JP2892094B2 - Metal component analyzer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal component analyzer capable of efficiently analyzing a trace metal component in ultrapure water by using an ion exchange separation method. "Prior Art" FIG. 9 shows a metal component analyzer proposed by the present inventors in Japanese Patent Application No. 63-180529. Reference numeral 1 in the figure denotes an automatic flow switching valve. A sample liquid supply path 30 is connected to an outlet of the automatic flow path switching valve 1. In the sample liquid supply path 30, a liquid sending pump 2, a reactor 3,
An overflow container 4, a three-way automatic switching valve 5, a pressure pump 6, and a pressure sensor 6A are attached. The sample liquid supply path 30 is finally connected to the first four-way automatic switching valve 7. The first four-way automatic switching valve 7 is connected to an inflow path 8a to the first concentration column 8, an inflow path 9a to the second concentration column 9, and an eluent supply path 31. The eluent supply path 31 is provided with a pressurizing pump 17 and an eluent reservoir 18. The outflow passage 8b from the first concentration column 8 and the outflow passage 9b from the second concentration column 9 are connected to a second four-way automatic switching valve 10.
It is connected to the. The second four-way automatic switching valve 10 includes:
Analysis means comprising a separation column 11 and an absorptiometer 12
A line 33 leading to 32 and a line 35 leading to a drain 34 are connected, and the flow meter 19 is attached to the line 35. That is, the first four-way automatic switching valve 7 is connected to the sample liquid supply path.
30 is provided at a branch portion branched to the inflow paths 8a and 9a,
The four-way automatic switching valve 10 is provided at the junction (branch) where the outflow passages 8b and 9b join the line 33,
9. A sample liquid and an eluent are selectively supplied to the analysis means 32 and the line 35 leading to the drain passage 34. Next, the operation of the metal component analyzer will be described. The automatic flow path switching valve 1 has six sample liquid inflow paths 1A to 1A.
1F is connected. And these sample liquid inflow channels 1A-1F
Is selectively connected to the sample liquid supply path 30. The sample liquid flowing into the sample liquid supply path 30 is sent to the reactor 3 by the liquid sending pump 2. On the upstream side of the reactor 3, a reaction solution storage unit 15 storing a reaction solution such as hydrochloric acid and a liquid sending pump 16 are provided.
The reaction solution supply path 37 is connected to the sample solution, and a reaction solution for ionizing metals in the sample solution is added to the sample solution. The sample solution to which the reaction solution has been added is supplied to the reactor 3
The mixture is heated to a predetermined temperature and mixed. The sample liquid that has passed through the reactor 3 is temporarily stored in the overflow container 4, and the sample liquid that has exceeded a predetermined storage amount is discharged to the drain 34 through a line indicated by reference numeral L ₂ . The sample liquid that has passed through the overflow container 4 reaches the three-way automatic switching valve 5. The three-way automatic switching valve 5 is connected to the sample liquid supply path 30.
A portion of the sample liquid flowing through, and guides the drainage channel 34 through a line denoted by reference numeral L _3. That is, when the automatic flow path switching valve 1 is switched and another sample liquid is supplied,
First, by switching the flow path to the line L ₃ side, completely washing away the previous sample liquid which remains between the automatic channel switching valve 1 and the three-way automatic switching valve 5. After that, the flow path is switched to flow the sample liquid along the sample liquid supply path 30. The sample liquid that has passed through the three-way automatic switching valve 5 is pressurized by a pressure pump 6. When the sample liquid is pressurized to a predetermined pressure or more by the pressurizing pump 6, a detection signal for stopping the operation of the pressurizing pump 6 is output from the pressure sensor 6A to the control unit C. It has become. The sample liquid pressurized by the pressure pump 6 is supplied to the first concentration column 8 or the second concentration column 8 by the first four-way automatic switching valve 7.
Is supplied to the concentration column 9. The first four-way automatic switching valve 7 and the second four-way automatic switching valve
Reference numeral 10 denotes a flow path for the metal ion concentration step in which the sample liquid supplied from the sample liquid supply path 30 is passed through the concentration column 8 or 9 and then led to the drain path 34 via the line 35;
After the eluent supplied from 31 is passed through the concentration column 9 or 8, the flow path of the metal ion elution step to be led to the analysis means 32 is formed alternately with the concentration columns 8 and 9. The switching of these four-way automatic switching valves 7 and 10
This is performed by a signal transmitted from the control unit C when the flow rate value of the sample liquid passing through the line 35 measured at 19 reaches a set value. When the sample solution passes through the concentration column 8 or 9, the metal ions in the sample solution are adsorbed on the concentration column 8 or 9. The metal ions adsorbed on the concentration column 8 or 9 are eluted from the concentration columns 8 and 9 by the eluent supplied from the eluent supply path 31 and carried to the analysis means 32. When the eluent is pressurized to a predetermined pressure or more by the pressurizing pump 17, a detection signal for stopping the operation of the pressurizing pump 17 is output from the pressure sensor 17A to the control unit C. It has become. Further, the metal ions carried to the analysis means 32 are purified by the separation column 11, then colored by the coloring solution from the coloring solution supply channel 38, and the concentration is measured by the absorptiometer 12. Note that the coloring liquid is supplied to the coloring liquid storage unit by a liquid sending pump indicated by reference numeral 20.
From 21, it is supplied to the coloring liquid supply path 38. "Problems to be Solved by the Invention" By the way, the above-mentioned metal component analyzer uses an acid such as hydrochloric acid as a reaction solution for ionizing insoluble metal components contained in a sample solution. Therefore, in the concentration column, ion capture and desorption by acid are competitively simultaneous, and the amount of ions secured in the concentration column decreases compared to the amount of ions in the sample liquid actually supplied, As a result, there is a problem that the analysis of ions becomes uncertain and the concentration efficiency is deteriorated. Further, in the above-mentioned metal component analyzer, the sample liquid is supplied to the concentration column, and the metal component in the sample liquid is adsorbed to the concentration column.
