JP6160526B2 - Gas chromatograph apparatus and gas chromatograph analysis system - Google Patents

Description

  The present invention relates to a gas chromatograph apparatus and a gas chromatograph analysis system including the apparatus, and more particularly, to a gas chromatograph apparatus suitable for analyzing a sample gas introduced from a sample pretreatment apparatus such as a headspace sampler and such an apparatus. Including gas chromatographic analysis system. The gas chromatograph apparatus here includes a gas chromatograph mass spectrometer whose detector is a mass spectrometer, as a matter of course, regardless of the type of detector.

  One of the sample introduction methods in gas chromatography analysis is the headspace method. The headspace method volatilizes components having a relatively low boiling point by heating a liquid sample or solid sample contained in a sealed sample container to a certain temperature for a certain time, and a sample containing these components from the upper space in the container. In this method, a certain amount of gas is collected and introduced into a column of a gas chromatograph apparatus. Gas chromatographic analysis using such a method is suitable, for example, for measurement of fragrances in foods and measurement of volatile organic compounds in water.

  When introducing a sample by the headspace method, it is common to connect a kind of sample pretreatment device called a headspace sampler to a gas chromatograph device equipped with a column, a detector and the like. FIG. 6 is a general block diagram of a gas chromatograph analysis system for introducing a sample by the headspace method. The gas chromatograph analysis system includes a head space sampler 1, a gas chromatograph 2, and a system control unit 3.

  Although not shown in FIG. 6, the gas chromatograph 2 includes a column for separating sample components, an injector (sample vaporization chamber) for introducing a sample into the column, a detector connected to the outlet of the column, and the like. . The headspace sampler 1 also temporarily holds a heating unit for heating a vial containing a sample solution, a needle for collecting a sample gas from an upper space in the sealed vial, and the collected sample gas. A sample loop, a valve for switching between a flow path for holding the sample gas sucked through the needle in the sample loop and a flow path for feeding the sample gas held in the sample loop to the column of the gas chromatograph 2 by the carrier gas flow, etc. . The system controller 3 is a personal computer equipped with dedicated control / processing software.

  In the headspace sampler 1, an inert gas such as helium is used to hold the sample gas in the sample loop or introduce the sample gas expelled from the sample loop into the column. This is performed by a flow controller mounted on the gas chromatograph 2 (see, for example, Patent Document 1). Therefore, the head space sampler 1 and the gas chromatograph 2 are connected to each other through a plurality of inter-device gas flow paths 4. In addition, the system control unit 3 and the head space sampler 1, and the system control unit 3 and the gas chromatograph 2 are connected by communication lines for exchanging signals with each other.

  In a normal gas chromatographic analysis in which the headspace sampler 1 is not used, the flow controller mounted on the gas chromatograph 2 supplies a carrier gas to the column through the injector at a constant linear velocity, or a flame ionization detector (FID). When a detector such as) is used, makeup gas or the like is supplied to the detector. When the analysis is executed normally, the flow rate and pressure of the gas controlled by the flow controller rarely fluctuate greatly, so if these fluctuate greatly during the analysis, there may be some abnormality in the analysis High nature. Therefore, in the conventional gas chromatograph apparatus, the fluctuation of the detection value by the pressure sensor or the flow sensor mounted on the flow controller is constantly monitored during the analysis, and the fluctuation exceeds the predetermined normal control range. In some cases, an abnormality detection process is performed in which it is recognized that the state is abnormal, for example, information indicating the occurrence of abnormality is left as an analysis log.

Therefore, when such a gas chromatograph apparatus is used in the system as shown in FIG. 6, there are the following problems.
That is, normally, the head space sampler 1 and the gas chromatograph 2 are connected by an inter-device gas flow path 4 for supplying a carrier gas or the like, but control signals are not exchanged through a communication line. The head space sampler 1 and the gas chromatograph 2 are configured to operate independently based on instructions from the system control unit 3. Therefore, even in the system as shown in FIG. 6, the control unit of the gas chromatograph 2 does not recognize that the headspace sampler 1 is connected.

