JP2014163882A - Concentration calculation device, concentration calculation method, and concentration calculation program - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a concentration calculation device, a concentration calculation method, and a concentration calculation program which allow calculation of a concentration of a target component in the middle of analysis.SOLUTION: Mass ratios of target components to reference components are stored per target component in a mass ratio storage unit 122. An area value in a graph showing a relation between intensity and time detected by a detector 5 is calculated by an area value calculation processing unit for a reference component identified by an identification processing unit 112. On the basis of the mass ratio stored in the mass ratio storage unit 122 in association with a target component identified by the identification processing unit 112 and the area value calculated by the area value calculation processing unit 113, a concentration of the target component is calculated by a concentration calculation processing unit 114. By using the mass ratio of the target component to the reference component, the concentration of the target component can be calculated even in the middle of analysis when the target component and the reference component are identified.

Description

  The present invention relates to a concentration calculation apparatus and a concentration calculation method for calculating the concentration of a target component in a sample based on a graph showing the relationship between the intensity and time of the target component and reference component contained in the sample detected by the detector. And a concentration calculation program.

  In gas chromatographs and liquid chromatographs, which are examples of analyzers, each component in a sample separated in the process of passing through a column is detected by a detector to show the relationship between detected intensity and time. A graph (chromatogram) is obtained. In addition to the target component to be analyzed, the sample includes, for example, a reference component that serves as a reference when calculating the concentration of the target component.

  The concentration of the target component contained in the sample can be calculated based on the area value of the target component in the graph obtained as described above (see, for example, Patent Document 1 below). Specifically, the concentration of the target component is calculated based on the ratio of the area value of the target component to the area value of the entire graph obtained by the analysis.

  In this type of analyzer, the intensity of each component detected by the detector changes due to deterioration of the column accompanying use. Therefore, the concentration of the target component can be calculated more accurately by using the ratio of the area value of the target component to the area value of the entire graph obtained by the analysis as a reference.

JP 2000-65797 A

  For example, when analysis is performed over a long period of time or when it is desired to check the concentration of a specific target component, the concentration of the target component detected up to that point can be calculated during the analysis. Configuration may be desired. In such a case, the calculated concentration of the target component does not necessarily have a high accuracy value, and if the concentration value is accurate to some extent, the next operation can be performed using the concentration value. Cases are also conceivable.

  However, as described above, in the case of a configuration in which the concentration of the target component is calculated based on the ratio of the area value of the target component to the area value of the entire graph obtained by analysis, the accuracy of the obtained concentration value Is high, but the area value of the entire graph cannot be obtained until the analysis is completed. Therefore, there is a problem that the concentration of the target component cannot be calculated until the analysis is completed. Such a problem is not limited to a gas chromatograph, a liquid chromatograph, or the like, and is a problem that similarly occurs in other various analyzers.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a concentration calculation apparatus, a concentration calculation method, and a concentration calculation program that can calculate the concentration of a target component during analysis.

  The inventor of the present application has found that the concentration of the target component can be calculated by using the mass ratio between the target component and the reference component as the sensitivity ratio. That is, the sensitivity ratio represented by the ratio between the area value of the target component and the area value of the reference component can be approximated by the mass ratio of the target component and the reference component, and the concentration of the target component can be calculated using the mass ratio. It has been found that a certainly accurate concentration value can be obtained by calculating.

  The concentration calculation apparatus according to the present invention calculates the concentration of a target component in a sample based on a graph showing the relationship between the intensity and time of the target component and reference component contained in the sample detected by the detector. A device for storing a mass ratio between a target component and a reference component for each target component; an identification processing unit for identifying a target component and a reference component detected by the detector; An area value calculation processing unit for calculating an area value in the graph of the reference component identified by the identification processing unit, and a mass stored in the mass ratio storage unit in association with the target component identified by the identification processing unit And a density calculation processing unit that calculates the concentration of the target component based on the ratio and the area value calculated by the area value calculation processing unit.