The eluted metal ions may remain in the concentration column as it is, whereby the metal ions of the sample solution to be measured next cannot be efficiently adsorbed to the concentration column, and the concentration efficiency is reduced. There was a problem of getting worse. The present invention has been made in view of the above circumstances, and provides a metal component analyzer capable of adsorbing a metal component (metal ion) with high efficiency to a concentration column and improving the concentration efficiency. With the goal. [Means for Solving the Problems] In the first invention, a sample liquid supply path to which a sample liquid containing a metal component is supplied, and a bifurcated and parallel branch in the middle of the sample liquid supply path A pair of parallel supply paths provided, first and second concentration columns provided in each parallel supply path to adsorb a metal component in a sample liquid, and provided at a branch of the parallel supply path located on the upstream side. A first four-way switching valve, a second four-way switching valve provided at a branch of the parallel supply path located downstream, and the first four-way switching valve connected to the first four-way switching valve and adsorbed to the concentration column. An eluent supply path through which an eluent for eluting a metal component is supplied; a discharge path connected to the second four-way switching valve to discharge the solution via each of the parallel supply paths; It is provided in the sample liquid supply channel located downstream of the valve, and is eluted by the eluent. The analysis means for detecting the concentration of the metal component in the sample liquid obtained, and the first and second four-way switching valves are respectively switched to selectively use the sample liquid or the eluent for the first and second columns. , And the sample solution passed through the first and second concentration columns,
A controller for selectively supplying an eluent to a discharge path or a sample liquid supply path leading to an analysis means, wherein a metal liquid in the sample liquid is supplied by supplying a sample liquid to the control unit. A replacement function of adsorbing the sample solution after adsorption of the metal component to one of the concentration columns and discharging the sample solution to the discharge path, and supplying an eluent to elute the metal component adsorbed to the one of the concentration columns; A washing function for discharging the eluent to the discharge path, and a concentration for supplying the sample liquid and adsorbing the metal component in the sample liquid to one of the concentration columns after the washing, and discharging the sample liquid after the adsorption to the discharge path. And an analysis function of supplying an eluent to elute the metal component adsorbed on one of the concentration columns after the washing, and guiding the eluent after the elution to a sample liquid supply path leading to an analysis means. Like that. In the second invention, a sample liquid supply pump for supplying a sample liquid to the sample liquid supply path and an eluent supply pump for supplying an eluent to the eluate supply path are provided, respectively. Stop the supply pumps respectively,
By switching the first and second four-way switching valves, respectively,
The sample liquid or the eluent is selectively supplied to the second column, and the sample liquid or the eluate passed through the first and second concentration columns is supplied to a discharge path or a sample liquid supply path leading to an analysis means. A control unit for selectively supplying the sample solution is further provided, and after supplying the sample solution to the first concentration column to adsorb the metal component, the control unit guides the sample solution to the discharge path, and 2
After supplying the eluent to the concentration column for washing, the eluent is guided to a sample liquid supply path leading to the analysis means, and a replacement / wash function, and the eluate is supplied to the first concentration column,
After eluting the adsorbed metal component, the eluent is guided to a discharge path, and the washing / stopping function of stopping the second concentration column by stopping the sample solution supply pump; and After supplying the sample liquid to the first concentrated column after washing to adsorb the metal component, the adsorbed sample liquid is guided to the discharge path, and the eluent supply pump is stopped to stop the eluent. A concentration / stop function for further stopping the second concentration column of the first concentration column;
After the eluent is supplied to the concentration column to elute the adsorbed metal component, the eluate is guided to a sample liquid supply path leading to the analysis means, and the stopped second concentration column is stopped. An analysis / substitution function for guiding the sample solution to a discharge path after supplying the sample solution to the sample solution and adsorbing the metal component, and a first concentration column after the analysis process by stopping the sample solution supply pump. Stopping and washing function of supplying the eluent to the second concentration column to elute the adsorbed metal component, and then guiding the eluent to a discharge path; and Further stopping the stopped first concentration column by stopping the supply pump; and
A stop and concentration function for supplying a sample liquid to the washed second concentration column to adsorb the metal component and then guiding the adsorbed sample liquid to a discharge path, and a first concentration during the stop After the sample solution is supplied to the column to adsorb the metal component, the sample solution is guided to a discharge path, and the eluent is supplied to the concentrated second concentration column, and the adsorbed metal is supplied to the second concentration column. After the components are eluted, a replacement / analysis function is provided to guide the eluent to a sample liquid supply passage leading to the analysis means. According to the third invention, the sample liquid supply path located upstream of the first four-way switching valve is provided with a liquid supply pump for supplying a neutralizing liquid for neutralizing the sample liquid. Adjust the pH
An adjusting unit, and a pH sensor for monitoring the pH of the sample solution adjusted by the pH adjusting unit are sequentially provided.
A pH adjusting function for adjusting the supply amount of the neutralizing solution by the liquid sending pump based on the detection data of the sensor is provided. According to the first aspect of the present invention, in each concentration column, a process such as “replacement” → “washing” is first performed, and a sample liquid to be measured in each concentration column is first passed. The metal ions in the sample solution were subjected to “concentration” → “analysis”, that is, the concentration column was once replaced with the metal ion to be measured next, and then the actual adsorption of the metal ion, Since the elution is performed, there is no metal ion of the measured sample solution remaining in the concentration column, thereby increasing the concentration efficiency of the concentration column. According to the second invention, the sample liquid supply pump and the elution supply pump are appropriately turned ON / OFF, and the first and second four-way switching valves are appropriately switched, so that “replacement → wash →
Concentration → analysis → stop → stop → replacement ”,“ washing → stop → stop → replacement → wash → concentration → analysis ”for the second concentration column
Since the processes are performed in correspondence with each other, the processes can be efficiently performed in cooperation with each other for the two columns. According to the third aspect of the present invention, the pH is adjusted by the pH adjuster and monitored by the pH sensor so that the pH is maintained neutral. (Metal ions) can be efficiently captured, and the concentration efficiency of metal components in the concentration column can be increased. Hereinafter, embodiments of the present invention will be described with reference to the drawings. The same components as those in the conventional example are denoted by the same reference numerals, and description thereof is omitted.

