S36. The control device 110 repeatedly performs the determination of step S37 until it is determined that the injection of the sample has been completed. When the control device 110 determines that the injection of the sample has been completed, it determines whether a predetermined analysis time has passed (step S38). The control device 110 repeatedly performs the determination of step S38 until it is determined that the analysis time has passed.

[0251] Next, the control device 110 determines whether the analysis method of the method file has been completed (step S40). When the control device 110 determines that the analysis method of the method file has not been completed, the control device 110 updates the variable N (step S41) and returns to the process of step S32.

[0252] As described above, in the modified example, when the control device 110 determines that no carry-over has occurred, the control device 110 does not execute cleaning in any of the cleaning modes 1 to 5 but advances the analysis process using the target analysis channel.

[0253] When the control device 110 determines that carryover has occurred in step S33, it cleans the analysis flow path corresponding to the setting according to the pre-set cleaning mode and cleaning timing, and advances the analysis process using the Nth analysis flow path (step S39). As a result, for example, according to the setting, Fig.23 Subsequently, when the control device 110 determines that the analysis method in the method file has been completely completed (Yes in step S40), the process based on this flowchart ends.

[0254] According to this modification, the analysis channel is cleaned according to the generation state of the residue, so it is possible to prevent the execution of unnecessary cleaning. In addition, the cleaning mode used for cleaning can be changed according to the degree of dirtiness when the residue is generated.

[0255] <Other Modifications>

[0256] (1) When cleaning the analytical flow path including the diverter valve 90, the cleaning portion of the diverter valve 90 may be switched between the port 95 connected to the detector 500 and the ports 96 and 97 connected to the waste liquid pipe. Fig.21 As shown, after the analytical flow path is cleaned in the second cleaning mode, it can also be cleaned in the third cleaning mode. Moreover, the switching of such cleaning modes can also be implemented based on a predetermined schedule. Alternatively, the switching of such cleaning modes can also be performed according to the generation of the residue.

[0257] (2) The number of high-pressure valves used in the liquid chromatography system 10 is not limited to four. For example, the number of high-pressure valves may be two, or five or more. As the number of high-pressure valves increases, the number of analytical flow paths that can be used for sample analysis can increase.

[0258] (3) The needle cleaning pump 20 may not be provided. The needle valve 260 may not be provided. In this case, the pipe extending from the sample loop 192 may be connected to the first switching valve 150 .

[0259] (4) A control unit for controlling the sample injection device 100 may be provided independently of the control device 110 for controlling the liquid chromatography system 10. In this case, the control device 110 may control the liquid chromatography system 10 including the sample injection device 100 in conjunction with the control unit.

[0260] (5) The stationary phase filled in the columns 230A to 230D may be the same or different as long as it can be used as a stationary phase for liquid chromatography analysis. The eluent filled in the containers 210A to 210D may be the same or different as long as it can be used as a mobile phase for liquid chromatography analysis.

[0261] (6) The display device 125 may display a setting screen for setting the cleaning mode for each of the first to fourth analysis channels 291A to 291D. In this case, the display device 125 may display items for setting the cleaning mode for each of the first to fourth analysis channels 291A to 291D on one screen.

[0262] (7) The cleaning mode, the type of cleaning method such as the cleaning solution, and the conditions for executing the cleaning may be set by the manager from the setting screen based on the target compound for cleaning.

[0263] (8) The detector 500 is, for example, a mass analyzer. The detector 500 may also be any one of an absorbance detector, a photodiode array (PDA) detector, a fluorescence detector, a differential refractive index detector, a conductivity detector, an evaporative light scattering detector, an electrochemical detector, an infrared spectrophotometer, an optical rotation detector, a circular dichroism detector, a hydrogen flame ionization detector, a radiation detector, a dielectric constant detector, a chemiluminescence detector, an atomic absorption spectrometer, an inductively coupled plasma emission spectrometer, a high-frequency plasma mass analyzer, a thermal detector, a light scattering detector, a viscosity detector, an ion electrode, an ultrasonic detector, and a nuclear magnetic resonance device.

[0264] [form]

[0265] Those skilled in the art will appreciate that the multiple exemplary embodiments described are specific examples of the following forms.