  According to such a configuration, the concentration of the target component can be calculated during the analysis by using the mass ratio between the target component and the reference component. That is, since the concentration of the target component can be calculated based on the mass ratio corresponding to the identified target component and the area value of the identified reference component, the target component and When the reference component is identified, the concentration of the target component can be calculated.

  In this case, the concentration calculation processing unit includes the mass ratio stored in the mass ratio storage unit in association with the target component identified by the identification processing unit, and the area value calculated by the area value calculation processing unit. And the concentration of the target component may be calculated.

  The concentration calculation apparatus may further include a correction coefficient storage unit that stores a correction coefficient for a mass ratio between the target component and the reference component for each target component. In this case, the concentration calculation processing unit associates the mass ratio stored in the mass ratio storage unit with the target component identified by the identification processing unit, and stores the correction factor storage unit in association with the target component. The concentration of the target component may be calculated based on the stored correction coefficient and the area value calculated by the area value calculation processing unit.

  According to such a configuration, the concentration of the target component can be calculated more accurately using the correction coefficient for the mass ratio between the target component and the reference component. Thereby, even during the analysis, a more accurate concentration value of the target component can be obtained, so that the next operation can be favorably performed using the concentration value.

  In this case, the concentration calculation processing unit associates the mass ratio stored in the mass ratio storage unit with the target component identified by the identification processing unit, and the correction coefficient storage unit in association with the target component. The density of the target component may be calculated by multiplying the correction coefficient stored in the area and the area value calculated by the area value calculation processing unit.

  The concentration calculation apparatus includes: an input reception processing unit that receives input of a molecular configuration of a target component and a reference component; and the target component based on the molecular configuration of the target component and the reference component that are input by the input reception processing unit. You may further provide the mass ratio calculation process part which calculates mass ratio with a reference | standard component. In this case, the mass ratio calculated by the mass ratio calculation processing unit may be stored in the mass ratio storage unit.

  According to such a configuration, just by inputting the molecular configuration of the target component and the reference component, the mass ratio between the target component and the reference component is automatically calculated based on the molecular configuration, and the calculated mass The concentration of the target component can be calculated using the ratio. Therefore, the mass ratio can be set easily and accurately, and the concentration of the target component can be calculated.

  The concentration calculation method according to the present invention is a concentration calculation for calculating the concentration of a target component in a sample based on a graph showing the relationship between the intensity and time of the target component and reference component contained in the sample detected by the detector. An identification processing step for identifying a target component and a reference component detected by the detector, and an area value calculation processing for calculating an area value in the graph of the reference component identified by the identification processing step Step, the mass ratio between the target component and the reference component associated with the target component identified by the identification processing step, and the area value calculated by the area value calculation processing step, And a concentration calculation processing step for calculating the concentration of the component.

  The concentration calculation program according to the present invention calculates the concentration of the target component in the sample based on a graph showing the relationship between the intensity and time of the target component and reference component contained in the sample detected by the detector. An identification processing step for identifying a target component and a reference component detected by the detector, and an area value calculation processing for calculating an area value in the graph of the reference component identified by the identification processing step Step, the mass ratio between the target component and the reference component associated with the target component identified by the identification processing step, and the area value calculated by the area value calculation processing step, And causing a computer to execute a concentration calculation processing step of calculating a concentration of the component.

  According to the present invention, by using the mass ratio between the target component and the reference component, the concentration of the target component can be calculated when the target component and the reference component are identified even during the analysis.

It is the schematic which shows the structural example of the analyzer with which the density | concentration calculation apparatus which concerns on one Embodiment of this invention was applied. It is a block diagram which shows the structural example of a density | concentration calculation apparatus. It is a flowchart which shows an example of the process by a data processing part. It is the schematic which shows an example of the chromatogram for demonstrating the aspect at the time of calculating the density | concentration of the target component. It is the schematic which shows an example of the chromatogram for demonstrating the aspect at the time of calculating the density | concentration of the target component.

  FIG. 1 is a schematic diagram illustrating a configuration example of an analyzer to which a concentration calculation apparatus 1 according to an embodiment of the present invention is applied. This analyzer comprises, for example, a gas chromatograph, a liquid chromatograph, etc., and the components in the sample are separated in the process of passing through the column 3 by introducing the sample into the column 3 from the sample introduction unit 2. The The column 3 is heated in, for example, a column oven 4.