  When analysis is being performed under the control of the system control unit 3, for example, in the headspace sampler 1, when a needle is inserted into a vial or a valve is switched, the gas flow connected to them is changed. The pressure and flow rate of gas in the passage may fluctuate greatly instantaneously. If this fluctuation exceeds the normal control range predetermined in the flow controller in the gas chromatograph 2, the control unit of the gas chromatograph 2 determines that an abnormality has occurred and analyzes the information to that effect. Record in the log. That is, when the conventional gas chromatograph apparatus is used in the system as shown in FIG. 6, this is abnormal even though the pressure and flow rate of the gas in the gas flow path fluctuate due to the normal operation of the headspace sampler 1. There is a possibility that it is erroneously determined to be in a state and remains in the analysis log.

JP 2013-68644 A

  The present invention has been made in view of the above-mentioned problems, and an object thereof is a case where a sample pretreatment device such as a headspace sampler is connected to the gas chromatograph device, and control of the gas chromatograph device. Even if the head unit does not recognize the presence of the headspace sampler and its operating state, the gas pressure and flow rate are not controlled by the flow controller on the gas chromatograph device side even though the headspace sampler is operating normally. It is an object of the present invention to provide a gas chromatograph apparatus and a gas chromatograph analysis system including the apparatus capable of avoiding erroneous determination as abnormal.

A first aspect of the gas chromatograph apparatus according to the present invention, which has been made to solve the above-mentioned problems, is a sample component separation column, a detector for detecting a component eluted from the column, and a supply to the column. A plurality of flow controllers including at least a flow controller for controlling a flow rate of the carrier gas, and a gas flow whose flow rate is controlled by at least one of the plurality of flow controllers may be used in an external device. In the gas chromatograph apparatus having a configuration that can be taken out to the outside,
a) a user setting unit for an analyzer to set a flow controller in which a gas flow path is connected to the external device among the plurality of flow controllers;
b) An abnormality determination unit that determines whether or not fluctuations in the pressure and / or flow rate of the gas to be controlled are abnormal for each of the plurality of flow controllers, and is set via the user setting unit For the flow controller, an abnormality determination unit that relaxes the threshold for determining whether or not the fluctuation of the gas pressure and / or the flow rate is abnormal than the normal state;
It is characterized by having.

  The above “normal state” means a state in which the setting that the gas flow path is connected to the external device is not performed in the user setting unit, that is, even if the flow controller is not used or used at all. This is a state that is used only inside the graph apparatus.

  In addition, the flow controller here refers to one that automatically controls the gas flow rate (AFC), one that substantially controls the flow rate by automatically controlling the gas pressure (APC), and gas pressure and gas. (AFC / APC) that automatically controls both the flow rate.

  The external device here is typically a sample pretreatment device such as a headspace sampler, and a flow controller is used to control a carrier gas for introducing the sample gas into the gas chromatograph device. When the external device is a headspace sampler, a flow controller is usually used for controlling a pressurized gas used for collecting a sample gas in addition to controlling a carrier gas.

  In the gas chromatograph apparatus according to the first aspect of the present invention, for example, the abnormality determination unit determines that the gas pressure controlled by the flow controller is normal when the gas pressure is within a predetermined control range centered on the control target value. When the gas pressure is out of this control range, it is determined that there is an abnormality. On the other hand, when it is set that one or more flow controllers are used to supply gas to an external device via the user setting unit, for the one or more flow controllers, It is determined that there is an abnormality when the gas pressure is out of the respective control ranges but not in the control range for a predetermined time.

  As a result, for example, in a headspace sampler that is an external device, even when the gas pressure fluctuates momentarily when the valve is switched, that is, when the gas pressure fluctuates beyond the control range, such fluctuation It is not recognized as abnormal, and no analysis log indicating that an abnormality has occurred remains. On the other hand, even when an external device is connected, if there is an abnormality such as a gas leak, the state where the gas pressure is out of the control range should continue for a predetermined time or more, so the abnormality determination unit Can reliably recognize that an abnormality has occurred and can leave an analysis log that an abnormality has occurred or warn an analyst that an abnormality has occurred.

