JP2000275232A - Chromatograph control device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chromatograph control device capable of calculating a concentration reanalysis by properly changing the gate time for the peak of a chromatogram and reflecting the gate time setting based on the calibration result and reanalysis calculation result on the chromatograph main body. SOLUTION: This chromatograph control device 200 connected to a chromatograph 100 to control it is provided with a chromato-data file 202 storing measured chromato-data and calibrated chromato-data, a means 204 for reading out the desired chromato-data from the chromato-data file 202, a means 206 for displaying a chromatogram based on the read-out chromato-data, a means 209 for selecting the desired peak included in the displayed chromatogram, a means 210 for optionally setting the gate on/off-time related to the selected peak, a means for calculating the reanalysis of the selected peak concentration based on the set gate on/off-time, and a means 211 for instructing the transfer of the reanalysis calculation definite data to the chromatograph 100.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chromatographic controller connected to a chromatograph and controlling the chromatograph, and more particularly to a reanalysis operation of a peak concentration value included in the chromatogram.

[0002]

2. Description of the Related Art A chromatograph is an apparatus configured to separate sample components based on a difference in affinity between a stationary phase and a mobile phase, and a liquid chromatograph, which uses a liquid as a mobile phase, is used as a mobile phase. Those that use a carrier gas such as nitrogen or helium are classified as gas chromatographs, and those that measure ionic components are classified as ion chromatographs.

The applicant of the present invention, as a system utilizing such a chromatograph, continuously measures the concentration of trace ion components in a steam system for rotating a turbine of a generator of a thermal power plant or a nuclear power plant online. An application was filed as Japanese Patent Application No. 07-102060 “Chromatographic Controller for Process”.

[0004] In nuclear power generation and thermal power generation, steam is used to turn a turbine. The steam that has passed through the turbine is returned to water by the condenser, then turned into steam again by the heating source and sent to the turbine. Condensate sent to the heating source contains Na ⁺ , C1 ⁺ , and SO ₄ ^2+, which causes corrosion of the boiler system. Therefore, pH is adjusted after ionic substances are removed by a desalination unit. Addition of hydrazine and the like is performed and controlled.

Conventionally, the control of ions in the condensate has been carried out by a so-called acid conductivity detection method in which a sample water is taken out from the outlet of the condenser and the conductivity is measured through a cationic resin in order to amplify the sensitivity. However, because the accuracy of measuring trace components was not good, the final judgment was based on the ion chromatograph method in the analytical laboratory.

[0006] However, water quality control by the conventional acid conductivity detection method or ion chromatography method can measure only ions dissolved in condensate water, and the ion exchange resin of the desalination apparatus deteriorates. However, since ions generated from the eluted ion exchange resin fine particles cannot be measured, there is a problem that ions generated from the ion exchange resin corrode the boiler, the steam generator, and the like.

Therefore, the applicant of the present invention has filed Japanese Patent Application No.
According to No. 060, the ion exchange resin degraded and eluted from the desalination device was irradiated with ultraviolet rays, and the amount of ion exchange resin contained in the condensate was determined by measuring the ions generated by the decomposition of the ion exchange resin. A chromatographic controller for the process that properly manages corrosive ions in condensate water was proposed.

FIG. 8 is a block diagram showing an example of such a process chromatograph controller. In the drawing, reference numeral 1 denotes a condenser for returning water vapor returned from the turbine to water, and reference numeral 2 denotes a condensate desalination device for desalinating chlorides, sulfates and the like from the condensate returned by the condenser 1.

Reference numeral 3 denotes a pump for taking out sample water from the outlet of the condensate desalination apparatus 2, reference numeral 4 denotes a first valve provided in the main flow path, and reference numeral 5 denotes a second valve provided in the bypass flow path. The first valve 4 is normally in an open state, and is in a state of measuring the ion concentration remaining in the fluid that has passed through the condensate desalination apparatus 2. At this time,
The second valve 5 is in a closed state.

The sample water introduced through the first valve 4 is sampled by the first sample valve 6 and sent to the cation measurement line 10, sampled by the second sample valve 7 and measured by the anion measurement Sent to line 20.

