JP7379426B2 - Sample analysis device and sample analysis method - Google Patents

Description

The present disclosure relates to a sample analysis device and a sample analysis method.

Conventionally, there has been known a technique for measuring the concentration of hexavalent chromium contained in a sample solution using an absorbance measurement method in order to monitor the quality of water such as various industrial wastewater and river water (see, for example, Patent Document 1). .

Japanese Patent Application Publication No. 2014-21056

For example, when producing aircraft parts made of metal materials such as aluminum alloys, surface treatment such as film treatment of the metal material is performed using a treatment liquid containing chromic acid. In order to perform desired surface treatment with a treatment liquid containing chromic acid, it is necessary to maintain the concentration of hexavalent chromium contained in the treatment liquid within a desired range. This is because hexavalent chromium contained in the treatment solution may be reduced to trivalent chromium, and trivalent chromium has an adverse effect on coating treatment. Therefore, for example, in a factory, a sample liquid is extracted from the processing liquid periodically (once a week, etc.), transported to a place where an analysis device is installed, and the analysis device is used to extract the sample liquid from the processing liquid. Analysis of hexavalent chromium and trivalent chromium concentrations is performed.

However, since a certain period (for example, one week) passes while the sample liquid is extracted from the processing liquid at the factory, the concentration of hexavalent chromium and trivalent chromium contained in the processing liquid may decrease due to some factor during this period. If it fluctuates greatly, it may become impossible to maintain the concentrations of hexavalent chromium and trivalent chromium contained in the treatment liquid within the desired range, and it may become impossible to perform appropriate surface treatment.

In addition, when analyzing the concentration of hexavalent chromium and trivalent chromium contained in a sample liquid using an analyzer, the trivalent chromium contained in the sample liquid is oxidized to hexavalent chromium, and the oxidized trivalent chromium is It is necessary to analyze the concentration of total chromium, including chromium. Therefore, it is necessary to oxidize trivalent chromium to hexavalent chromium, and to install a sample solution containing oxidized trivalent chromium into an analyzer, and the workers who perform these tasks and the analyzer must be installed. It is necessary to secure space. However, in factories, it is not easy to secure space for workers who perform various tasks and for installing analysis equipment.

The present disclosure has been made in view of the above circumstances, and it is possible to oxidize trivalent chromium contained in a sample solution to hexavalent chromium without securing a worker or a space to perform the work. It is an object of the present invention to provide a sample analysis device and a sample analysis method that can appropriately analyze the concentrations of trivalent chromium and hexavalent chromium contained in a treatment liquid while maintaining them within a desired range.

A sample analyzer according to one aspect of the present disclosure includes an oxidation reaction unit that oxidizes trivalent chromium contained in a sample liquid extracted from a treatment liquid for surface treatment of a metal material to hexavalent chromium; a detection unit that respectively detects the concentration of trivalent chromium and the concentration of hexavalent chromium contained in the oxidation reaction unit; a first supply mode that supplies the first sample liquid passed through the oxidation reaction unit to the detection unit; a control unit that selectively executes a second supply mode in which the second sample liquid that does not pass through the oxidation reaction unit is supplied to the detection unit; detecting a first concentration of hexavalent chromium contained in the sample liquid and a second concentration of hexavalent chromium contained in the second sample liquid; Detects the concentration of trivalent chromium.

A sample analysis method according to one aspect of the present disclosure is a sample analysis method for detecting the concentration of hexavalent chromium contained in a sample liquid using a sample analysis device, the sample analysis device performing surface treatment on a metal material. an oxidation reaction unit that oxidizes trivalent chromium contained in a sample liquid extracted from a processing liquid for performing the treatment to hexavalent chromium, and a detection unit that detects the concentration of hexavalent chromium contained in the sample liquid, a first supply mode in which a first sample liquid that has passed through the oxidation reaction section is supplied to the detection section; and a second supply mode in which a second sample liquid that does not pass through the oxidation reaction section is supplied to the detection section. a control step of selectively executing a mode, and a control step of selectively performing a first concentration of hexavalent chromium contained in the first sample liquid and a second concentration of hexavalent chromium contained in the second sample liquid by the detection unit; and a detection step of detecting the concentration of trivalent chromium contained in the second sample liquid based on the first concentration and the second concentration.

According to the present disclosure, it is possible to oxidize trivalent chromium and hexavalent chromium contained in a processing liquid without securing a worker or a space to perform the work of oxidizing trivalent chromium contained in a sample liquid to hexavalent chromium. It is possible to provide a sample analysis device and a sample analysis method that can appropriately analyze the concentration of the sample while maintaining it within a desired range.

FIG. 1 is a schematic configuration diagram showing a sample analysis system. FIG. 1 is a diagram showing a schematic configuration of a sample analyzer. 3 is a block diagram showing the configuration of a control section shown in FIG. 2. FIG. 1 is a flowchart showing a sample analysis method according to the present embodiment.

A sample analysis system according to one embodiment of the present disclosure will be described below with reference to the drawings. FIG. 1 is a schematic configuration diagram showing a sample analysis system of the present disclosure. As shown in FIG. 1, the sample analysis system includes a sample analysis device 100 and a surface treatment device 200. The detailed configuration of the sample analyzer 100 will be described later.

The surface treatment apparatus 200 is an apparatus that performs surface treatment on a metal component 300 formed of a metal material. The metal part (target part) 300 is, for example, an aircraft part made of an aluminum alloy. The surface treatment apparatus 200 includes a crane 210, a plurality of processing tanks 220 arranged at intervals along the transport direction TD, and a plurality of valves 230 provided corresponding to each processing tank 220.

The surface treatment apparatus 200 is, for example, an apparatus that performs anodizing treatment (aluminum anodization treatment) in order to form a film on the surface of an aircraft component made of an aluminum alloy. A processing solution containing chromic acid is used as a processing solution for performing the anodizing treatment.

A first processing tank 221 included in the plurality of processing tanks 220 holds a processing liquid for performing an anodization process. The second processing tank 222 and the third processing tank 223 hold pure water. The surface treatment apparatus 200 suspends the metal parts 300 by a crane 210 and holds them in each treatment tank in the order of a first treatment tank 221, a second treatment tank 222, and a third treatment tank 223 by vertical movement while moving them in the transport direction TD. immerse it in the treatment solution.

Further, the fourth treatment tank 224, the fifth treatment tank 225, and the sixth treatment tank 226 each hold a treatment liquid for performing other surface treatments. The surface treatment apparatus 200 performs a desired surface treatment on the metal component 300 by sequentially immersing the metal component 300 in the treatment liquid in the order of the first to sixth treatment tanks along the transport direction TD. Note that the number of treatment tanks 220 that the surface treatment apparatus 200 has can be any number.

As shown in FIG. 1, each of the first treatment tank 221, the second treatment tank 222, the third treatment tank 223, the fourth treatment tank 224, the fifth treatment tank 225, and the sixth treatment tank 226 are filled with water from the treatment liquid. A first pipe SL1, a second pipe SL2, a third pipe SL3, a fourth pipe SL4, a fifth pipe SL5, and a sixth pipe SL6 are connected to guide the extracted sample liquid to the sample analyzer 100.