A second aspect of the gas chromatograph apparatus according to the present invention, which has been made to solve the above problems, is a sample component separation column, a detector for detecting a component eluted from the column, and a supply to the column. A plurality of flow controllers including at least a flow controller for controlling a flow rate of the carrier gas, and a gas flow whose flow rate is controlled by at least one of the plurality of flow controllers may be used in an external device. In the gas chromatograph apparatus having a configuration that can be taken out to the outside,
a) Analyzing information on timings at which fluctuations in the pressure and / or flow rate of the gas to be controlled can occur during analysis of a flow controller having a gas flow path connected to the external device among the plurality of flow controllers. An information acquisition unit that is received prior to or prior to the time when the gas pressure and / or flow rate fluctuations may occur during analysis.
b) An abnormality determination unit that determines whether or not fluctuations in the pressure and / or flow rate of the gas to be controlled are abnormal for each of the plurality of flow controllers, based on information received by the information acquisition unit Whether or not the fluctuation of the gas pressure and / or flow rate is abnormal at least in a predetermined time range before and after the timing at which the fluctuation of the gas pressure and / or flow rate may occur, for the specific one or more flow controllers An abnormality determination unit that relaxes the threshold for determining
It is characterized by having.

As one form of the gas chromatograph device according to the second aspect of the present invention, the information acquisition unit includes information indicating which of the flow controllers is a flow controller having a gas flow path connected to an external device among a plurality of flow controllers. Further, it is possible to adopt a configuration in which information regarding timing at which fluctuations in the pressure and / or flow rate of the gas that is the control target can occur during analysis is received from the control devices that respectively control the operations of the gas chromatograph device and the external device. .

The gas chromatograph analysis system according to the present invention, which has been made to solve the above-mentioned problems, is controlled in flow rate by the gas chromatograph apparatus according to the second aspect of the present invention and a flow controller provided in the gas chromatograph apparatus. A gas chromatograph analysis system including an external device using a gas flow and a control device for controlling each of the devices,
The control device is set in advance to control the gas chromatograph device and the external device, respectively, prior to the analysis or before the timing at which the gas pressure and / or flow rate may fluctuate during analysis. An information notification unit that sends out information on timing at which fluctuations in gas pressure and / or flow rate may occur with respect to the flow controller in which a gas flow path is connected to the external device, based on the information indicating the analyzed conditions,
The information acquisition unit of the gas chromatograph apparatus receives information sent from the information notification unit.

  In the case of adopting a system configuration in which a control device controls both a gas chromatograph device and an external device such as a headspace sampler, as in the gas chromatograph analysis system according to the present invention, the control device uses a valve in the external device when performing analysis. The timing to switch between is understood as analysis conditions. Therefore, in the gas chromatograph analysis system according to the present invention, the control device indicates information indicating that the gas pressure fluctuation is possible for the specific flow controller in real time, for example, during analysis execution with respect to the gas chromatograph device. Is sent out. The information acquisition unit of the gas chromatograph device receives this information sent from the control device through the communication line. Then, the abnormality determination unit of the gas chromatograph apparatus is not when the gas pressure is out of the control range only during a predetermined time range before and after the time when the gas flow can greatly fluctuate for the designated flow controller. It is determined that there is an abnormality when a state outside the control range continues for a predetermined time.

  Alternatively, before starting the analysis, the control device is information for identifying the flow controller connected to the gas flow path to the external device and the time during which a large fluctuation in gas pressure can occur in the flow controller. And time information indicating that. In the gas chromatograph device, the information acquisition unit stores the information received from the control device in a storage unit or the like. When the analysis is performed, the abnormality determination unit, based on the information stored in the storage unit, causes the gas pressure to deviate from the respective control range only in a predetermined time range before and after the predetermined time for a specific flow controller. It is determined that there is an abnormality when a state out of the control range continues for a predetermined time, not when the control range is exceeded.

  As a result, in the gas chromatograph analysis system using the gas chromatograph apparatus according to the second aspect, in the same manner as the gas chromatograph apparatus according to the first aspect, for example, in the head space sampler that is an external apparatus, Even when a large gas pressure or flow rate fluctuation occurs, such a fluctuation is not recognized as abnormal, and no analysis log indicating that an abnormality has occurred remains. On the other hand, for all flow controllers regardless of whether or not they are connected to an external device, the abnormality determination unit determines whether the gas pressure or flow rate is not likely to occur instantaneously in the external device. Recognize that large fluctuations in the flow rate over a short period of time are abnormal. This makes it possible to reliably leave an analysis log indicating that an abnormality has occurred when an abnormality or failure actually occurs, or to warn an analyst that an abnormality has occurred.

  According to the gas chromatograph device of the present invention, when an external device such as a headspace sampler is connected to the gas chromatograph device, the gas pressure and flow rate in the flow controller are instantaneous for normal operation in the external device. Even if a large fluctuation occurs, it can be avoided that it is determined to be abnormal. As a result, although there is no actual abnormality, information indicating abnormality is not left in the analysis log. On the other hand, when a problem that affects the analysis result occurs, information on the occurrence of an abnormality due to the problem can be reliably left in the analysis log.