[0266] (Item 1) One form of the method is a method for cleaning a liquid chromatography system. The liquid chromatography system includes: a first column and a second column for separating samples; a needle for extracting samples for injection into the first column and the second column; and an injection valve portion connecting the first column and the second column, the injection valve portion including a first injection valve connected to the first column and a second injection valve connected to the second column, the liquid chromatography system also includes: a first pump for supplying an eluent to the first injection valve; a second pump for supplying an eluent to the second injection valve; a first analysis flow path configured to allow the eluent to flow from the first injection valve toward the first column; a second analysis flow path configured to allow the eluent to flow from the second injection valve toward the second column; and a switching valve connected to the first column and the second column to switch a connection object to a detector between the first column and the second column, the cleaning method of the liquid chromatography system includes the following steps: switching a connection object to a detector between the first analysis flow path and the second analysis flow path by controlling the switching valve; and allowing a cleaning solution or a blank sample to flow to the switching valve, thereby using the cleaning solution flowing through the first analysis flow path to clean the switching valve.

[0267] According to the method described in the first item, the generation of carryover can be reduced, or when carryover is generated, the carryover can be eliminated.

[0268] (Item 2) Another form of a liquid chromatography system includes: a first column and a second column for separating samples; a needle for extracting samples for injection into the first column and the second column; and an injection valve portion connecting the first column and the second column, the injection valve portion including a first injection valve connected to the first column and a second injection valve connected to the second column, the liquid chromatography system also includes: a first pump for supplying an eluent to the first injection valve; a second pump for supplying an eluent to the second injection valve; a first analysis flow path configured to allow the eluent to flow from the first injection valve toward the first column; a second analysis flow path configured to allow the eluent to flow from the second injection valve toward the second column; a switching valve connected to the first column and the second column for switching the connection object to the detector between the first analysis flow path and the second analysis flow path; and a control device, the control device enables the switching valve to be cleaned using the cleaning liquid flowing through the first analysis flow path by allowing the cleaning liquid or a blank sample to flow to the switching valve.

[0269] According to the liquid chromatography system described in the second aspect, the generation of carry-over can be reduced, or the carry-over can be eliminated when it is generated.

[0270] (Item 3) In the liquid chromatography system described in Item 2, the switching valve has a main port connected to the detector, a first port connected to the first column, and a second port connected to the second column, and is configured to switch the connection target of the main port between the first port and the second port. When the main port is connected to the first port, the control device can use a cleaning fluid flowing through the first analysis flow path to clean the flow path including the main port and the first port of the switching valve, and when the main port is separated from the first port, the control device can use a cleaning fluid flowing through the first analysis flow path to clean the flow path including the first port of the switching valve.

[0271] According to the liquid chromatography system described in the third item, the port of the switching valve can be cleaned in a state where the main port toward the detector and the first port toward the first column are connected, and the main port and the first port are cleaned in a state where they are separated, so the switching valve can be cleaned finely.

[0272] (Item 4) In the liquid chromatography system described in Item 2 or Item 3, the control device can use the eluent flowing through the first analysis flow path to clean the switching valve by driving the first pump.

[0273] According to the liquid chromatography system described in the fourth aspect, blank washing using an eluent can be performed, thereby equilibrating the inside of the column.

[0274] (Item 5) In the liquid chromatography method according to any one of Items 2 to 4, the control device can clean the switching valve by allowing a blank sample to flow to the first injection valve or the second injection valve.

[0275] According to the liquid chromatography system described in the fifth item, the generation of carryover can be reduced in the switching valve by using a blank sample, or the carryover can be eliminated when it is generated.

[0276] (Item 6) In the liquid chromatography system described in any one of Items 2 to 5, it also includes: a first cleaning pump, which supplies cleaning liquid to the first injection valve; and a second cleaning pump, which supplies cleaning liquid to the second injection valve. The control device drives the first cleaning pump and the second cleaning pump to clean the switching valve using the cleaning liquid flowing through the first analysis flow path and the cleaning liquid flowing through the second analysis flow path.

[0277] According to the liquid chromatography system described in the sixth aspect, the flow path that passes through the first analysis flow path and includes the switching valve and the flow path that passes through the second analysis flow path and includes the switching valve can be cleaned efficiently.

[0278] (Item 7) In the liquid chromatography system described in any one of Items 2 to 6, it also includes: a third column; a third injection valve connected to the third column; a third pump supplying eluent to the third injection valve; and a third analysis flow path, configured to allow the eluent to flow from the third injection valve toward the third column, a switching valve connected to the third column, and switching the connection object to the detector between the first column, the second column and the third column.

[0279] According to the liquid chromatography system described in item 7, the third analysis channel is used in addition to the first analysis channel and the second analysis channel, thereby making it possible to more efficiently analyze the sample.

[0280] (Item 8) In the liquid chromatography system described in Item 3, the switching valve also includes a discharge pipe port connected to the discharge pipe, and when the main port and the first port are separated, the first port is connected to the discharge pipe port.