[Structure for removing insoluble metal components]

FIG. 1 shows a first embodiment of the metal component analyzer of the present invention. A flow path switching valve 41 is connected to the sample liquid supply path 30a downstream of the liquid feed pump 2. The flow path switching valve 41 is connected to one end of a flow path 42 and one end of a filtration path 43, respectively. The other ends of the flow path 42 and the filtration path 43 are connected to the sample liquid supply path 30b via flow path switching valves 44, respectively. The switching operation of the flow path switching valve 41 and the flow path switching valve 44 is controlled by the control unit C, respectively. Further, in the middle of the filtration path 43, a filtration unit 45 having a built-in filtration filter for filtering insoluble metal components in the sample liquid is provided. When the sample liquid passes through the filtration path 43, filtration is performed. The part 45 filters insoluble metal components in the sample liquid. According to the metal component analyzer configured as described above,
When the sample liquid is passed through the flow path 42 by the flow path switching valves 41 and 44, the sample liquid is sent out to the sample liquid supply path 30b, and then the reaction liquid is supplied. As a result, all of the metal components contained in the sample solution are ionized, and thereafter, the analysis means 32 analyzes all the metal components. When the sample liquid is passed through the filtration path 43 by the flow path switching valves 41 and 44, only the insoluble metal component contained in the sample liquid is filtered by the filtration unit 45, and the sample liquid is filtered. After being sent out to the supply path 30b, the analysis means 32 analyzes the metal component in the sample liquid. That is, since the insoluble metal component is removed from the sample solution passed through the filtration path 43, only the metal component dissolved in the sample solution is analyzed in this case.