The schematic block diagram of one Example (1st Example) of GC analysis system using the gas chromatograph apparatus which concerns on this invention. The flowchart of the abnormality determination process performed in the control part of the gas chromatograph in the GC analysis system of 1st Example. The figure which shows an example of the pressure fluctuation of the carrier gas in the GC analysis system of 1st Example. The schematic block diagram of other Example (2nd Example) of GC analysis system using the gas chromatograph apparatus which concerns on this invention. Explanatory drawing of the abnormality determination process performed in the control part of the gas chromatograph in the GC analysis system of 2nd Example. The general block block diagram of the GC analysis system which introduces the sample by the head space method.

[First embodiment]
An embodiment of a GC analysis system using a gas chromatograph apparatus according to the present invention will be described with reference to the accompanying drawings.

FIG. 1 is a schematic configuration diagram of a GC analysis system according to the present embodiment.
This GC analysis system includes a head space sampler (HS) 1, a gas chromatograph (GC) 2, and a system control unit 3, similarly to the block configuration shown in FIG. 6.

  The headspace sampler 1 includes one or a plurality of vials 11 housed in a rack 10, a needle 12 that sucks a sample gas from an upper space in the sealed vial 11, and a state indicated by a dotted line and a solid line in FIG. 1. One end is connected to the port 13 of the valve 13 and the sample loop 14 having a predetermined internal volume connected between the ports b and e of the valve 13 and the 6-port 2-position valve 13 which can be switched to the state shown in FIG. Two electromagnetic valves 15 and 16 and an HS controller 17 for controlling the operation of each part in the headspace sampler 1 are included. The needle 12 can be moved up and down by a lifting mechanism (not shown). Further, the rack 10 is horizontally oriented with respect to the vertical movement position of the needle 12 by a driving mechanism (not shown) so that sample gas can be collected from any one of the plurality of vials 11 stored in the rack 10. Can be moved to.

The gas chromatograph 2 includes a column 22 housed in a column oven 20, an injector 21 provided at the inlet end of the column 22, a detector 23 provided at the outlet end of the column 22, and first to third pluralities. Flow controllers (FC) 25A, 25B, and 25C, a GC control unit 26 that controls the entire gas chromatograph 2 including these flow controllers 25A, 25B, and 25C, an operation unit 27 that is a user interface, and a display unit 28. The GC analysis system of this embodiment, the first flow controller 25A controls the gas pressure and flow rate of the pressurized gas, the second flow controller 25 B is adapted to control the gas pressure and flow rate of carrier gas, The gas flow paths connected to the flow controllers 25 </ b> A and 25 </ b> B are connected to the head space sampler 1. On the other hand, the third flow controller 25C is used for supplying makeup gas to the detector 23.
Although only three flow controllers are illustrated in FIG. 1, a configuration in which more flow controllers can be mounted may be employed.

  The system control unit 3 is a personal computer on which dedicated control / processing software is installed, and is connected to the headspace sampler 1 and the gas chromatograph 2 through communication lines.

First, a sample introduction operation in the headspace sampler 1 will be schematically described.
The vial 11 accommodated in the rack 10 is heated to a predetermined temperature, whereby the sample components in the sample solution are vaporized and accumulated in the upper space in the vial 11. When the valve 13 is in the state indicated by the dotted line in FIG. 1, the needle 12 is lowered and inserted into the upper space in the vial 11 to be analyzed. When the electromagnetic valve 15 is opened in this state, the pressurized gas supplied while the flow rate is adjusted by the first flow controller 25A of the gas chromatograph 2 passes through the ports a and b of the valve 13, the sample loop 14, and the ports e and f. It flows into the upper space in the vial 11 from the needle 12. Thereby, the sample gas in the vial 11 is pressurized.

Next, when the electromagnetic valve 15 is closed and the electromagnetic valve 16 is opened, the sample gas pressurized in the vial 11 flows through the ports f and e, the sample loop 14 and the ports b and a of the valve 13. As a result, the sample loop 14 is filled with a predetermined amount of sample gas.
When the valve 13 is in the state indicated by the dotted line in FIG. 1, the carrier gas supplied while the flow rate is adjusted by the second flow controller 25B of the gas chromatograph 2 passes through the ports c and d of the valve 13 and is supplied to the gas chromatograph 2. , And flows to the column 22 through the sample introduction tube 24 and the injector 21. Therefore, the carrier gas can be continuously supplied to the column 22 at a constant flow rate before the sample gas is introduced into the column 22.