The first pipe SL1, the second pipe SL2, the third pipe SL3, the fourth pipe SL4, the fifth pipe SL5, and the sixth pipe SL6 have a first valve 231, a second valve 232, a third valve 233, and a fourth valve, respectively. A valve 234, a fifth valve 235, and a sixth valve 236 are provided. The control unit 60 of the sample analyzer 100 extracts the processing liquid from any processing tank from among the plurality of processing tanks 220 by switching the open/close states of the plurality of valves 230 (first to sixth valves), and It can be supplied to the analyzer 100.

Next, details of the sample analyzer 100 of this embodiment will be explained with reference to FIG. 2. FIG. 2 is a diagram showing a schematic configuration of the sample analysis device 100. As shown in FIG. 2, the sample analyzer 100 includes a syringe pump 10, a flow path switching valve (flow path switching section) 20, a mixing container 30, a detection section 40, a three-way valve 50, and a control section 60. , an oxidation reaction section 70, and a decomposition section 80.

The syringe pump 10 is a device that is disposed in the main pipe Lm and sucks or delivers a predetermined amount of liquid. The syringe pump 10 uses a motor 13 to adjust the length of insertion of a plunger 12, which has a gasket 12a attached to the tip that contacts the inner circumferential surface of the outer cylinder 11, into an outer cylinder 11, thereby controlling the suction amount of liquid. and adjust the delivery amount.

The flow path switching valve 20 is a device that has a main port Pm and a plurality of sub-ports Ps (Ps1-Ps12), and switches the sub-port Ps connected to the main port Pm. The main port Pm and the sub-port Ps are flow paths for flowing liquid. The flow path switching valve 20 switches to connect any one of the plurality of sub ports Ps (Ps1 to Ps12) to the main port Pm in accordance with a control signal transmitted from the control unit 60.

The sample port Ps1 is a port connected to the sample pipe Ls1 to which a sample liquid obtained by extracting the processing liquid held in one of the plurality of processing tanks 220 is supplied. The detection port Ps2 is a port connected to the detection pipe Ls2 in which the detection section 40 is arranged. The oxidation reaction reagent port Ps3 is supplied with an oxidation reaction reagent solution (a solution containing nitric acid and potassium permanganate) for oxidizing trivalent chromium contained in the sample solution to hexavalent chromium from the oxidation reaction reagent container Co3. This is a port connected to the reaction reagent pipe Ls3.

The coloring reagent port Ps4 is a port connected to the coloring reagent piping Ls4 to which a coloring reagent solution (for example, diphenylcarbazide solution) is supplied from the coloring reagent container Co4. The oxidation reaction port Ps5 is a port connected to the oxidation reaction piping Ls5 in which the oxidation reaction container Co5 is arranged. The decomposition reaction port Ps6 is a port connected to the decomposition reaction pipe Ls6 in which the decomposition reaction vessel Co6 is arranged.

The decomposition reagent port Ps7 is a port connected to the decomposition reagent piping Ls7 to which the decomposition reagent liquid (mixed solution of sodium nitrite and urea) held in the decomposition reagent liquid container Co7 is supplied. The waste liquid port Ps8 is a port connected to a waste liquid pipe Ls8 for discharging unnecessary reagent liquid and the like. The first dilution port Ps9 is a port connected to the first dilution pipe Ls9 to which a sample liquid diluted with pure water is supplied. The second dilution port Ps10 is a port connected to the second dilution pipe Ls10 to which a sample liquid diluted with pure water is supplied.

The standard port Ps11 is a port connected to a standard piping Ls11 to which a standard solution containing hexavalent chromium at a known concentration (predetermined concentration) is supplied from a standard solution container Co11. The pure water port Ps12 is a port connected to the pure water pipe Ls12 to which pure water is supplied from the pure water container Co12.

The mixing container 30 is a loop-shaped (coil-shaped) container provided in the main piping Lm between the syringe pump 10 and the main port Pm. When the control unit 60 controls the three-way valve 50 to connect the main pipe Lm on the side of the mixing container 30 and the syringe pump 10, liquid is sucked into the mixing container 30 from the main port Pm according to the operation of the syringe pump 10. Alternatively, the liquid is delivered from the mixing container 30 to the main port Pm.

The detection unit 40 is a device that detects the concentrations of trivalent chromium and hexavalent chromium contained in a sample liquid extracted from a treatment liquid for performing surface treatment on an aluminum alloy. The detection unit 40 detects the concentration of hexavalent chromium by measuring the amount of light that passes when a mixture of a sample liquid and a coloring reagent liquid is irradiated with light of a specific wavelength.

The detection unit 40 detects the first concentration of hexavalent chromium contained in the mixed liquid (first sample liquid) that has passed through the oxidation reaction unit 70 and the mixed liquid (second sample liquid) that has not passed through the oxidation reaction unit 70. A second concentration of hexavalent chromium contained in the second concentration of hexavalent chromium is detected. By passing through the oxidation reaction section 70, trivalent chromium contained in the sample liquid is oxidized to hexavalent chromium. Therefore, the first concentration includes not only hexavalent chromium contained in the sample solution but also hexavalent chromium oxidized from trivalent chromium.

The detection unit 40 can obtain the concentration of hexavalent chromium oxidized from trivalent chromium contained in the sample liquid extracted from the processing tank 220 from the value obtained by subtracting the second concentration from the first concentration. Then, the detection unit 40 detects the concentration of trivalent chromium contained in the sample liquid using a predetermined calibration curve. In this way, the detection unit 40 detects the concentration of trivalent chromium contained in the mixed liquid (second sample liquid) that is not allowed to pass through the oxidation reaction unit 70 based on the first concentration and the second concentration.

The three-way valve 50 is a device that switches between a first state in which the mixing container 30 side of the main pipe Lm and the syringe pump 10 are connected, and a second state in which the syringe pump 10 is connected to the pure water container Co12 side of the main pipe Lm. It is. In the first state, when the syringe pump 10 performs a suction operation to suck the liquid, the liquid is guided from the main port Pm to the mixing container 30. When the syringe pump 10 performs an operation of sucking liquid in the second state, pure water is guided from the pure water container Co12 to the syringe pump 10.

The control unit 60 is a device that controls the entire sample analyzer 100 including the syringe pump 10, the flow path switching valve 20, and the three-way valve 50. As shown in FIG. 3, the control unit 60 is a computer system, and includes a CPU 61, a ROM (Read Only Memory) 62 for storing programs executed by the CPU 61, and a workpiece when each program is executed. It includes a RAM (Random Access Memory) 63 that functions as an area, a hard disk drive (HDD) 64 as a mass storage device, and a communication section 65 for connecting to a network or the like. These parts are connected via a bus 66.

The oxidation reaction section 70 is a device that oxidizes trivalent chromium contained in the sample liquid to hexavalent chromium. The oxidation reaction section 70 includes an oxidation reaction container Co5, an oxidation catalyst (for example, manganese dioxide) installed inside the oxidation reaction container Co5, and a sample liquid held in the oxidation reaction container Co5 at a temperature ( For example, it has a heating section that heats to 50° C.).