[Configuration of pH adjustment unit, reducing agent supply unit, pH sensor]

In the figure, what is indicated by reference numeral 50 is a pH adjusting unit 50.
The pH adjusting section 50 has a structure in which an ion exchange membrane is provided inside a hollow container.
Two spaces are formed inside the container. A sample solution to which a reaction liquid (acid solution) is added is supplied to one side of these two spaces, and a neutralizing solution for pH adjustment is supplied to the other space as a neutralizing solution for pH adjustment. A solution, for example, a 0.1 to 1 N tetramethylammonium hydroxide solution is supplied, and chloride ions (those contained in hydrochloric acid of the reaction solution) are transferred from the sample solution into the neutralization solution via the ion exchange membrane. Then, hydroxyl ions move from the neutralizing solution into the sample solution. That is, ion exchange is performed between the two, and the concentration of hydrogen ions in the sample solution decreases, and the pH increases to approach neutrality. The supply and discharge of the neutralizing solution to and from the pH adjusting unit 50 are performed through a neutralizing solution supply channel 55 and a neutralizing solution outflow channel 56, respectively. The neutralizing solution supply passage 55 is configured to suck up the neutralizing solution from the neutralizing solution storage unit 57 by the solution sending pump 58, and the neutralized solution after the ion exchange is supplied to the neutralizing solution outflow passage. 56
Through the drain 34. Further, a reducing agent supply unit is provided downstream of the pH adjustment unit 50. This reducing agent supply section is a reducing agent (ascorbic acid solution) that reduces the iron component from trivalent to divalent state
And a liquid feed pump 59 for adding the reducing agent to the sample liquid supply path 30 (30c) via the reducing agent supply path 60a. Further, the reducing agent supply path 60a and the sample liquid supply path 30 (30c)
A pH sensor 61 is provided on the downstream side of the junction with the above. The pH sensor 61 monitors the pH of the sample solution whose pH has been adjusted by the pH adjusting unit 50.
The controller C controls the amount of the neutralizing solution sent by the solution sending pump 58 based on the detection signal output from 61. The installation position of the pH adjuster 50 is not limited to the above-described embodiment, and may be any position as long as it is upstream of the concentration columns 8, 9 in the pipe through which the sample solution flows. Of course. When the pH of the sample solution is high, an acid may be used as the neutralizing solution.

[Configuration of cooling unit]

Sample liquid supply path 30c between the pH adjusting unit 60 and the reactor 3
Is formed in a coil shape, and cooling air is supplied from a cooling fan 49 provided on a side of the coil portion 30c 'formed in the coil shape. That is, when the sample liquid heated by the reactor 3 passes through the coil portion 30c ', it is cooled by the cooling air supplied from the cooling fan 49. Thus, the vapor generated in the sample liquid is extinguished. The reactor 3 is also provided with a cooling fan 62. The cooling fan 62 is a drum-shaped heater (not shown).
The entirety of the reactor 3 formed by spirally winding the sample liquid supply path 30b from the surroundings is cooled when the analysis of the metal component is completed.