  Subsequently, the valve 13 is switched to the state shown by the solid line in FIG. Then, the carrier gas supplied while the flow rate is adjusted by the second flow controller 25B of the gas chromatograph 2 flows through the ports c and b of the valve 13, the sample loop 14, and the ports e and d. As a result, the sample gas filled in the sample loop 14 immediately before is pushed by the carrier gas and sent to the gas chromatograph 2, and introduced into the column 22 through the sample introduction tube 24 and the injector 21. In this manner, a predetermined amount of sample gas collected from the upper space in the vial 11 can be sent to the column 22.

In the gas chromatograph 2, the sample gas introduced into the column 22 travels through the column 22 on the carrier gas flow, and in the process, the sample components in the sample gas are separated in the time direction. The makeup gas supplied while the flow rate is adjusted by the third flow controller 25C is added to the gas containing each component thus separated and introduced into the detector 23. The detector 23 outputs a detection signal corresponding to the amount of components contained in the introduced gas.
Thus, in the GC analysis system of the present embodiment, a detection signal for a component in the sample gas generated from the sample solution in the vial 11 can be obtained.

  In the above analysis, the GC control unit 26 of the gas chromatograph 2 instructs the control target values of the gas pressure and the flow rate to the first to third flow controllers 25A, 25B, and 25C, respectively, and the flow controllers 25A and 25B. , 25C finely control the opening of the valve so that the detected value by the pressure sensor or flow sensor of each of them corresponds to the instructed control target value.

  When the headspace sampler 1 and other sample pretreatment devices are not connected to the gas chromatograph 2, and the gas controlled by the flow controllers 25A, 25B, and 25C is used only inside the gas chromatograph 2. For example, even if there is a disturbance such as vibration, the actual gas pressure and flow rate do not greatly deviate from the control target value. On the other hand, in the case where there is a gas leak due to the gas pipe joint being disconnected or the seal being deteriorated, the gas pressure and the flow rate greatly deviate from the control target value. Therefore, the GC control unit 26 reads detection values of pressure sensors and flow sensors provided in the flow controllers 25A, 25B, and 25C, and the control range in which the detection values allow for a predetermined margin above and below the control target value. It is repeatedly determined whether it is within the range. When these detected values deviate from the predetermined control range, it is recognized that some abnormality has occurred, and information indicating the occurrence of the abnormality is recorded as an analysis log.

  However, as in the GC analysis system shown in FIG. 1, the flow path is switched by the valve 13 which is the connection destination of the gas flow path connected to the flow controllers 25 </ b> A and 25 </ b> B, or the needle 12 is located in the upper part of the vial 11. If it is inserted into the space, the gas pressure and flow rate may temporarily fluctuate greatly in the flow controllers 25A and 25B. Since these are normal operations in the headspace sampler 1, it is inappropriate for the gas chromatograph 2 to retain information on the occurrence of an abnormality in the analysis log at that time. Therefore, in the GC analysis system of the present embodiment, characteristic abnormality determination processing is performed so that such inappropriate abnormality determination is not performed. FIG. 2 is a flowchart of the abnormality determination process, and FIG. 3 is a diagram illustrating an example of carrier gas pressure fluctuation in the GC analysis system of the present embodiment.

  Prior to the execution of the analysis, the analyst performs a predetermined operation on the operation unit 27 of the gas chromatograph 2, and any of a plurality of flow controllers (25A, 25B, 25C in this example) mounted on the gas chromatograph 2 is selected. Is used for the headspace sampler 1. For example, in the example of FIG. 1, two of the first and second flow controllers 25 </ b> A and 25 </ b> B are used in the headspace sampler 1, so that effect is set. This setting information is stored in a storage unit inside the GC control unit 26.