A liquid mixture of a sample liquid and an oxidation reaction reagent liquid is supplied to the oxidation reaction section 70 from an oxidation reaction port Ps5 via an oxidation reaction pipe Ls5. The oxidation reaction section 70 uses a heating section to heat the mixed liquid to a temperature required for the oxidation reaction (for example, 50° C.), and oxidizes trivalent chromium contained in the sample liquid to hexavalent chromium.

The decomposition unit 80 is a device that decomposes the oxidation reaction reagent liquid contained in the mixed liquid (first sample liquid) in which trivalent chromium is oxidized to hexavalent chromium after passing through the oxidation reaction unit 70. The decomposition section 80 has a decomposition reaction container Co6, and performs a decomposition reaction on the mixed liquid that has passed through the oxidation reaction section 70 and the decomposition reaction reagent (mixed solution of sodium nitrite and urea) held in the decomposition reagent liquid container Co7. Hold in container Co6. As a result, the oxidation reaction reagent liquid remaining in the mixed liquid that has passed through the oxidation reaction section 70 is reductively decomposed.

Next, a sample analysis method using the sample analysis device 100 of this embodiment will be described with reference to the flowchart shown in FIG. FIG. 4 is a flowchart showing the sample analysis method of this embodiment. Each process shown in FIG. 4 is executed by the control unit 60 operating a control program. Note that, unless otherwise specified below, the control unit 60 controls the three-way valve 50 to enter the first state in which the mixing container 30 side of the main pipe Lm and the syringe pump 10 are connected.

In FIG. 4, the steps from step S101 to step S105 are performed when the control unit 60 executes the first supply mode in which the sample liquid (first sample liquid) passed through the oxidation reaction unit 70 is supplied to the detection unit 40. This is the process. The steps from step S106 to step S108 are steps when the control section 60 executes the second supply mode in which the sample liquid (second sample liquid) that is not allowed to pass through the oxidation reaction section 70 is supplied to the detection section 40.

The step S109 is a step in which the control section 60 executes the third supply mode for supplying the standard solution held in the standard solution container Co11 to the detection section 40. The control unit 60 selectively executes the first supply mode, the second supply mode, and the third supply mode.

In FIG. 4, the control unit 60 executes the second supply mode after executing the first supply mode, but may execute the first supply mode after executing the second supply mode. Note that in the process shown in FIG. 4, the sample liquid used in the first supply mode and the sample liquid used in the second supply mode are extracted from the same processing tank 220.

Next, the first supply mode executed by the control unit 60 will be explained.
In step S101, the control unit 60 mixes the sample liquid and pure water to generate a diluted liquid (first dilution step). The control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the sample port Ps1. Further, the control unit 60 controls the syringe pump 10 to draw the sample liquid from the sample pipe Ls1 into the mixing container 30. As a result, a predetermined amount of sample liquid is held in the mixing container 30.

Next, the control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the pure water port Ps12. Further, the control unit 60 controls the syringe pump 10 to draw pure water from the pure water pipe Ls12 to the mixing container 30. As a result of the above, a state is reached in which a predetermined amount of sample liquid and a predetermined amount of pure water are held in the mixing container 30.

Next, the control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the first dilution port Ps9. Further, the control unit 60 controls the syringe pump 10 to supply the diluent from the mixing container 30 to the first dilution container Co9 connected to the first dilution pipe Ls9. As a result of the above, the diluent is held in the first dilution container Co9.

When further diluting the diluent held in the first dilution container Co9 with pure water, the control unit 60 executes the following process. Specifically, the control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the first dilution port Ps9. Further, the control unit 60 controls the syringe pump 10 to draw the diluent from the first dilution pipe Ls9 into the mixing container 30. As a result, a predetermined amount of diluent is held in the mixing container 30.

Next, the control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the pure water port Ps12. Further, the control unit 60 controls the syringe pump 10 to draw pure water from the pure water pipe Ls12 to the mixing container 30. As a result of the above, a state is reached in which a predetermined amount of diluent and a predetermined amount of pure water are held in the mixing container 30.

Next, the control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the second dilution port Ps10. The control unit 60 also controls the syringe pump 10 to supply the diluent from the mixing container 30 to the second dilution container Co10 connected to the second dilution pipe Ls10.

As a result of the above, the diluent is held in the second dilution container Co10. After diluting the sample liquid using the first dilution container Co9, it can be further diluted using the second dilution container Co10. Therefore, the sample liquid can be diluted at a wide range of magnifications so that the sample liquid becomes a desired dilution liquid suitable for detection by the detection unit 40.

Note that if there is no need to dilute the sample liquids extracted from the plurality of processing tanks 220, the dilution step of step S101 may be omitted. When the dilution process is omitted, the sample liquid sucked into the mixing container 30 from the sample pipe Ls1 is sent to the oxidation reaction section 70 in the oxidation process of step S102.

In step S102, the control unit 60 oxidizes trivalent chromium contained in the diluent to hexavalent chromium (oxidation step). The control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the first dilution port Ps9 or the second dilution port Ps10. Further, the control unit 60 controls the syringe pump 10 to draw the diluent into the mixing container 30 from the first dilution pipe Ls9 or the second dilution pipe Ls10. As a result, a predetermined amount of diluent is held in the mixing container 30.

Next, the control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the oxidation reaction reagent port Ps3. Further, the control unit 60 controls the syringe pump 10 to draw the oxidation reaction reagent from the oxidation reaction reagent container Co3 into the mixing container 30 via the oxidation reaction reagent piping Ls3. As a result, a predetermined amount of the oxidation reaction reagent liquid is held in the mixing container 30.

Next, the control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the oxidation reaction port Ps5. Further, the control unit 60 controls the syringe pump 10 to supply a mixed liquid of the diluent and the oxidation reaction reagent liquid from the mixing container 30 to the oxidation reaction section 70 disposed in the oxidation reaction pipe Ls5. The oxidation reaction section 70 heats the mixed liquid to a temperature necessary for the oxidation reaction (for example, 50° C.) using a heating section, and causes the sample liquid to flow through an interior filled with an oxidation catalyst (for example, manganese dioxide). Oxidizes the trivalent chromium contained into hexavalent chromium.

In step S103, the control unit 60 decomposes the oxidation reaction reagent liquid remaining in the mixed liquid that has passed through the oxidation reaction unit 70 (decomposition step). The control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the oxidation reaction port Ps5. Further, the control unit 60 controls the syringe pump 10 to draw the mixed liquid from the oxidation reaction unit 70 into the mixing container 30. As a result, a predetermined amount of the mixed liquid is held in the mixing container 30.

Next, the control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the decomposition reagent port Ps7. Further, the control unit 60 controls the syringe pump 10 to draw the decomposition reagent liquid from the decomposition reagent liquid container Co7 into the mixing container 30 via the decomposition reagent piping Ls7. As a result, a predetermined amount of the decomposition reagent liquid is held in the mixing container 30.

Next, the control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the decomposition reaction port Ps6. The control unit 60 also controls the syringe pump 10 so as to supply a mixture of the sample liquid and the decomposition reagent liquid that have passed through the oxidation reaction unit 70 from the mixing container 30 to the decomposition unit 80 disposed in the decomposition reaction pipe Ls6. control. The decomposition unit 80 reductively decomposes the oxidation reaction reagent liquid remaining in the mixed liquid that has passed through the oxidation reaction unit 70.