  Each component in the sample separated in the column 3 is detected by the detector 5. The concentration calculation device 1 is electrically connected to the detector 5, and a detection signal from the detector 5 is continuously input to the concentration calculation device 1 during analysis. Thereby, the concentration calculation apparatus 1 can acquire measurement data based on the detection signal input from the detector 5, and can calculate the density | concentration of the target component in a sample based on the said measurement data.

  The concentration calculation apparatus 1 includes a data processing unit 11, a storage unit 12, an operation unit 13, a display unit 14, and the like. The concentration calculation device 1 may be configured by, for example, a computer provided separately from the analysis device, or may be configured to be incorporated in the analysis device.

  The data processing unit 11 includes, for example, a CPU (Central Processing Unit), and the data processing unit 11 functions as various functional units when the CPU executes a program. The storage unit 12 can be configured by, for example, a hard disk or a RAM (Random Access Memory).

  The operation unit 13 includes a keyboard or a mouse, for example, and an operator can perform an input operation by operating the operation unit 13. The display unit 14 can be configured by a liquid crystal display, for example, and can display the result of processing by the data processing unit 11 on the display unit 14.

  FIG. 2 is a block diagram illustrating a configuration example of the density calculation apparatus 1. In the present embodiment, analysis by an analyzer is performed using a sample that includes a target component to be analyzed and a reference component that serves as a reference for calculating the concentration of the target component. .

  The concentration calculation device 1 determines the target component in the sample based on a graph (chromatogram) showing the relationship between the intensity (signal intensity) of the target component and reference component contained in the sample detected by the detector 5 and time. The concentration is calculated. Any component can be used as the target component and the reference component contained in the sample. For example, when a petroleum component is contained in the sample, the concentration of the target component can be suitably calculated. The target component and the reference component contained in the sample may each be one type or a plurality of types.

  The data processing unit 11 functions as, for example, a measurement processing unit 111, an identification processing unit 112, an area value calculation processing unit 113, a concentration calculation processing unit 114, an input reception processing unit 115, a mass ratio calculation processing unit 116, and the like. Yes. In addition, a measurement data storage unit 121, a mass ratio storage unit 122, a correction coefficient storage unit 123, and the like are allocated to the storage unit 12.

  The measurement processing unit 111 measures a change over time in the signal intensity based on the detection signal input from the detector 5, and performs processing for storing the measurement data in the measurement data storage unit 121. The measurement data stored in the measurement data storage unit 121 can be displayed on the display unit 14 as a chromatogram during or after analysis, for example.

  The identification processing unit 112 performs processing for identifying the target component and the reference component detected by the detector 5. Specifically, the peak of the target component and the reference component is detected based on the detection signal from the detector 5, and each component can be identified based on the retention time corresponding to each peak.

  The area value calculation processing unit 113 performs a process for calculating an area value in the chromatogram for the reference component identified by the identification processing unit 112. For example, in a chromatogram with the vertical axis representing intensity and the horizontal axis representing time, the area between the peak of the reference component and the horizontal axis is obtained.

  The concentration calculation processing unit 114 performs processing for calculating the concentration of the target component. In the present embodiment, the purpose is based on the mass ratio stored in the mass ratio storage unit 122, the correction coefficient stored in the correction coefficient storage unit 123, and the area value calculated by the area value calculation processing unit 113. The concentration of the component is calculated.

Here, the mass ratio storage unit 122 stores the mass ratio between the target component and the reference component for each target component. As the mass ratio, a ratio between the molecular weight of the target component and the molecular weight of the reference component can be used. For example, when the target component is methane (CH ₄ ) and the reference component is ethylene (C ₂ H ₄ ), the molecular weight of the target component is “16” and the molecular weight of the reference component is “28”. Can be calculated as “16/28”. The mass ratio can be set, for example, by operating the operation unit 13. In this example, the mass ratio corresponding to each target component is stored in the mass ratio storage unit 122 in association with the identification information (target component ID) of each target component.