[0281] According to the liquid chromatography system described in the eighth aspect, when the main port and the first port are separated, the first port is connected to the drain pipe port.

[0282] Although the embodiments of the present invention have been described, the embodiments disclosed this time should be considered to be illustrative in all aspects and not restrictive. The scope of the present invention is indicated by the claims, and is intended to include all modifications within the meaning and scope equivalent to the claims.

Claims

1. A method for cleaning a liquid chromatography system, wherein Liquid chromatography system includes: The first column and the second column are used to separate the sample; a needle for extracting a sample for injection into the first column and the second column; and The injection valve part connects the first pipe column and the second pipe column, The injection valve unit includes a first injection valve connected to the first pipe column and a second injection valve connected to the second pipe column. The liquid chromatography system also includes: a first pump, supplying an eluent to the first injection valve; a second pump, supplying an eluent to the second injection valve; a first analytical flow path configured to direct the eluent from the first injection valve toward the first column; a second analysis flow path configured to direct the eluent from the second injection valve toward the second column; and a switching valve connected to the first column and the second column, and switching a connection object to the detector between the first column and the second column, The switching valve has a main port connected to the detector, a first port connected to the first column, and a second port connected to the second column, and is configured to switch a connection destination of the main port between the first port and the second port. In a state where the main port is connected to the first port, the flow path including the main port and the first port of the switching valve can be cleaned using a cleaning liquid flowing through the first analysis flow path. In a state where the main port and the first port are separated, the flow path including the first port of the switching valve can be cleaned using a cleaning liquid flowing through the first analysis flow path. The cleaning method of the liquid chromatography system comprises the following steps: By controlling the switching valve, a connection destination to the detector is switched between the first analysis flow path and the second analysis flow path; and The cleaning solution or the blank sample is caused to flow to the switching valve, thereby cleaning the switching valve using the cleaning solution flowing through the first analysis channel.

2. A liquid chromatography system, comprising: The first column and the second column are used to separate the sample; a needle for extracting a sample for injection into the first column and the second column; as well as The injection valve part connects the first pipe column and the second pipe column, The injection valve unit includes a first injection valve connected to the first pipe column and a second injection valve connected to the second pipe column. The liquid chromatography system also includes: a first pump, supplying an eluent to the first injection valve; a second pump, supplying an eluent to the second injection valve; a first analytical flow path configured to direct the eluent from the first injection valve toward the first column; a second analysis flow path configured to direct the eluent from the second injection valve toward the second column; a switching valve connected to the first column and the second column, and switching a connection target to a detector between the first analysis flow path and the second analysis flow path; and Control device, The switching valve has a main port connected to the detector, a first port connected to the first column, and a second port connected to the second column, and is configured to switch a connection destination of the main port between the first port and the second port. The control device allows the cleaning liquid or the blank sample to flow to the switching valve, thereby using the cleaning liquid flowing through the first analysis flow path to clean the switching valve. The control device can clean the flow path including the main port and the first port of the switching valve using the cleaning liquid flowing through the first analysis flow path in a state where the main port is connected to the first port. The control device can clean the flow path including the first port of the switching valve using the cleaning liquid flowing through the first analysis flow path in a state in which the main port and the first port are separated. 3 . The liquid chromatography system according to claim 2 , wherein the control device can clean the switching valve using the eluent flowing through the first analysis flow path by driving the first pump. 4 . The liquid chromatography system according to claim 2 , wherein the control device is capable of cleaning the switching valve by allowing a blank sample to flow to the first injection valve or the second injection valve.

5. The liquid chromatography system according to claim 2 or 3, further comprising: a first cleaning pump, supplying cleaning liquid to the first injection valve; as well as a second cleaning pump, supplying cleaning liquid to the second injection valve; The control device can clean the switching valve using the cleaning liquid flowing through the first analysis flow path and the cleaning liquid flowing through the second analysis flow path by driving the first cleaning pump and the second cleaning pump.

6. The liquid chromatography system according to claim 2 or 3, further comprising: The third pipe column; a third injection valve connected to the third pipe column; a third pump, supplying an eluent to the third injection valve; as well as The third analysis flow path is configured to allow the eluent to flow from the third injection valve toward the third column. The switching valve is further connected to the third column, and switches a connection destination to the detector among the first column, the second column, and the third column.

7. The liquid chromatography system according to claim 2, wherein The switching valve further includes a drain pipe port connected to a drain pipe. When the main port and the first port are separated, the first port is connected to the drain pipe port.

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