In step S104, the control unit 60 mixes the liquid mixture obtained by decomposing the oxidation reaction reagent liquid by the decomposition unit 80 and the coloring reagent liquid (first mixing step). The control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the decomposition reaction port Ps6. Further, the control unit 60 controls the syringe pump 10 to draw the mixed liquid from the decomposition reaction container Co6 to the mixing container 30 via the decomposition reaction pipe Ls6. As a result, a predetermined amount of the mixed liquid is held in the mixing container 30.

Next, the control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the coloring reagent port Ps4. Further, the control unit 60 controls the syringe pump 10 to draw the coloring reagent liquid from the coloring reagent pipe Ls4 into the mixing container 30. As a result, a predetermined amount of the coloring reagent solution is held in the mixing container 30. As described above, the liquid mixture obtained by decomposing the oxidation reaction reagent liquid by the decomposition unit 80 and the coloring reagent liquid are mixed.

In step S105, the control unit 60 sends the mixture of the decomposed oxidation reaction reagent liquid and the coloring reagent liquid to the detection unit 40, and transmits a specific wavelength to the sample liquid that has passed through the oxidation reaction unit 70. The detection unit 40 is controlled to measure the first amount of light that passes when the light is irradiated (first measurement step).

The control section 60 sends out the mixed liquid (first sample liquid) held in the mixing container 30 to the detection section 40 . The control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the detection port Ps2. Further, the control unit 60 controls the syringe pump 10 to supply the mixed liquid from the mixing container 30 to the detection unit 40 via the detection pipe Ls2. As described above, the mixed liquid held in the mixing container 30 is sent to the detection section 40. The detection unit 40 irradiates the mixed liquid sent out from the mixing container 30 with light of a specific wavelength when it passes through the detection unit 40, and measures the amount of first light that passes when the mixed liquid is irradiated with light. .

Next, the second supply mode executed by the control unit 60 will be explained.
In step S106, the control unit 60 mixes the sample liquid and pure water to generate a diluted liquid (second dilution step). The process executed by the control unit 60 in step S106 is the same as the process executed by the control unit 60 in step S101, so a description thereof will be omitted.

In step S107, the control unit 60 mixes the diluted liquid generated in step S101 and the coloring reagent liquid (second mixing step). The control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the first dilution port Ps9 or the second dilution port Ps10. Further, the control unit 60 controls the syringe pump 10 to draw the diluent into the mixing container 30 from the first dilution pipe Ls9 or the second dilution pipe Ls10. As a result, a predetermined amount of diluent is held in the mixing container 30.

Next, the control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the coloring reagent port Ps4. Further, the control unit 60 controls the syringe pump 10 to draw the coloring reagent liquid from the coloring reagent pipe Ls4 into the mixing container 30. As a result, a predetermined amount of the coloring reagent solution is held in the mixing container 30.

In step S108, the control unit 60 sends the mixture of the diluent and the coloring reagent liquid to the detection unit 40, and the sample liquid that does not pass through the oxidation reaction unit 70 is irradiated with light of a specific wavelength. The detection unit 40 is controlled to measure two amounts of light (second measurement step).

The control unit 60 sends out the mixed liquid (second sample liquid) held in the mixing container 30 to the detection unit 40 . The control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the detection port Ps2. Further, the control unit 60 controls the syringe pump 10 to supply the mixed liquid from the mixing container 30 to the detection unit 40 via the detection pipe Ls2. As described above, the mixed liquid held in the mixing container 30 is sent to the detection section 40. The detection unit 40 irradiates the mixed liquid sent out from the mixing container 30 with light of a specific wavelength when it passes through the detection unit 40, and measures the amount of second light that passes when the mixed liquid is irradiated with light. .

In step S109, the control unit 60 controls the first concentration of hexavalent chromium contained in the sample liquid (first sample liquid) that has passed through the oxidation reaction unit 70, and the first concentration of hexavalent chromium contained in the sample liquid (second sample liquid) that has not passed through the oxidation reaction unit 70. The detection unit 40 is controlled to detect the second concentration of hexavalent chromium contained in the sample liquid). Then, the detection unit 40 detects the concentration of trivalent chromium contained in the sample liquid (second sample liquid) that is not allowed to pass through the oxidation reaction unit 70 based on the first concentration and the second concentration.

The control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the standard port Ps11. Further, the control unit 60 controls the syringe pump 10 to draw the standard solution from the standard piping Ls11 into the mixing container 30. As a result, a predetermined amount of the standard solution is held in the mixing container 30.

Next, the control unit 60 sends the standard solution held in the mixing container 30 to the detection unit 40. The control unit 60 controls the flow path switching valve 20 to connect the main port Pm and the detection port Ps2. Further, the control unit 60 controls the syringe pump 10 to supply the standard solution from the mixing container 30 to the detection unit 40 via the detection pipe Ls2. As described above, the standard solution held in the mixing container 30 is sent to the detection section 40.

Next, the control section 60 irradiates the standard solution with light of a specific wavelength when the standard solution sent out from the mixing container 30 passes through the detection section 40, and controls the control section 60 to irradiate the standard solution with light of a specific wavelength, and to obtain a third amount of light that passes when the standard solution is irradiated with light. Measure. The detection unit 40 detects the amount of light contained in the sample liquid that has passed through the oxidation reaction unit 70 based on the first light intensity measured from the sample liquid that has passed through the oxidation reaction unit 70 and the third light intensity measured from the standard solution. detecting a first concentration of hexavalent chromium; The detection unit 40 detects the concentration of hexavalent chromium in the first sample liquid by calculating the ratio of the first light amount to the third light amount measured from a standard solution in which the concentration of hexavalent chromium is known.

Next, the detection unit 40 detects the sample liquid that does not pass through the oxidation reaction unit 70 based on the second light intensity measured from the sample liquid that does not pass through the oxidation reaction unit 70 and the third light intensity measured from the standard solution. A second concentration of hexavalent chromium contained is detected. The detection unit 40 detects the concentration of hexavalent chromium in the second sample liquid by calculating the ratio of the second light amount to the third light amount measured from a standard solution with a known concentration of hexavalent chromium.

The detection unit 40 can obtain the concentration of hexavalent chromium oxidized from trivalent chromium contained in the sample liquid from the value obtained by subtracting the second concentration from the first concentration. Then, the detection unit 40 detects the concentration of trivalent chromium contained in the sample liquid extracted from the processing tank 220 using a predetermined calibration curve. In this way, the detection unit 40 detects the concentration of trivalent chromium contained in the sample liquid (second sample liquid) that is not allowed to pass through the oxidation reaction unit 70 based on the first concentration and the second concentration. The concentration of trivalent chromium and the concentration of hexavalent chromium contained in the sample liquid extracted from the processing tank 220 detected by the detection unit 40 are transmitted to the control unit 60.

The control unit 60 displays the detection result of the detection unit 40 on a display device (not shown), or notifies a predetermined notification destination of the detection result via the communication unit 65. For example, if the concentration of trivalent chromium or the concentration of hexavalent chromium detected by the detection unit 40 exceeds a predetermined setting value, the control unit 60 warns the operator via a display screen or the like.