  The correction coefficient storage unit 123 stores a correction coefficient for the mass ratio between the target component and the reference component for each target component. This correction coefficient can be set to an arbitrary value by the operator based on past experience or the like. For example, the correction coefficient can be set by operating the operation unit 13. In this example, the correction coefficient corresponding to each target component is stored in the correction coefficient storage unit 123 in association with the identification information (target component ID) of each target component.

  When setting the mass ratio or the correction coefficient by operating the operation unit 13, an input screen for inputting the mass ratio or the correction coefficient may be displayed on the display unit 14. In this case, an input screen (for example, a list or the like) on which at least one of a mass ratio and a correction coefficient can be input is displayed on the display unit 14 in association with identification information (target component ID) of each target component. It may be a configuration.

  In the concentration calculation processing unit 114, the mass ratio R stored in the mass ratio storage unit 122 in association with the target component identified by the identification processing unit 112 is stored in the correction coefficient storage unit 123 in association with the target component. The concentration of the target component is calculated based on the correction coefficient F and the area value S calculated by the area value calculation processing unit 113. Specifically, the concentration value of the target component is calculated based on the obtained value (R × F × S) by multiplying the mass ratio R, the correction coefficient F, and the area value S corresponding to the identified target component. can do.

  When calculating the concentration of the target component by the concentration calculation processing unit 114, for example, a calibration curve can be used. The calibration curve can be created based on, for example, a reference component having a known concentration and an area value in the chromatogram of the reference component. In this case, the concentration of the target component may be calculated by multiplying the value (R × F × S) obtained as described above by the gradient of the calibration curve.

  The input reception processing unit 115 receives an input of the molecular configuration of the target component and the reference component. That is, when the molecular configuration of the target component and the reference component is input using the operation unit 13, processing for the input signal is performed by the input reception processing unit 115. The display unit 14 may display an input screen for inputting the molecular composition of the target component and the reference component.

  The mass ratio calculation processing unit 116 performs processing for calculating a mass ratio R between the target component and the reference component based on the molecular configuration of the target component and the reference component received by the input reception processing unit 115. The mass ratio R calculated by the mass ratio calculation processing unit 116 is stored in the mass ratio storage unit 122 for each target component, and can be used when the concentration calculation processing unit 114 calculates the concentration of the target component.

For example, when the target component is methane, “CH ₄ ” is input as the molecular configuration of the target component using the operation unit 13, and the molecular weight “16” of the target component is calculated based on the molecular configuration. Is done. When the reference component is ethylene, “C ₂ H ₄ ” is input as the molecular configuration of the reference component using the operation unit 13, so that the molecular weight “28” of the target component is based on the molecular configuration. Is calculated. And by calculating the ratio of these molecular weights as “16/28”, the mass ratio R between the target component and the reference component can be calculated.

  As described above, in this embodiment, just by inputting the molecular configuration of the target component and the reference component, the mass ratio R between the target component and the reference component is automatically calculated based on the molecular configuration. The concentration of the target component can be calculated using the mass ratio R. Therefore, the mass ratio R can be set easily and accurately, and the concentration of the target component can be calculated.

  In the present embodiment, the mass ratio storage unit 122 and the correction coefficient storage unit 123 are assigned to different storage areas of the storage unit 12, respectively. The mass ratio R and the correction coefficient F may be stored in a common storage area in association with the component ID).

  Further, the configuration in which the correction coefficient storage unit 123 is omitted may be used. In this case, the concentration calculation processing unit 114 calculates the mass ratio R stored in the mass ratio storage unit 122 in association with the target component identified by the identification processing unit 112 and the area value calculation processing unit 113. Based on the area value S, the concentration of the target component may be calculated. Specifically, the mass ratio R and the area value S corresponding to the identified target component are multiplied, and the concentration value of the target component is calculated based on the obtained value (R × S). May be.

  FIG. 3 is a flowchart illustrating an example of processing performed by the data processing unit 11. 4A and 4B are schematic diagrams showing an example of a chromatogram for explaining an aspect when calculating the concentration of the target component.

