JPS60161558A - Detecting method of abnormality of reaction chamber - Google Patents

Abstract

PURPOSE:To obtain a stable result of analysis, by detecting a pressure applied on a reaction chamber, and by detecting automatically the state of abnormality of the reaction chamber on the basis of the absolute value of the detected pressure and the variation thereof. CONSTITUTION:In an analyzing apparatus, a solution 3 in a solution tank 2 is sent to a column 6 through an injector 4 and a pressure sensor 5 by a pump 1, while a sample injected from the injector 4 into the solution is sent to the column 6. A reaction liquid passing through the column 6 is measured by a detector 7 and drained into a drain tank 8. The absolute value of the pressure applied to the column 6 and the variation thereof per unit time are detected from an output of the pressure sensor 5 by a controller 9, and the state of abnormality is detected automatically from the absolute value of the pressure and the variation thereof. When a damage or clogging of the column or any other elements is detected, the operation of the apparatus is stopped, and when the instrusion of an air bubble is detected, the operations of the pump 1, the injector 4 and the detector 7 are controlled by the controller 9.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for detecting abnormality in a reaction chamber in flow injection type analysis applying liquid chromatography.

Conventional technology In a method of separating and analyzing a sample by applying liquid chromatography and flowing it through a reaction chamber containing a predetermined phase-forming substance, for example, a column packed with a particulate packing material, using a 70-ind. Abnormalities such as air bubbles entering and column clogging may occur. When such an abnormality occurs, the solution such as a sample does not flow uniformly within the column, and the reaction becomes non-uniform, resulting in problems such as unreliability of analysis results. For this reason, analyzers using this type of analysis method can accurately detect abnormalities such as the intrusion of air bubbles into the column or clogging. Make sure that the air bubbles disappear, and if clogging occurs, stop the equipment and replace the column, or flow the solution through the column in the opposite direction to remove the insoluble substances that are the cause of the clogging. When a solution leaks due to damage to a flow line including a column, it is necessary to take measures appropriate to the abnormal condition, such as immediately stopping the apparatus.

Therefore, for example, high performance liquid chromatography equipment (HPL)
Regarding (3), conventionally, a pressure sensor is provided on the upstream side of the column at the 7-mer line to detect the pressure applied to the column, and the operator determines the occurrence of an abnormality based on the detected pressure and takes action.

In other words, when a solution flows through a column at a constant rate, if the column is normal, there is a predetermined relationship between the pressure applied between the pump and the column for transporting the solution to one column and the flow rate of the solution. If there is no change in the shape or volume of the filler, there is a nearly linear proportional relationship as shown in FIG.

Therefore, if a pressure sensor is provided on the upstream side of the column, the pressure in normal conditions is determined by the flow rate, so it is possible to easily detect the occurrence of an abnormality from the detected pressure. However, in the past, even if an abnormal pressure was detected by a pressure sensor, the cause of the abnormality, that is, the abnormal state, could only be guessed by the operator, and the countermeasures were also left to the operator's judgment, so individual differences could occur. This is a problem that occurs easily, and therefore, appropriate measures may not be taken, making it difficult to obtain stable analysis results.

OBJECTS OF THE INVENTION An object of the present invention is to provide a method for detecting an abnormality in a reaction chamber, which solves the above-mentioned problems and allows appropriate measures to be taken according to the abnormal state.

SUMMARY OF THE INVENTION The present invention detects an abnormality in a reaction chamber containing a predetermined in-phase substance in a fushi-injection type analysis applying liquid chromatography, detects the pressure applied to the reaction chamber, and detects the detected pressure. The present invention is characterized in that an abnormal state of the reaction chamber is automatically detected based on the absolute value of and its change.

In the present invention, the pressure applied to the reaction chamber is detected, and the inventors conducted experiments under various abnormal conditions in a flow injection analyzer having a column and examined this pressure in detail.1. -r- However, as shown in the table below and FIG.

In other words, when air bubbles enter the column, the air bubbles pass through the column while deforming in various ways, or dissolve into the solution and disappear. The pressure does not change minutely from P, then rises, then falls and returns to the normal pressure value P□.

On the other hand, if clogging occurs, the flow of the solution becomes poor, and as shown in Figure 2B, the pressure rises from the normal pressure value P and does not return to its original value (also, the column When a solution leaks due to damage such as the following, the pressure changes variously depending on the damage situation, but the absolute value decreases in any case.

Therefore, by capturing the absolute value of these pressures and their changes, it is possible to automatically detect abnormal conditions, which enables appropriate countermeasures without individual differences, and provides stable analysis results. Obtainable.