The control unit 60 can set the frequency of the sample analysis process shown in FIG. 4 to an arbitrary frequency. For example, the control unit 60 calculates the concentration per unit time based on the concentration of trivalent chromium or hexavalent chromium detected in the previous sample analysis process and the concentration of trivalent chromium or hexavalent chromium detected in the current sample analysis process. The rate of increase can be calculated, and the frequency of the sample analysis process can be set so that the higher the rate of increase, the shorter the interval until the next sample analysis process is performed. This means that if the rate of increase in the concentration of trivalent chromium or hexavalent chromium is high, the sample analysis processing frequency must be shortened to ensure that the concentration of trivalent chromium or hexavalent chromium exceeds the predetermined set value at the appropriate time. This is because there is a possibility that it cannot be detected.

The functions and effects of the sample analyzer 100 of this embodiment described above will be explained.
According to the sample analyzer 100 of the present embodiment, the control unit 60 controls the first supply mode in which the first sample liquid that has passed through the oxidation reaction unit 70 is supplied to the detection unit 40, and the first supply mode in which the first sample liquid is not allowed to pass through the oxidation reaction unit 70. A second supply mode in which the second sample liquid is supplied to the detection unit 40 is selectively executed. The detection unit 40 detects a first concentration of hexavalent chromium contained in the first sample liquid and a second concentration of hexavalent chromium contained in the second sample liquid, and detects The concentration of trivalent chromium contained in the second sample liquid is detected.

According to the sample analyzer 100 of the present embodiment, trivalent chromium contained in the sample liquid is oxidized to hexavalent chromium by the oxidation reaction section 70 without any work by an operator. There is no need to secure a worker or space to perform the work of oxidizing chromium to hexavalent chromium. In addition, since the concentration of trivalent chromium and hexavalent chromium contained in the second sample solution are detected respectively, the concentration of trivalent chromium and hexavalent chromium contained in the processing solution must be kept within the desired range. A sample analysis device 100 that can perform appropriate analysis can be provided.

Further, according to the sample analyzer 100 of the present embodiment, the first amount of light that passes when the first sample liquid is irradiated with light of a specific wavelength and the second sample liquid is irradiated with light of a specific wavelength. The concentration of hexavalent chromium contained in the first sample liquid and the second sample liquid can be appropriately detected based on the amount of second light that passes therethrough.

Further, according to the sample analyzer 100 of the present embodiment, in the first supply mode, the first sample liquid that has passed through the oxidation reaction section 70 is supplied to the detection section 40 after passing through the decomposition section 80. Therefore, the oxidation reaction reagent liquid for oxidizing trivalent chromium to hexavalent chromium contained in the first sample liquid is decomposed, and the detection result of the concentration of hexavalent chromium detected by the detection unit 40 by the oxidation reaction reagent liquid is It is possible to prevent adverse effects.

Further, according to the sample analyzer 100 of the present embodiment, by controlling the syringe pump 10 and the flow path switching valve 20, in the first supply mode, the sample is drawn from the sample port Ps1 and the oxidation reaction reagent port Ps3 into the mixing container 30. A sample liquid and an oxidation reaction reagent liquid can be supplied to the oxidation reaction section 70, and a first sample liquid in which trivalent chromium is oxidized to hexavalent chromium can be supplied to the detection section 40. In the second supply mode, the sample liquid drawn into the mixing container 30 from the sample port Ps1 is supplied to the detection unit 40, and a second sample liquid in which trivalent chromium is not oxidized to hexavalent chromium is supplied to the detection unit 40. be able to.

Further, according to the sample analyzer 100 of the present embodiment, a standard solution containing hexavalent chromium at a predetermined concentration is prepared, and the amount of third light that passes when the standard solution is irradiated with light of a specific wavelength is measured. The concentration of hexavalent chromium contained in each of the first sample liquid and the second sample liquid can be accurately detected based on the first light quantity, the second light quantity, and the third light quantity.

Further, according to the sample analyzer 100 of the present embodiment, the sample liquid and pure water are drawn into the mixing container 30, and the main port Pm and the first dilution port Ps9 or the second dilution port Ps10 are connected to each other. By supplying the diluent to the first dilution container Co9 or the second dilution container Co10, the sample liquid can be appropriately diluted and held in the first dilution container Co9 or the second dilution container Co10.

The sample analysis device described in this embodiment described above can be understood, for example, as follows.
A sample analyzer (100) according to one aspect of the present disclosure includes an oxidation reaction unit (70) that oxidizes trivalent chromium contained in a sample liquid extracted from a treatment liquid for surface treatment of a metal material to hexavalent chromium. ), a detection unit (40) that respectively detects the concentration of trivalent chromium and hexavalent chromium contained in the sample liquid, and a first sample liquid that has passed through the oxidation reaction unit to the detection unit. a control unit (60) that selectively executes a first supply mode in which the sample liquid is supplied and a second supply mode in which the second sample liquid that does not pass through the oxidation reaction unit is supplied to the detection unit; The detection unit detects a first concentration of hexavalent chromium contained in the first sample liquid and a second concentration of hexavalent chromium contained in the second sample liquid, and detects a first concentration of hexavalent chromium contained in the first sample liquid and a second concentration of hexavalent chromium contained in the second sample liquid. The concentration of trivalent chromium contained in the second sample liquid is detected based on the concentration.

According to the sample analyzer according to one aspect of the present disclosure, the control unit controls the first supply mode in which the first sample liquid that has passed through the oxidation reaction unit is supplied to the detection unit, and the second supply mode in which the first sample liquid that has passed through the oxidation reaction unit is not passed through the oxidation reaction unit. A second supply mode of supplying the sample liquid to the detection unit is selectively executed. The detection unit detects a first concentration of hexavalent chromium contained in the first sample liquid and a second concentration of hexavalent chromium contained in the second sample liquid, and detects a second concentration of hexavalent chromium contained in the first sample liquid and a second concentration of hexavalent chromium contained in the second sample liquid. The concentration of trivalent chromium contained in the second sample solution is detected.

According to the sample analyzer according to one aspect of the present disclosure, trivalent chromium contained in the sample liquid is oxidized to hexavalent chromium by the oxidation reaction part without any work by an operator. There is no need to secure a worker or space for the work of oxidizing valent chromium to hexavalent chromium. In addition, since the concentration of trivalent chromium and hexavalent chromium contained in the second sample solution are detected respectively, the concentration of trivalent chromium and hexavalent chromium contained in the processing solution must be kept within the desired range. A sample analysis device capable of performing appropriate analysis can be provided.

In the sample analyzer according to one aspect of the present disclosure, the detection unit measures a first amount of light that passes when the first sample liquid is irradiated with light of a specific wavelength, and Measure the amount of second light that passes when the light of the specific wavelength is irradiated, and based on the first amount of light and the second amount of light, the amount of light contained in each of the first sample liquid and the second sample liquid. It may also be configured to detect the concentration of hexavalent chromium.
According to the sample analyzer according to this configuration, the first amount of light that passes when the first sample liquid is irradiated with light of a specific wavelength and the amount of light that passes when the second sample liquid is irradiated with light of a specific wavelength. The concentration of hexavalent chromium contained in the first sample liquid and the second sample liquid can be appropriately detected based on the second light amount.