Reference numeral 8 denotes an ultraviolet irradiation device for decomposing the ion-exchange resin flowing out of the condensate desalination device 2, which irradiates sample water introduced through the second valve 5 with, for example, ultraviolet light having a high intensity, and Decompose the ion exchange resin. Second
The sample water sent out to the ultraviolet irradiation device 8 through the valve 5 is irradiated with ultraviolet light, then sampled by the first sample valve 6 and the second sample valve 7, and connected to the cation measurement line 10 and the negative electrode. Ion measurement line 2
0. At this time, the first valve 4
It is closed.

In the cation measurement line 10, 11 is a cation separation column, 12 is a cation suppressor,
Reference numeral 3 denotes a positive ion detector. Anion measurement line 20
In the above, 21 is an anion separation column, 22 is a suppressor for anions, and 23 is a detector for anions.

After the background of the cations separated by the cation column 11 is reduced by the cation suppressor 12, the conductivity is detected by the cation detector 13.
A chromatogram for each separated ion is obtained. On the other hand, after the background of the anions separated by the anion column 21 is reduced by the anion suppressor 22, the conductivity is detected by the anion detector 23, and the chromatogram of each separated ion is obtained. can get.

The chromatograms obtained by the detectors 13 and 23 in this manner contain ions generated by decomposing the ion-exchange resin with respect to the chromatogram obtained without irradiation with ultraviolet rays. The components generated by decomposition of the ion exchange resin are a sulfate ion generated from a sulfone group of the cation exchange resin, an ammonium ion and a nitrate ion generated from an ammonium group of the anion exchange resin. By measuring the concentration of these ions, the elution amount of the ion exchange resin contained in the condensed water can be known.

FIG. 9 is a characteristic diagram showing the relationship between the irradiation time of ultraviolet rays and sulfate ions generated by decomposition of the cation exchange resin. The measurement conditions were as follows: a standard solution of 1 μM sodium didodecylbenzenesulfonate was flowed at 30 mL / min, and the irradiation distance was 20 to 4 using a 30 W ultraviolet lamp.
This is the case where 0 mm is set. It can be seen that if the UV irradiation time is about 10 minutes, sodium didodecylbenzenesulfonate can be almost completely decomposed.

As described above, the ion exchange resin degraded and eluted from the desalination apparatus is irradiated with ultraviolet rays, and the ions generated by the decomposition of the ion exchange resin are measured. Therefore, corrosion factors in condensate water can be controlled including ions generated by ion exchange resin, which is optimal for the management of power generation equipment with strict water quality standards.

The ions of the sample water injected into the separation columns 11 and 21 are sequentially eluted from those having a low affinity for the ion exchange resin packed in the separation columns 11 and 21. The affinity depends on the type of ion and the separation column 1.
It depends on the type of the ion exchange resin filled in 1, 21.

The ion elution time depends on the affinity,
It is determined by the concentration of the eluent, the flow rate of the eluent, and the temperature of the separation columns 11 and 21. By keeping these conditions accurately and constant, the same type of ions are always eluted at the same time, and the type of ions contained in the sample water can be confirmed from these elution times.

FIG. 10 is an example of a chromatogram displaying the concentration of the eluted ions along the time axis. These ion concentration detections are performed mainly by measuring the conductivity of the eluate.

In qualitative quantification of each ion concentration,
A standard chromatogram obtained by analyzing a standard sample having a known ionic component and a measurement chromatogram obtained by analyzing a sample water to be measured are added to a data processing unit (not shown), based on a peak position of the standard chromatogram. To identify the type of ion at the peak position of the measurement chromatogram. Then, set the gate time for cutting out the peak so that the peak height and peak area corresponding to the known concentration can be calculated individually for each peak of the standard chromatogram, and measure the chromatogram based on the set gate time. The height and area of each peak are calculated to calculate the concentration.

Here, the elution time of the ions is the affinity,
If it changes due to changes in the concentration of the eluent, the flow rate of the eluent, the temperature of the separation columns 11 and 21, etc., the gate time for calculating the concentration of each peak in the measured chromatogram must also be changed.

[0022]

However, in the conventional configuration, in order to set a gate time required for obtaining an accurate concentration calculation result for each peak of the standard chromatogram,
There is a problem that workability is poor because trial and error must be repeated several times. Therefore, under the present circumstances, a standard sample is appropriately measured to obtain a standard chromatogram, and a correction coefficient for a known standard area is calculated by obtaining an area of each peak of the standard chromatogram based on a preset gate time, A correction operation based on the correction coefficient is performed on the calculation result of the area of each peak of the measurement chromatogram. However, in order to obtain a highly accurate measurement result, the latest correction coefficient must be obtained each time. In addition, the conventional chromatograph alone does not consider performing the concentration calculation by appropriately changing the gate time for the peak of the measured chromatogram.