Embodiment FIG. 8 shows a flow injector 4 implementing the present invention.
and transported to column 6 via pressure sensor 5,
The sample injected from the injector 4 into this solution is transported to the column 6, and the reaction liquid that has passed through the column 6 is sent to the detector? The photometer is photometrically measured and discharged into the drainage tank 8. In exceptional cases, the controller 9 detects the absolute value of the pressure applied to the column 6 and its change per unit time from the output of the pressure sensor 6, and automatically detects an abnormal state from the absolute value of the pressure and its change. The pump is controlled by the controller 9 to stop one device when damage or clogging of the column filter, etc. is detected, and to transport the solution as is or at a higher speed when the intrusion of air bubbles is detected. 1. Controls the operation of the injector 4 and detector 7. Note that the setting of the unit time for detecting a change in the absolute value and the number of measurements are appropriately set in consideration of the analysis time, the type of column 6, and the transport speed of the solution 8 by the pump 1.

FIG. 4 shows the configuration of another example of a flow injection analyzer implementing the present invention.

This analyzer has a function to automatically recover from clogging, and in normal analysis, the solution 18 in the solution tank 12 is injected into the injector 14 by the pump 11. At the same time, the sample injected from the injector 14 into this solution is transported to the column 17 via the valve 15 and the pressure sensor 16, and the sample is transferred to the column 17.
The reaction liquid that has passed through 7 is sent to a pressure sensor 18 and a pulp 19.
The liquid is photometered by a detector 20 and discharged to a drainage tank 22 via a backpressure device 21.

The output of the pressure sensor 16 is supplied to the controller 28 to automatically detect an abnormal state based on its absolute value and change per unit time, and when clogging is detected, the valve 1 is
5 and 19 and operate the pump 24,
This causes the solution 26 in the solution tank 25 to flow back through the column 17 through the pulp 19 and the pressure sensor 18, and removes insoluble substances that cause clogging from the pressure sensor 16. Discharge via valve 15 and back pressure device 27 to drain tank 28. At this time, the controller 28 detects whether the pressure has returned to normal pressure based on the output of the pressure sensor 18, that is, whether the clogging has been recovered, and when the pressure has recovered, the operation of the pump 24 is stopped and the pulp 1519 is switched to its original state and normal analysis operation is performed. Further, as in the above embodiment, when the controller 28 detects damage to the column 17, etc., the operation of the device is stopped, and when the intrusion of air bubbles is detected, the solution 18 is transported as is or at a higher speed. The controller 28 controls the pump 11. Injector 14. Controls the operation of the detector 20 and the like. In addition, even in non-example, the setting of the unit time for detecting the change in the absolute value of pressure by the pressure sensor 16 and the number of measurements are determined taking into consideration the analysis time, the type of column 17, the transport speed of the solution 13 by the pump 11, etc. Set as appropriate: 0 FIG. 5 shows the configuration of an example of a pressure sensor used in each of the embodiments described above. This pressure sensor 81 includes a piezoelectric ring 88 displaceably provided in the connector unit 32 so as to define a flow path, and a signal output section 84 that converts the displacement of the piezoelectric ring 88 into an electrical signal and outputs it. The connector unit 82 can be installed in the flow line by connecting the tear tubes 8B and 8B forming the flow line to both ends of the connector unit 82 via the adders 7' and a7 and 38, respectively.

Note that the invention is not limited to the above-mentioned example, and numerous changes and modifications are possible.

For example, the installation position of the pressure sensor that detects the pressure applied to the column in order to detect an abnormal state may be on the column inlet side. Therefore, in FIG. In FIG. 4, it may be between the pump 11 and the injector 14 or between the injector 14 and the valve 15. In addition, in FIG. 4, air bubbles can also be discharged by backflowing the solution 26 through the column 17 in the same way as clogging recovery. Since the condition is automatically detected, it is possible to always take appropriate measures without causing individual differences, and therefore stable analysis results can be obtained.

[Brief explanation of drawings]

Figure 1 is a diagram showing the relationship between the flow rate and the pressure applied to the column. Figure 2 A and B are diagrams showing changes in the pressure applied to the column under abnormal conditions. Figure 8 is a 70-injection analysis to carry out the invention. FIG. 4 is a diagram showing the configuration of an example of the apparatus, FIG. 4 is a diagram showing the configuration of another example, and FIG. 5 is a diagram showing the configuration of an example of the pressure sensor used to implement the invention. 1... Pump 2... Solution tank 4... Injector 5... Pressure sensor 6... Column 7... Detector 8... Drain tank 9... Controller 11, 2
4... Pump 12, 25... Solution tank 14.
...Injector 15, 19...Valve 16.1
81...Pressure sensor 17...Column 20...Detector jl, l...Back pressure device 22,
28...Drainage tank 28...Controller 81.
...Pressure sensor 82...Connector unit 88...
・Piezoelectric ring 84...Signal output section 85, 86...
・Teflon tube 8'l, 88...Adapter Figure 1 Figure 2

Claims (1)

[Claims] 1. When detecting an abnormality in a reaction chamber containing a predetermined solid-phase substance in a flow injection method analysis applying liquid chromatography, the pressure applied to the reaction chamber is detected, and the absolute value of the detected pressure and its change are detected. A method for detecting an abnormality in a reaction chamber, characterized in that an abnormal state of the reaction chamber is automatically detected based on the following.