  During the analysis, the identification processing unit 112 performs processing for identifying the target component and the reference component (steps S101 and S102: identification processing step). If the target component is identified (Yes in step S101), it is determined whether or not the reference component has already been identified (step S103). If the reference component has not yet been identified (No in step S103). ), Steps S101 and S102 are performed again.

  On the other hand, when the reference component is identified (Yes in step S102), the area value S of the reference component is calculated by the area value calculation processing unit 113 (step S104: area value calculation processing step). Thereafter, it is determined whether the target component has already been identified (step S105). If the target component has not yet been identified (No in step S105), the processes in steps S101 and S102 are performed again.

  As in the example shown in FIG. 4A, when the target components P1, P2, and P3 are identified (Yes in Step S101), if the reference component P4 is not yet identified (No in Step S103), Step S101 and The process of S102 is performed again. Thereafter, when the reference component P4 is identified (Yes in step S102), the area value S of the reference component P4 is calculated by the area value calculation processing unit 113 (step S104).

  When the area value S is calculated, for example, as shown by hatching in FIG. 4A, the peak value of the reference component P4 and the horizontal axis are between the time immediately before the peak of the reference component P4 appears and the time immediately after the peak appears. The area between the axes is determined. The area value calculated by the area value calculation processing unit 113 may be an area value obtained as described above, or may be a value calculated from the area.

  At the time T1 when the reference component P4 is identified, the target components P1, P2, and P3 have already been identified (Yes in step S105), so the concentration calculation processing unit 114 calculates the concentrations of the target components P1, P2, and P3. (Step S106: Density calculation processing step). Specifically, the correction factors associated with the mass ratio R stored in the mass ratio storage unit 122 in association with the already identified target components P1, P2, and P3 and the respective target components P1, P2, and P3. Based on the correction coefficient F stored in the storage unit 123 and the area value S of the reference component P4 calculated by the area value calculation processing unit 113, the concentrations of the target components P1, P2, and P3 are calculated.

  When the target components P5, P6, and P7 are identified after the reference component P4 is identified as in the example illustrated in FIG. 4B (Yes in step S101), the reference component P4 has already been identified ( When the target components P5, P6, and P7 are identified T2, T3, and T4, the concentration calculation processing unit 114 calculates the concentrations of the target components P5, P6, and P7 (Yes in step S103) (step S106: concentration). Calculation processing step).

  That is, when the reference component P4 is identified, the area value S of the reference component P4 indicated by hatching in FIG. 4B has already been calculated by the area value calculation processing unit 113. The concentrations of the target components P5, P6, and P7 can be calculated. Specifically, the mass ratio R stored in the mass ratio storage unit 122 in association with each target component P5, P6, P7 and the correction coefficient storage unit 123 in association with each target component P5, P6, P7. Based on the correction coefficient F and the area value S of the reference component P4 calculated by the area value calculation processing unit 113, the densities of the target components P5, P6, and P7 are calculated.

  Thus, for the target components P1, P2, and P3 identified prior to the reference component P4, each target component P1 is based on the area value S of the reference component P4 at the time T1 when the reference component P4 is identified. , P2 and P3 can be calculated. On the other hand, for the target components P5, P6, and P7 identified after the reference component P4, the concentrations of the target components P5, P6, and P7 at the time points T2, T3, and T4 when the target components P5, P6, and P7 are identified are the areas of the reference component P4. It can be calculated sequentially based on the value S.

  In the present embodiment, by using the mass ratio R between the target component and the reference component, the concentration of the target component can be calculated during the analysis. For example, in the example of FIG. 4A, the concentrations of the target components P1, P2, and P3 can be calculated at the time T1 when the reference component P4 is identified. In the example of FIG. 4B, the target components P5, P6, and P7 are identified. At the time points T2, T3, and T4, the concentrations can be calculated.

  That is, in the present embodiment, the concentration of the target component can be calculated based on the mass ratio R corresponding to the identified target component and the area value S of the identified reference component. Even when the target component and the reference component are identified, the concentration of the target component can be calculated at the time points T1, T2, T3, and T4.