  When the analysis is started, the GC control unit 26 repeatedly executes the abnormality determination process cycle shown in FIG. That is, the GC control unit 26 first acquires either or both of the pressure detection value and the flow rate detection value for each flow controller (step S1). Then, it is determined whether or not the detected value is within a control range that allows margins above and below the control target value (step S2). In FIG. 3, the control target value is indicated by Ptg and the margin is indicated by ΔP. This control target value is determined according to the analysis conditions. The margin for determining the control range may be determined in advance as a default value for each flow controller so that an analyst can set an appropriate value using the operation unit 27 instead of the default value. If the detected value is within the control range (Yes in step S2), there is no abnormality, so the cycle of this abnormality determination process is terminated through step S8 described later. Specifically, in FIG. 3, when the detected value of the gas pressure fluctuates as indicated by the symbol a, for example, this is within the control range Ptg ± ΔP. Become.

  On the other hand, if it is determined in step S2 that the detected value of the pressure or flow rate is out of the control range, the GC control unit 26 determines that the abnormality determination target is based on the setting information stored in the storage unit. It is determined whether or not a certain flow controller is used in the headspace sampler 1 (step S3). If it is determined that the flow controller is not used in the headspace sampler 1 (No in step S3), it is determined that there is a possibility of an abnormality. Then, the process proceeds from step S3 to S7, the occurrence of an abnormal state is recorded in the analysis log together with the occurrence time, etc., and the cycle of the abnormality determination process is terminated.

  On the other hand, if it is determined in step S3 that the flow controller that is the abnormality determination target is used in the headspace sampler 1, the GC control unit 26 counts up the abnormal state duration (step S4), and after It is determined whether or not the abnormal state duration exceeds a time threshold determined as described later (step S5). If the abnormal state duration does not exceed the time threshold (No in step S5), the abnormality determination process cycle is terminated as it is. As described above, when it is determined No in step S5 and the cycle of the abnormality determination process is ended, the abnormal state duration counted up is maintained as it is (that is, not reset), and the next abnormality determination process is performed. To the next cycle.

  As described above, in the headspace sampler 1 during execution of the analysis, the needle 12 is inserted into the upper space in the vial 11 to be analyzed or the valve 13 is switched. At that time, the pressure and flow rate of the gas flowing in the gas flow path may fluctuate greatly temporarily. However, the pressure and flow rate control function of the flow controller itself, the pressure and flow rate are quickly near the control target value. Return to. Therefore, it is desirable to determine the time threshold according to the control responsiveness of the flow controller. When pressure fluctuation or flow fluctuation exceeding the control range occurs due to normal operation, the pressure and flow rate are controlled. It may be longer than the time required to return to the vicinity of the target value. In addition, since the time required for the greatly fluctuating pressure and flow rate to return to the vicinity of the control target value may vary depending on the viscosity of the sample gas and the like, the analyst can set it appropriately from the operation unit 27 in the same manner as the margin ΔP. You may be able to do it.

  If a large change in pressure or flow rate that exceeds the control range occurs during normal operation of the headspace sampler 1, it is determined No in step S2, and further proceeds in steps S3 → S4 → S5, but the abnormal state duration time is increased. Before the threshold value is exceeded, Yes is determined in step S2. Specifically, in FIG. 3, when the detected value of the gas pressure fluctuates as indicated by the symbol b, for example, the fluctuation deviates from the control range Ptg ± ΔP, but the detected value has passed the time threshold t. It returns to the control range Ptg ± ΔP before the operation. In such a case, the process proceeds from step S2 to S8, the abnormal state duration is reset, and the abnormality determination processing cycle is terminated. Therefore, an abnormal state is not recorded in the analysis log.

  On the other hand, if the headspace sampler 1 is not in a normal operation and a large change in pressure or flow rate is caused by some abnormality, the pressure or flow rate is controlled by the control function of the flow controller or the flow rate control function. Does not return near the value. In such a case, in the process of repeating the abnormality determination process cycle, it is continuously determined No in step S2, and therefore the abnormal state duration is repeatedly counted up. Eventually, the abnormal state duration exceeds the time threshold (Yes in step S5), and the process proceeds to steps S6 and S7. Specifically, in FIG. 3, when the detected value of the gas pressure fluctuates as indicated by the symbol c, for example, the state where the pressure fluctuation deviates from the control range Ptg ± ΔP continues for the time threshold t or more. In such a case, the process proceeds from step S5 to S6, and after resetting the abnormal state duration, the fact that the abnormal state has occurred is recorded in the analysis log together with the time of occurrence, and the cycle of this abnormality determination process is terminated.