The sample analyzer according to one aspect of the present disclosure includes a decomposition unit (80) that decomposes a reagent solution for oxidizing trivalent chromium contained in the first sample liquid to hexavalent chromium, and the control unit In the first supply mode, the first sample liquid that has passed through the oxidation reaction section may be supplied to the detection section after passing through the decomposition section.
According to the sample analyzer according to this configuration, in the first supply mode, the first sample liquid that has passed through the oxidation reaction section is supplied to the detection section after passing through the decomposition section. Therefore, the reagent solution for oxidizing trivalent chromium contained in the first sample solution to hexavalent chromium is decomposed, and the reagent solution does not adversely affect the detection result of the concentration of hexavalent chromium detected by the detection unit. It can be prevented.

A sample analyzer according to one aspect of the present disclosure includes a pump (10) disposed in a main pipe (Lm), a main port (PM) connected to the main pipe, and a plurality of sub ports (Ps). and a flow path switching unit (20) that switches the sub-port connected to the main port, and a reagent solution for oxidizing trivalent chromium contained in the sample solution to hexavalent chromium, mixed with the sample solution. a mixing container (30), the mixing container is provided in the main piping between the pump and the main port, and the plurality of sub ports are provided in the sample piping to which the sample liquid is supplied. (Ls1), a reagent port (Ps3) connected to the reagent pipe (Ls3) to which the reagent liquid is supplied, and a detection pipe (Ls2) in which the detection section is arranged. and an oxidation reaction port (Ps5) connected to the oxidation reaction pipe (Ls5) in which the oxidation reaction section is disposed, and the control section is configured to control the first supply mode. The sample liquid and the reagent liquid are drawn into the mixing container from the sample port and the reagent port, and the sample liquid and the reagent liquid are supplied to the oxidation reaction section through the main port and the oxidation reaction port. and controlling the pump and the flow path switching unit to supply the first sample liquid from the oxidation reaction unit to the detection unit, and in the second supply mode, supplying the sample from the sample port to the mixing container. The pump and the flow path switching unit may be controlled to draw in a liquid and supply the second sample liquid from the mixing container to the detection unit.

According to the sample analyzer according to this configuration, by controlling the pump and the flow path switching unit, in the first supply mode, the sample liquid and reagent liquid drawn into the mixing container from the sample port and the reagent port are transferred to the oxidation reaction unit. A first sample liquid in which trivalent chromium is oxidized to hexavalent chromium can be supplied to the detection unit. Furthermore, in the second supply mode, the sample liquid drawn into the mixing container from the sample port can be supplied to the detection section, and a second sample liquid in which trivalent chromium is not oxidized to hexavalent chromium can be supplied to the detection section.

In the sample analyzer according to the above configuration, the plurality of sub-ports have a standard port (Ps11) connected to a standard piping (Ls11) to which a standard solution containing the hexavalent chromium at a predetermined concentration is supplied, and the The control unit connects the main port and the standard port to draw the standard solution from the standard piping to the mixing container, and connects the main port and the detection port to draw the standard solution from the mixing container to the detection unit. A third supply mode for supplying the standard solution is executable, and the detection unit measures a third amount of light that passes when the standard solution is irradiated with light of the specific wavelength, and compares the amount with the first amount of light. The concentration of hexavalent chromium contained in each of the first sample liquid and the second sample liquid may be detected based on the second light amount and the third light amount.

According to the sample analyzer according to this aspect, a standard solution containing hexavalent chromium at a predetermined concentration is prepared, the amount of third light that passes when the standard solution is irradiated with light of a specific wavelength is measured, and the first The concentration of hexavalent chromium contained in each of the first sample liquid and the second sample liquid can be accurately detected based on the light amount, the second light amount, and the third light amount.

In the sample analyzer according to the above configuration, the plurality of sub-ports include a pure water port (Ps12) connected to a pure water pipe (Ls12) to which pure water is supplied, and a pure water port (Ps12) where the sample liquid and the pure water are mixed. a dilution port (Ps9) connected to a dilution container (Co9) that holds a diluted liquid; draw the sample liquid into the mixing container by connecting the main port and the pure water port, drawing the pure water from the pure water piping into the mixing container, and connecting the main port and the dilution port to the mixing container. The pump and the flow path switching section may be controlled so as to supply the diluent from the diluent to the dilution container.

According to the sample analyzer according to this embodiment, the sample liquid and pure water are drawn into the mixing container, the main port and the dilution port are connected, and the diluent is supplied from the mixing container to the dilution container, so that the sample liquid is properly mixed. It can be diluted and stored in a dilution container.

The sample analysis method described in this embodiment described above can be understood, for example, as follows.
A sample analysis method according to one aspect of the present disclosure is a sample analysis method for detecting the concentration of hexavalent chromium contained in a sample liquid using a sample analysis device, the sample analysis device performing surface treatment on a metal material. an oxidation reaction unit that oxidizes trivalent chromium contained in a sample liquid extracted from a processing liquid for performing the treatment to hexavalent chromium, and a detection unit that detects the concentration of hexavalent chromium contained in the sample liquid, a first supply mode in which a first sample liquid that has passed through the oxidation reaction section is supplied to the detection section; and a second supply mode in which a second sample liquid that does not pass through the oxidation reaction section is supplied to the detection section. a control step of selectively executing a mode, and a control step of selectively performing a first concentration of hexavalent chromium contained in the first sample liquid and a second concentration of hexavalent chromium contained in the second sample liquid by the detection unit; and a detection step of detecting the concentration of trivalent chromium contained in the second sample liquid based on the first concentration and the second concentration.

According to the sample analysis method according to one aspect of the present disclosure, the first supply mode supplies the first sample liquid that has passed through the oxidation reaction section to the detection section, and the second supply mode does not allow the first sample liquid to pass through the oxidation reaction section. A second supply mode of supplying the sample liquid to the detection unit is selectively executed. The detection step detects a first concentration of hexavalent chromium contained in the first sample liquid and a second concentration of hexavalent chromium contained in the second sample liquid, and detects the second concentration of hexavalent chromium contained in the first sample liquid and the second concentration of hexavalent chromium contained in the second sample liquid. The concentration of trivalent chromium contained in the liquid is detected.

According to the sample analysis method according to one aspect of the present disclosure, trivalent chromium contained in the sample liquid is oxidized to hexavalent chromium by the oxidation reaction part without any work by an operator. There is no need to secure a worker or space for the work of oxidizing valent chromium to hexavalent chromium. In addition, since the concentration of trivalent chromium and hexavalent chromium contained in the second sample solution are detected respectively, the concentration of trivalent chromium and hexavalent chromium contained in the processing solution must be kept within the desired range. A sample analysis method that allows appropriate analysis can be provided.