  In particular, in the present embodiment, the concentration of the target component can be calculated more accurately using the correction coefficient F for the mass ratio R between the target component and the reference component. Thereby, even during the analysis, a more accurate concentration value of the target component can be obtained, so that the next operation can be favorably performed using the concentration value.

  In the above embodiment, for example, a gas chromatograph, a liquid chromatograph, and the like have been described as examples of the analysis apparatus. However, the concentration calculation apparatus according to the present invention can be applied to other various analysis apparatuses. In particular, the concentration calculation apparatus according to the present invention can be suitably used for an analysis apparatus that performs gel permeation chromatography (GPC) in addition to an analysis apparatus that performs automatic analysis or continuous analysis.

  It is also possible to provide a program (concentration calculation program) for causing a computer to function as the above-described concentration calculation device. In this case, the program may be provided in a state stored in a storage medium, or may be configured such that the program itself is provided.

DESCRIPTION OF SYMBOLS 1 Concentration calculation apparatus 2 Sample introducing part 3 Column 4 Column oven 5 Detector 11 Data processing part 12 Storage part 13 Operation part 14 Display part 111 Measurement processing part 112 Identification processing part 113 Area value calculation processing part 114 Concentration calculation processing part 115 Input Reception processing unit 116 Mass ratio calculation processing unit 121 Measurement data storage unit 122 Mass ratio storage unit 123 Correction coefficient storage unit

Claims (5)

A concentration calculation device that calculates the concentration of a target component in a sample based on a graph showing the relationship between the intensity and time of the target component and reference component contained in the sample detected by the detector,
A mass ratio storage unit that stores the mass ratio of the target component and the reference component for each target component;
An identification processing unit for identifying a target component and a reference component detected by the detector;
An area value calculation processing unit for calculating an area value in the graph of the reference component identified by the identification processing unit;
Based on the mass ratio stored in the mass ratio storage unit in association with the target component identified by the identification processing unit and the area value calculated by the area value calculation processing unit, the concentration of the target component A concentration calculation apparatus comprising: a concentration calculation processing unit that calculates A correction coefficient storage unit that stores a correction coefficient for the mass ratio of the target component and the reference component for each target component;
The concentration calculation processing unit is stored in the correction coefficient storage unit in association with the mass ratio stored in the mass ratio storage unit in association with the target component identified by the identification processing unit, and in association with the target component. The concentration calculation apparatus according to claim 1, wherein the concentration of the target component is calculated based on the correction coefficient and the area value calculated by the area value calculation processing unit. An input reception processing unit that receives input of the molecular configuration of the target component and the reference component;
A mass ratio calculation processing unit that calculates a mass ratio between the target component and the reference component based on the molecular configuration of the target component and the reference component received by the input reception processing unit;
The concentration calculation apparatus according to claim 1, wherein the mass ratio storage unit stores a mass ratio calculated by the mass ratio calculation processing unit. A concentration calculation method for calculating the concentration of a target component in a sample based on a graph showing the relationship between the intensity and time of the target component and reference component contained in the sample detected by the detector,
An identification processing step for identifying a target component and a reference component detected by the detector;
An area value calculation processing step for calculating an area value in the graph of the reference component identified by the identification processing step;
Based on the mass ratio between the target component and the reference component associated with the target component identified by the identification processing step, and the area value calculated by the area value calculation processing step, the concentration of the target component A density calculation method comprising: a density calculation processing step for calculating A concentration calculation program for calculating the concentration of a target component in a sample based on a graph showing the relationship between the intensity and time of the target component and reference component contained in the sample detected by the detector,
An identification processing step for identifying a target component and a reference component detected by the detector;
An area value calculation processing step for calculating an area value in the graph of the reference component identified by the identification processing step;
Based on the mass ratio between the target component and the reference component associated with the target component identified by the identification processing step, and the area value calculated by the area value calculation processing step, the concentration of the target component A density calculation program for causing a computer to execute a density calculation processing step of calculating

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