The present invention has solved such a problem, and an object of the present invention is to perform a concentration reanalysis operation by appropriately changing a gate time for a peak of a measured chromatogram, and perform a calibration result and a reanalysis. An object of the present invention is to provide a chromatographic control device in which a gate time setting based on a calculation result is reflected in a chromatographic main body.

[0024]

According to the present invention, there is provided a chromatographic control device connected to a chromatograph for controlling a chromatograph, wherein the chromatographic control device includes a measuring chromatographic data and a calibration chromatographic data. A chromatographic data file for storing data, means for retrieving desired chromatographic data from the chromatographic data file, means for displaying a chromatogram based on the recalled chromatographic data, and selection of a desired peak contained in the displayed chromatogram Means, means for arbitrarily setting the gate on / off time associated with the selected peak, and arithmetic means for performing reanalysis calculation of the selected peak concentration based on the set gate on / off time. For instructing to transfer the reanalysis calculation final data to the chromatograph And it has a.

In such a configuration, the chromatographic data calling unit arbitrarily calls a calibration chromatogram or a measured chromatogram stored in the chromatographic data file and displays it on the chromatogram display unit. The peak selection section selects the target peak from the chromatogram displayed on the chromatogram display section, and the gate setting section sets the gate on / off time for each selected peak, changes the gate time, and changes the peak time. This is reflected in the chromatogram calculation unit that performs the density calculation. The data transfer instructor transfers the reanalysis calculation results performed on the measurement chromatogram and calibration chromatogram called from the chromatographic data file to the chromatograph main unit and updates the gate time data set in the chromatograph I do.

As a result, the main body of the chromatograph operates under the control of the chromatograph controller, and the result of the reanalysis operation is reflected, so that a highly accurate measurement result can be obtained.

According to a second aspect of the present invention, there is provided the chromatographic control device according to the first aspect, wherein a measuring chromatogram operation unit and a calibration chromatogram operation unit are provided as operation means.

With such a configuration, each operation unit is specialized for each operation purpose, so that each operation can be efficiently executed and processed.

According to a third aspect of the present invention, there is provided the chromatographic control device according to the first aspect, wherein the measuring chromatogram operation unit and the calibration chromatogram operation unit are shared as operation means.

According to such a configuration, since the chromatogram calculation unit is shared for measurement and calibration, the configuration can be simplified.

[0031]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a configuration block diagram showing an embodiment of the present invention. In the figure, 100 is a chromatograph such as an ion chromatograph or a gas chromatograph, and 200 is a chromatograph controller connected to the chromatograph 100 to control the chromatograph 100.

In the chromatographic control device 200,
The communication control unit 201 controls the exchange of data with the chromatograph 100. Specifically, chromatograph 1
The measurement data of “00” is transmitted to the chromatograph control device 200, and the setting data and calculation results of the chromatograph control device 200 are transmitted to the chromatograph 100.

The chromatographic data file 202 stores measurement chromatographic data and calibration chromatographic data under the control of the chromatographic data file control unit 203. The chromatographic data calling unit 204 calls the desired measurement chromatographic data or calibration chromatographic data from the chromatographic data file 202, and outputs it to the chromatogram display unit 206 via the chromatogram display control unit 205.
The data is output to the measurement chromatogram calculation unit 207 and the calibration chromatogram calculation unit 208 via the chromatogram data file control unit 203.

The chromatogram display unit 206 displays a chromatogram based on the chromatographic data called from the chromatographic data file 202. Peak selector 20
9 selects a desired peak from a plurality of peaks included in the chromatogram displayed on the chromatogram display unit 206, and outputs the selected data to the measurement chromatogram calculation unit 207 and the calibration chromatogram calculation unit 208. I do. The gate setting unit 210 arbitrarily sets the gate on / off time associated with the peak selected by the peak selection unit 209, and outputs setting data to the measurement chromatogram calculation unit 207 and the calibration chromatogram calculation unit 208.

The measurement chromatogram calculation unit 207 performs gate setting for the peak selected by the peak selection unit 209 from the peaks included in the measurement chromatogram based on the desired measurement chromatographic data called from the chromatographic data file 202. The reanalysis calculation of the density is performed based on the gate on / off time set by the unit 210. The calibration chromatogram operation unit 208 uses the gate setting unit 210 for the peak selected by the peak selection unit 209 from the peaks included in the calibration chromatogram based on the desired calibration chromatographic data called from the chromatographic data file 202. A re-analysis calculation of the density is performed based on the set gate on / off times.