In the sample analysis method according to one aspect of the present disclosure, the detection step includes measuring the amount of first light that passes when the first sample liquid is irradiated with light of a specific wavelength; Measure the amount of second light that passes when the light of the specific wavelength is irradiated, and based on the first amount of light and the second amount of light, the amount of light contained in each of the first sample liquid and the second sample liquid. It may also be configured to detect the concentration of hexavalent chromium.
According to the sample analysis method according to this configuration, the first amount of light that passes when the first sample liquid is irradiated with light of a specific wavelength and the amount of light that passes when the second sample liquid is irradiated with light of a specific wavelength. The concentration of hexavalent chromium contained in the first sample liquid and the second sample liquid can be appropriately detected based on the second light amount.

In the sample analysis method according to one aspect of the present disclosure, the sample analysis device includes a decomposition unit that decomposes a reagent solution for oxidizing trivalent chromium contained in the first sample liquid to hexavalent chromium; The control step may include, in the first supply mode, supplying the first sample liquid that has passed through the oxidation reaction section to the detection section after passing through the decomposition section.
According to the sample analysis method according to this configuration, in the first supply mode, the first sample liquid that has passed through the oxidation reaction section is supplied to the detection section after passing through the decomposition section. Therefore, it is possible to prevent the reagent solution for oxidizing trivalent chromium contained in the first sample solution into hexavalent chromium from being decomposed and adversely affecting the concentration detection results detected by the detection unit due to the reagent solution. can.

In the sample analysis method according to one aspect of the present disclosure, the sample analysis device includes a pump disposed in a main pipe, a main port connected to the main pipe and a plurality of sub ports, and a flow path switching unit for switching the sub-port to be connected; and a mixing container for mixing the sample liquid with a reagent liquid for oxidizing trivalent chromium contained in the sample liquid to hexavalent chromium; The container is provided in the main piping between the pump and the main port, and the plurality of sub-ports are connected to a sample port connected to the sample piping to which the sample liquid is supplied, and a container to which the reagent liquid is supplied. a reagent port connected to the reagent piping to be supplied; a detection port connected to the detection piping in which the detection section is arranged; an oxidation reaction port connected to the oxidation reaction piping in which the oxidation reaction section is arranged; The control step includes, in the first supply mode, drawing the sample liquid and the reagent liquid from the sample port and the reagent port into the mixing container, and drawing the sample liquid and the reagent liquid into the mixing container through the main port and the oxidation reaction port. controlling the pump and the flow path switching unit to supply the sample liquid and the reagent liquid to the oxidation reaction section, and supplying the first sample liquid from the oxidation reaction section to the detection section; In the supply mode, the pump and the flow path switching unit may be controlled to draw the sample liquid from the sample port into the mixing container and supply the second sample liquid from the mixing container to the detection unit. good.

According to the sample analysis method according to the present configuration, by controlling the pump and the flow path switching unit, in the first supply mode, the sample liquid and reagent liquid drawn into the mixing container from the sample port and the reagent port are transferred to the oxidation reaction unit. A first sample liquid in which trivalent chromium is oxidized to hexavalent chromium can be supplied to the detection unit. Furthermore, in the second supply mode, the sample liquid drawn into the mixing container from the sample port can be supplied to the detection section, and a second sample liquid in which trivalent chromium is not oxidized to hexavalent chromium can be supplied to the detection section.

In the sample analysis method according to the above configuration, each of the plurality of sub-ports has a standard port connected to a standard piping to which a standard solution containing the hexavalent chromium at a predetermined concentration is supplied, and the control step includes the main port. A port and the standard port are connected to draw the standard solution from the standard piping to the mixing container, and the main port and the detection port are connected to supply the standard solution from the mixing container to the detection section. A third supply mode can be executed, and the detection step measures a third amount of light that passes when the standard solution is irradiated with light of the specific wavelength, and the first amount of light, the second amount of light, and the amount of light that passes through the standard solution are measured. The concentration of hexavalent chromium contained in each of the first sample liquid and the second sample liquid may be detected based on the third amount of light.

According to the sample analysis method according to this aspect, a standard solution containing hexavalent chromium at a predetermined concentration is prepared, the amount of third light that passes when the standard solution is irradiated with light of a specific wavelength is measured, and the first The concentration of hexavalent chromium contained in each of the first sample liquid and the second sample liquid can be accurately detected based on the light amount, the second light amount, and the third light amount.

In the sample analysis method according to the above configuration, the plurality of sub-ports include a pure water port (Ps12) connected to a pure water pipe (Ls12) to which pure water is supplied, and a pure water port (Ps12) where the sample liquid and the pure water are mixed. a dilution port (Ps9) connected to a dilution container (Co9) that holds a diluted liquid; draw the sample liquid into the mixing container by connecting the main port and the pure water port, drawing the pure water from the pure water piping into the mixing container, and connecting the main port and the dilution port to the mixing container. The pump and the flow path switching section may be controlled so as to supply the diluent from the diluent to the dilution container.

According to the sample analysis method according to this aspect, the sample liquid and pure water are drawn into the mixing container, the main port and the dilution port are connected, and the diluent is supplied from the mixing container to the dilution container, so that the sample liquid is properly mixed. It can be diluted and stored in a dilution container.

10 Syringe pump 20 Flow path switching valve (flow path switching section)
30 Mixing container 40 Detection section 50 Three-way valve 60 Control section 70 Oxidation reaction section 80 Decomposition section 100 Sample analysis device 200 Surface treatment device 220 Treatment tank 300 Metal parts Co3 Oxidation reaction reagent container Co4 Coloring reagent container Co5 Oxidation reaction container Co6 Decomposition reaction container Co7 Decomposition reagent liquid container Co9 First dilution container Co10 Second dilution container Co11 Standard solution container Co12 Pure water container Lm Main pipe Ls1 Sample pipe Ls2 Detection pipe Ls3 Oxidation reaction reagent pipe Ls4 Coloring reagent pipe Ls5 Oxidation reaction pipe Ls6 Decomposition reaction pipe Ls7 Decomposition reagent piping Ls8 Waste liquid piping Ls9 First dilution piping Ls10 Second dilution piping Ls11 Standard piping Ls12 Pure water piping Pm Main port Ps Sub port Ps1 Sample port Ps2 Detection port Ps3 Oxidation reaction reagent port Ps4 Coloring reagent port Ps5 Oxidation reaction port Ps6 Decomposition Reaction port Ps7 Decomposition reagent port Ps8 Waste liquid port Ps9 First dilution port Ps10 Second dilution port Ps11 Standard port Ps12 Pure water port TD Transport direction