  Thus, in the GC analysis system of the present embodiment, the flow controllers 25A and 25B used in the headspace sampler 1 are determined to be abnormal if the gas pressure and flow rate are normal. Even if the value fluctuates to the value, no abnormality occurrence information remains in the analysis log as long as the pressure and flow rate fluctuate due to normal operation of the headspace sampler 1. On the other hand, when an abnormality actually occurs rather than a change in pressure or flow rate due to the normal operation of the headspace sampler 1, abnormality occurrence information remains reliably in the analysis log. For the flow controller 25C that is not used in the headspace sampler 1, abnormality occurrence information remains in the analysis log even if there is a short-term abnormality as usual. Thus, the analyst can recognize the occurrence of some abnormality related to the gas supply.

  In the GC analysis system of the first embodiment, it is possible to add the functions described above to the conventional GC analysis system by changing the program (firmware) that defines the operation in the GC control unit 26, and the system control There is no need to change the control software installed in the unit 3. On the other hand, as will be described below, the abnormality determination process similar to that in the first embodiment can be performed by changing the control software installed in the system control unit 3 together.

[Second Embodiment]
FIG. 4 is a schematic configuration diagram of the GC analysis system of the second embodiment using the chromatographic analyzer according to the present invention, and FIG. 5 is an explanation of the abnormality determination process performed by the GC control unit in the GC analysis system of the second embodiment. FIG.

The system control unit 3 comprehensively controls the operations of both the head space sampler 1 and the gas chromatograph 2, and the analysis schedule storage unit 32 of the system control unit 3 describes analysis procedures, analysis conditions, and the like. An analysis schedule is stored in advance. When the analysis is started, the system control unit 3 sends a control signal to the head space sampler 1 and the gas chromatograph 2 in accordance with the analysis schedule, thereby realizing an analysis in which both are linked.
In the GC analysis system of the second embodiment, the system control unit 3 further includes a process change time notification unit 31. In addition, the GC control unit 260 in the gas chromatograph 2 receives a signal sent from the process change time notification unit 31 and sets a time range for changing the abnormality determination process according to the signal. 261 and an abnormality determination processing unit 262 that switches the abnormality determination processing sequence between the set time range and outside the time range.

  When the analysis is started, the system control unit 3 outputs control signals to the head space sampler 1 and the gas chromatograph 2 in accordance with the analysis conditions set in the analysis schedule. This is the same as a normal GC analysis system. At the same time, the processing change time notification unit 31 uses the pressure and flow rate of the gas such as needle insertion and valve switching for the flow controller (25A and 25B in the first embodiment) used in the headspace sampler 1. The GC control unit 260 of the gas chromatograph 2 is notified that the execution timing (see FIG. 5A) of the operation that may fluctuate has come. Receiving this notification, the process change time notification receiving unit 261 of the gas chromatograph 2 generates a signal having a predetermined time width (see FIG. 5B).

  The abnormality determination processing unit 262 determines whether or not the pressure detection value and / or the flow rate detection value is within a predetermined control range for each of the flow controllers 25A, 25B, and 25C during the execution of the analysis, as in the first embodiment. The abnormality determination process is repeated, but when the signal of the predetermined time width is given from the process change time notification receiving unit 261, the pressure detection value and / or the flow rate detection value for the flow controller exceeds the control range. Is determined to be abnormal when a predetermined time threshold has elapsed. That is, in the first embodiment, the flow controller used in the headspace sampler 1 is abnormal when the pressure detection value and / or flow rate detection value exceeds the control range for a predetermined time threshold. In the second embodiment, the flow controller used in the headspace sampler 1 is determined only at the timing when operations such as needle insertion and valve switching are executed in the flow controller. When a state in which the pressure detection value and / or the flow rate detection value exceeds the control range passes a predetermined time threshold, it is determined to be abnormal. Thereby, in this 2nd Example, malfunctions, such as a gas leak of the gas channel connected to the flow controller currently used for headspace sampler 1, can be detected more certainly.

  In the GC analysis system of the second embodiment, the system control unit 3 informs the GC control unit 260 of the gas chromatograph 2 of the execution timing of the operation that may cause the gas pressure and flow rate to fluctuate substantially in real time during the execution of the analysis. Before starting the analysis, the gas chromatograph 2 summarizes the specific information of the flow controller used in the headspace sampler 1 and the time information when the gas pressure and flow rate fluctuate greatly in the flow controller. Then, the above-described abnormality determination process may be executed by reading from the system control unit 3 and using the information.