The data transfer instructing unit 211 includes a measurement chromatogram operation unit 207 and a calibration chromatogram operation unit 2
08, the communication control unit 201 and the communication control unit 201 transmit the re-analysis calculation final data in the calibration chromatogram operation unit 208 to the chromatograph 100 while re-storing the re-analysis operation final data in the chromatographic data file 202.
It instructs the measurement chromatogram operation unit 207 and the calibration chromatogram operation unit 208.

The chromatograph 100 rewrites and updates the reference concentration data, the peak reference area data, and the gate on / off time data of the corresponding standard sample by transferring the reanalysis calculation final data in the calibration chromatogram calculation unit 208. And prepare for the next measurement calculation.

FIG. 2 is an example of a screen for a reanalysis calculation of the peak concentration value included in the measured chromatogram on the chromatogram display unit 206 of the chromatograph controller 200. The title bar displays the screen name, and when a chromatogram is displayed, the task number and the task name are displayed. The peak list display section displays peak numbers, peak names, and concentration values included in the displayed chromatogram. In FIG. 2, three peaks “CH3OOO” and “CHO3
O "and" NO3 ", indicating that the first peak" CH3OOOO "is selected as a re-analysis calculation target.

The gate ON time portion displays the gate ON time of the selected peak, and the gate OFF time portion displays the gate OFF time of the selected peak. In FIG. 2, the gate ON time of the selected peak “CH3OOO” is “444.0”.
S "and the gate OFF time is" 504.0S ". The ON and OFF times of these gates can be changed individually. These changes can be made by entering a numerical value from the keyboard or by dragging a range on the chromatogram screen.

The detection slope section displays the detection slope of the selected peak. In FIG. 2, the selected peak “C
The detection slope of “H3OOO” is “0.100 ns”. The data of the detection slope can be edited with the keyboard by selecting automatic by designating the integration range.

The gating section displays a gating method for the selected peak. Here, when automatic is selected by designating the integration range, four types of slope gate, time gate, slope / time and zone can be set, and when manual is selected, the time gate is displayed regardless of the setting. In FIG. 2, “slope” is set as the gate processing method for the selected peak “CH3OOO”.

The peak ON time part is the ON state of the selected peak.
When the time is displayed and the reanalysis button is clicked, the ON time of the reanalyzed peak is displayed. The peak OFF time section displays the OFF time of the selected peak, and when the reanalysis button is clicked, displays the OFF time of the reanalyzed peak. In FIG. 2, the O of the selected peak "CH3OOO"
The N time is “458.0 s”, and the OFF time is “508.0 s”.
s ".

The area / height display section displays whether to use the area value or the peak height in the density calculation. Figure 2
Then, the concentration calculation of the selected peak “CH3OOO” uses the “area”. The integration processing section
Either the sectioning method or the perpendicular method is displayed as the integration processing method. In FIG. 2, "cutting method" is selected as an integration processing method for the selected peak "CH3OOO". The peak height section indicates the height of the selected peak. In FIG. 2, the height display of the selected peak “CH3OOO” is “6.700”.

The area value section displays an area value. In FIG. 2, the area value of the selected peak “CH3OOO” is “1”.
3.400 ". The density value part displays the density,
When the reanalysis button is clicked, the result of executing the density calculation under the current setting conditions is displayed. In FIG. 2, the concentration value display of the selected peak “CH3OOO” before re-analysis is “5.
012 ppb ”. The holding time section displays a holding time. In FIG. 2, the selected peak “CH3OO”
The retention time of “O” is “474.0 s”.

The chromatogram display area displays a chromatogram to be re-analyzed. The chromatogram in FIG. 2 has three components “CH3OOO” and “CHO” as described above.
O "and" NO3 "peaks. The gate ON / OFF time for each peak can be arbitrarily changed and set by dragging the mouse on the screen.

FIGS. 3 to 6 show gate ON / OFF by dragging.
FIG. 9 is an explanatory diagram of a time change procedure. In FIG. 3, the peak
Since the gate set for Cl is shifted, the gate must be changed in order to calculate the area accurately. To make the change, first click the range setting button on the toolbar as shown in FIG. 4, and then drag the gate range rightward with the mouse so that the peak is completely within the gate range as shown in FIG. When the mouse is released after dragging, the gate range is changed as shown in FIG. 6, and the display of the gate ON / OFF time is automatically updated.