Claims (10)

an oxidation reaction unit that oxidizes trivalent chromium contained in a sample solution extracted from a treatment solution for surface treatment of metal materials to hexavalent chromium;
a detection unit that respectively detects the concentration of trivalent chromium and the concentration of hexavalent chromium contained in the sample liquid;
a first supply mode in which a first sample liquid that has passed through the oxidation reaction section is supplied to the detection section; and a second supply mode in which a second sample liquid that does not pass through the oxidation reaction section is supplied to the detection section. a control unit that selectively executes the mode;
A pump placed in the main piping,
a flow path switching unit having a main port connected to the main piping and a plurality of sub ports, and switching the sub ports connected to the main port;
a mixing container for mixing a reagent solution for oxidizing trivalent chromium contained in the sample solution into hexavalent chromium into the sample solution;
The detection unit detects a first concentration of hexavalent chromium contained in the first sample liquid and a second concentration of hexavalent chromium contained in the second sample liquid, and detects the first concentration and the second concentration of hexavalent chromium contained in the second sample liquid. detecting the concentration of trivalent chromium contained in the second sample solution based on the concentration of
The mixing container is provided in the main piping between the pump and the main port,
The plurality of secondary ports are
a sample port connected to a sample pipe to which the sample liquid is supplied;
a reagent port connected to a reagent pipe to which the reagent solution is supplied;
a detection port connected to a detection pipe in which the detection section is arranged;
an oxidation reaction port connected to the oxidation reaction piping in which the oxidation reaction section is arranged,
The control unit includes:
In the first supply mode, the sample liquid and the reagent liquid are drawn into the mixing container from the sample port and the reagent port, and the sample liquid and the reagent liquid are drawn into the mixing container through the main port and the oxidation reaction port. controlling the pump and the flow path switching unit to supply the first sample liquid to the oxidation reaction unit and from the oxidation reaction unit to the detection unit;
In the second supply mode, the pump and the flow path switching unit are controlled to draw the sample liquid from the sample port into the mixing container and supply the second sample liquid from the mixing container to the detection unit. Sample analyzer. The detection unit measures a first amount of light that passes when the first sample liquid is irradiated with light of a specific wavelength, and measures a first amount of light that passes when the second sample liquid is irradiated with light of the specific wavelength. According to claim 1, the concentration of hexavalent chromium contained in each of the first sample liquid and the second sample liquid is detected based on the first light amount and the second light amount. Sample analyzer as described. comprising a decomposition unit that decomposes the reagent solution,
3. The control unit supplies the first sample liquid that has passed through the oxidation reaction unit to the detection unit after passing through the decomposition unit in the first supply mode. Sample analyzer as described. The plurality of sub-ports have a standard port connected to standard piping to which a standard solution containing the hexavalent chromium at a predetermined concentration is supplied,
The control section connects the main port and the standard port to draw the standard solution from the standard piping to the mixing container, and connects the main port and the detection port to draw the standard solution from the mixing container to the detection section. a third supply mode of supplying the standard solution to the
The detection unit measures a third light amount that passes when the standard solution is irradiated with light of the specific wavelength, and measures the first light amount based on the first light amount, the second light amount, and the third light amount. The sample analyzer according to claim 2, wherein the sample analysis device detects the concentration of hexavalent chromium contained in each of the sample liquid and the second sample liquid. The plurality of sub-ports include a pure water port connected to a pure water pipe to which pure water is supplied, and a dilution port connected to a dilution container holding a diluted liquid in which the sample liquid and the pure water are mixed. , has
The control unit connects the main port and the sample port to draw the sample liquid from the sample pipe into the mixing container, and connects the main port and the pure water port to draw the sample liquid from the pure water pipe to the mixing container. Claim 1 : Controlling the pump and the flow path switching unit to draw the pure water into a mixing container, connect the main port and the dilution port, and supply the diluent from the mixing container to the dilution container. 5. The sample analysis device according to claim 4 . A sample analysis method for detecting the concentration of hexavalent chromium contained in a sample liquid using a sample analysis device,
The sample analysis device includes:
an oxidation reaction unit that oxidizes trivalent chromium contained in the sample liquid extracted from a treatment liquid for surface treatment of metal materials to hexavalent chromium;
a detection unit that detects the concentration of hexavalent chromium contained in the sample liquid;
A pump placed in the main piping,
a flow path switching unit having a main port connected to the main piping and a plurality of sub ports, and switching the sub ports connected to the main port;
a mixing container for mixing a reagent solution for oxidizing trivalent chromium contained in the sample solution into hexavalent chromium into the sample solution;
The mixing container is provided in the main piping between the pump and the main port,
The plurality of secondary ports are
a sample port connected to a sample pipe to which the sample liquid is supplied;
a reagent port connected to a reagent pipe to which the reagent solution is supplied;
a detection port connected to a detection pipe in which the detection section is arranged;
an oxidation reaction port connected to the oxidation reaction piping in which the oxidation reaction section is arranged,
a first supply mode in which a first sample liquid that has passed through the oxidation reaction section is supplied to the detection section; and a second supply mode in which a second sample liquid that does not pass through the oxidation reaction section is supplied to the detection section. a control process for selectively executing the mode;
The detection unit detects a first concentration of hexavalent chromium contained in the first sample liquid and a second concentration of hexavalent chromium contained in the second sample liquid, and detects the first concentration and the second concentration of hexavalent chromium contained in the second sample liquid. a detection step of detecting the concentration of trivalent chromium contained in the second sample liquid based on the second concentration ,
The control step includes:
In the first supply mode, the sample liquid and the reagent liquid are drawn into the mixing container from the sample port and the reagent port, and the sample liquid and the reagent liquid are drawn into the mixing container through the main port and the oxidation reaction port. controlling the pump and the flow path switching unit to supply the first sample liquid to the oxidation reaction unit and from the oxidation reaction unit to the detection unit;
In the second supply mode, the pump and the flow path switching unit are controlled to draw the sample liquid from the sample port into the mixing container and supply the second sample liquid from the mixing container to the detection unit. sample analysis method. The detection step includes measuring a first amount of light that passes when the first sample liquid is irradiated with light of a specific wavelength, and measuring a first amount of light that passes when the second sample liquid is irradiated with light of the specific wavelength. According to claim 6 , the concentration of hexavalent chromium contained in each of the first sample liquid and the second sample liquid is detected based on the first light amount and the second light amount. Sample analysis method described. The sample analyzer includes a decomposition unit that decomposes the reagent liquid,
According to claim 6 or 7 , in the control step, in the first supply mode, the first sample liquid that has passed through the oxidation reaction section is supplied to the detection section after passing through the decomposition section. Sample analysis method described. The plurality of sub-ports have a standard port connected to standard piping to which a standard solution containing the hexavalent chromium at a predetermined concentration is supplied,
The control step includes connecting the main port and the standard port to draw the standard solution from the standard piping into the mixing container, and connecting the main port and the detection port to draw the standard solution from the mixing container to the detection section. a third supply mode of supplying the standard solution to the
The detection step includes measuring a third light amount that passes when the standard solution is irradiated with light of the specific wavelength, and detecting the first light amount based on the first light amount, the second light amount, and the third light amount. 8. The sample analysis method according to claim 7, wherein the concentration of hexavalent chromium contained in each of the sample liquid and the second sample liquid is detected. The plurality of sub-ports include a pure water port connected to a pure water pipe to which pure water is supplied, and a dilution port connected to a dilution container holding a diluted liquid in which the sample liquid and the pure water are mixed. , has
The control step includes connecting the main port and the sample port to draw the sample liquid from the sample pipe into the mixing container, and connecting the main port and the pure water port to draw the sample liquid from the pure water pipe to the mixing container. Claim 6 : Controlling the pump and the flow path switching unit to draw the pure water into the mixing container, connect the main port and the dilution port, and supply the diluent from the mixing container to the dilution container. 10. The sample analysis method according to claim 9 .