  Moreover, although the said Example is a GC analysis system which supplies sample gas to a gas chromatograph with a head space sampler, it uses the gas by which the gas pressure and flow volume were controlled using the flow controller mounted in the gas chromatograph. The present invention can be applied to a GC analysis system using various types of sample pretreatment devices other than the headspace sampler.

  Moreover, since the said Example is an example of this invention, even if it corrects, changes, and adds suitably in the range of the meaning of this invention, it is clear that it is included by the claim of this application.

1 ... Headspace sampler (HS)
DESCRIPTION OF SYMBOLS 10 ... Rack 11 ... Vial 12 ... Needle 13 ... Valve 14 ... Sample loop 15, 16 ... Electromagnetic valve 17 ... HS control part 2 ... Gas chromatograph (GC)
DESCRIPTION OF SYMBOLS 20 ... Column oven 21 ... Injector 22 ... Column 23 ... Detector 24 ... Sample introduction pipe 25A, 25B, 25C ... Flow controller 26, 260 ... GC control part 27 ... Operation part 28 ... Display part 3 ... System control part 31 ... Processing Change time notification unit 32 ... analysis schedule storage unit 4 ... inter-device gas flow path

Claims (4)

A column for sample component separation, a detector for detecting a component eluted from the column, and a plurality of flow controllers including at least a flow controller for controlling the flow rate of the carrier gas supplied to the column. In the gas chromatograph apparatus having a configuration in which the gas flow whose flow rate is controlled by at least one of the plurality of flow controllers can be taken out so as to be usable in the external apparatus,
a) a user setting unit for an analyzer to set a flow controller in which a gas flow path is connected to the external device among the plurality of flow controllers;
b) An abnormality determination unit that determines whether or not fluctuations in the pressure and / or flow rate of the gas to be controlled are abnormal for each of the plurality of flow controllers, and is set via the user setting unit For the flow controller, an abnormality determination unit that relaxes the threshold for determining whether or not the fluctuation of the gas pressure and / or the flow rate is abnormal than the normal state;
A gas chromatograph apparatus comprising: The gas chromatograph apparatus according to claim 1,
In the normal state, the abnormality determining unit determines that the gas pressure and / or flow rate controlled by the flow controller is out of a predetermined control range centered on a control target value, and determines that the user setting is abnormal. About the flow controller set via the unit, the gas chromatograph apparatus determines that the gas pressure and / or flow rate is abnormal when a state where the gas pressure and / or flow rate is out of the control range continues for a predetermined time. A column for sample component separation, a detector for detecting a component eluted from the column, and a plurality of flow controllers including at least a flow controller for controlling the flow rate of the carrier gas supplied to the column. In the gas chromatograph apparatus having a configuration in which the gas flow whose flow rate is controlled by at least one of the plurality of flow controllers can be taken out so as to be usable in the external apparatus,
a) Analyzing information on timings at which fluctuations in the pressure and / or flow rate of the gas to be controlled can occur during analysis of a flow controller having a gas flow path connected to the external device among the plurality of flow controllers. An information acquisition unit that is received prior to or prior to the time when the gas pressure and / or flow rate fluctuations may occur during analysis.
b) An abnormality determination unit that determines whether or not fluctuations in the pressure and / or flow rate of the gas to be controlled are abnormal for each of the plurality of flow controllers, based on information received by the information acquisition unit Whether or not the fluctuation of the gas pressure and / or flow rate is abnormal at least in a predetermined time range before and after the timing at which the fluctuation of the gas pressure and / or flow rate may occur, for the specific one or more flow controllers An abnormality determination unit that relaxes the threshold for determining
A gas chromatograph apparatus comprising:
A gas chromatograph analysis system comprising: the gas chromatograph device according to claim 3; an external device that uses a gas flow whose flow rate is controlled by a flow controller provided in the gas chromatograph device; and a control device that controls each of the devices. Because
The control device is set in advance to control the gas chromatograph device and the external device, respectively, prior to the analysis or before the timing at which the gas pressure and / or flow rate may fluctuate during analysis. An information notification unit that sends out information on timing at which fluctuations in gas pressure and / or flow rate may occur with respect to the flow controller in which a gas flow path is connected to the external device, based on the information indicating the analyzed conditions,
The gas chromatograph analysis system, wherein the information acquisition unit of the gas chromatograph device receives information sent from the information notification unit.

Images