In FIG. 2 again, when the “reanalysis” button is clicked, the result is displayed on the screen. If the result is not satisfactory, the gate ON / OFF time and the detection slope, which are editable data, are changed again and re-analysis is repeated. When the “gate transfer” button is clicked, the gate ON / OFF time and the detection slope data of the peak currently re-analyzed are transferred to the chromatograph 100. When the “confirm” button is clicked, the result currently being re-analyzed is confirmed and stored in the chromatographic data file 203. Clicking the "Cancel" button cancels the currently executing re-analysis process.

FIG. 7 is an example of a screen for reanalyzing the peak concentration value included in the calibration chromatogram in the chromatogram display unit 206 of the chromatograph controller 200, and is basically a measurement chromatogram shown in FIG. This is the same as the re-analysis screen.

The reference density display section displays a value preset as a calibration condition as it is. In FIG. 7, the peak “C
This indicates that the reference concentration of “H3OOO” is set to “10.000 ppb”. Note that this reference concentration is
Since there is a case where the setting is erroneously input, it can be edited by a keyboard.

When the “Calibration data transfer” button is clicked, the gate ON / OFF time, the detection slope, the reference concentration, and the area / height designation of the peak currently re-analyzed are “area”, and the area data, “ In the case of "height", the height data is transferred to the chromatograph 100. Also, “1” is always transferred as the calibration coefficient. As a result, the results of the calibration re-analysis are reflected in the subsequent measurement by the chromatograph 100.

[0051]

As described above, according to the present invention,
The main body of the chromatograph operates under the control of the chromatograph controller, and the measurement result reflects the reanalysis operation result in the chromatograph controller, so that a highly accurate measurement result can be obtained. The present invention is applicable to liquid chromatograph, gas chromatograph, ion chromatograph, etc.
It is effective for improving the accuracy of the measurement results of various chromatographs.

[Brief description of the drawings]

FIG. 1 is a configuration block diagram showing one embodiment of the present invention.

FIG. 2 is an example of a reanalysis screen of a measured chromatogram in the present invention.

FIG. 3 is a diagram for explaining a change of a gate time of a measurement chromatogram.

FIG. 4 is a diagram for explaining a change of a gate time of a measurement chromatogram.

FIG. 5 is a diagram for explaining a change of a gate time of a measurement chromatogram.

FIG. 6 is a diagram for explaining a change of a gate time of a measurement chromatogram.

FIG. 7 is an example of a reanalysis screen of a calibration chromatogram in the present invention.

FIG. 8 is a configuration diagram showing an example of a process chromatograph.

FIG. 9 is a characteristic diagram showing a relationship between irradiation time of ultraviolet rays and sulfate ions generated by decomposition of a cation exchange resin.

FIG. 10 is an example of a chromatogram displaying an eluted ion concentration along a time axis.

[Explanation of symbols]

 Reference Signs List 100 Chromatograph 200 Chromatograph control device 201 Communication control unit 202 Chromatographic data file 203 Chromatographic data file control unit 204 Chromatographic data calling unit 205 Chromatogram display control unit 206 Chromatogram display unit 207 Measurement chromatogram calculation unit 208 Calibration chromatogram calculation unit 209 Peak selection unit 210 Gate setting unit 211 Data transfer instruction unit

Claims (3)

[Claims] 1. A chromatograph controller connected to a chromatograph for controlling a chromatograph, comprising: a chromatographic data file for storing measured chromatographic data and calibration chromatographic data; and means for calling desired chromatographic data from the chromatographic data file. , Means for displaying a chromatogram based on the called chromatographic data, means for selecting a desired peak included in the displayed chromatogram, and arbitrarily setting a gate on / off time associated with the selected peak Means for performing a re-analysis operation of the peak concentration value selected based on the set ON / OFF time of the gate; and means for instructing to transfer the re-analysis operation finalized data to the chromatograph. Chromatographic controller. 2. The chromatographic control device according to claim 1, wherein a measuring chromatogram calculating section and a calibration chromatogram calculating section are provided as the calculating means. 3. The chromatograph control device according to claim 1, wherein the calculation means shares a measurement chromatogram calculation unit and a calibration chromatogram calculation unit.