[Configuration of Check Valve 63] A check valve 63 is provided in the middle of the flow passage 30e leading to the drainage passage 34 of the three-way automatic switching valve 5. The check valve 63 is opened by the discharge pressure of the sample liquid discharged from the pH adjuster 50. And when the check valve 63 is provided in this way,
Due to the siphon phenomenon, all the sample liquid in the supply path 30c does not flow to the discharge path 34 that leads to the drain. Although the three-way automatic switching valve 5 is provided between the pH sensor 61 and the check valve 63 in FIG. 1, a three-way joint 47 and a check valve 48 as shown in FIG. good. To explain the three-way joint 47 and the check valve 48, the three-way joint 47 is connected to one end of the sample liquid supply path 30c, and the other two ends are connected to the discharge path 34 and the sample liquid supply path 30d, respectively. Have been. The check valve 48 is provided on the sample liquid supply path 30c on the upstream side of the pressurizing pump 6. The check valve 48 is opened when the pressure of the sample liquid supply passage 30d becomes equal to or less than a predetermined value due to the operation of the pressurizing pump 6. Further, when the pressurizing pump 6 stops to analyze the metal component in the sample liquid, the pressure in the sample liquid supply path 30d increases, and the check valve 48 closes.

[About the control contents of the control unit]

Next, the control contents of the control unit C will be described with reference to the flowcharts of FIGS. 3 to 7, the timing chart of FIG. 8 (A), and the table of FIG. 8 (B). The control unit C has a timer (not shown). The control unit C includes a pH sensor 61, pressure switches 6A and 17A,
The detection data from the flow meter 19 and the absorption photometer 12 are input,
In addition, a temperature sensor (not shown) provided in the reactor 3 and a liquid level sensor (not shown) provided in each of the storage sections 15, 60, 57, 18, and 21 for detecting the amount of each stored liquid are provided. Detection data is input. Also, from the control unit C, based on the various detection data, the automatic flow switching valve 1 (sampling valve in FIGS. 3 to 8), the three-way automatic switching valves 41 and 44, and the three-way automatic switching valve 5 (the 3 to 8, a three-way valve), a four-way automatic switching valve 7, 10 (a four-way valve in FIGS. 3 to 8), a liquid feed pump 2, 16, 59, 58, 20, a pressure pump 6, 17. A control signal for controlling the heater of the reactor 3, the cooling fans 49 and 62, and the (zero point) of the absorptiometer 12 is output. Further, the control unit C calculates the concentration of the metal component based on the detection data from the absorptiometer 12, and this concentration value is supplied to a data recording unit indicated by D and recorded. I'm becoming. Further, the control unit includes:
A graphic display B for displaying the various data and the current analysis process is provided. Further, by connecting the control unit C to a personal computer or a large-sized computer A, it is possible to remotely change analysis conditions, record data, and print data. Output and various data can be monitored. Also, “P ₁ ” shown in FIGS. 3 to 8 except for FIG.
~P ₄ "corresponds respectively to the liquid feed pump 2, 16, 59, 58," P ₅ · P ₆ "will correspond to the pressure pump 6, 17,
P ₇ corresponds to the liquid feed pump 20. Further, "P ₁ shown in FIG. 6
· P ₂ "corresponds respectively to the detected value of the pressure sensor 6A · 17A. In the following description, SP (step) 1 to SP13
Indicates a process of “warm-up operation from start”, SP14 to SP40 indicate a process of “replacement-washing-concentration-analysis”, and SP41 to SP44 indicate a final process, respectively. <SP1-6> After the main switch (not shown) is turned on to start (SP1), the absorptiometer 12, the flow meter 19 and the pH sensor 61 are turned on (SP2). After that, a menu of various measurement conditions of the metal component is displayed on the graphic display of B (SP3), and it is determined whether the analysis is performed under the currently set conditions with or without revising the conditions (SP4). ). If it is determined in SP4 that the analysis is to be performed under the currently set conditions, after the start button is turned ON (SP5), the sampling valve 1 is set to the first position (when the sample liquid inflow path 1A is selected). ), Pump 2.16.
59 is turned on, and then the pump 6 is turned on. At the same time, the heater of the reactor 3 is turned on, and the three-way valve 5 is turned on (set to the dotted line side) (SP6) (shown by T in FIG. 8 (A)). timing). Note that this state is an operation state indicating warm-up operation. Under this state, the four-way valves 7 and 10 are both set to the L side indicated by the dotted line in FIG. After the metal solution is adsorbed on the sample liquid supplied to the concentration column 8, the sample liquid is drained to a drain 34 through a line 35. At this time, the pressurizing pump 17
Since it is not turned on, no eluent is supplied to the concentration column 9. The four-way valves 7 and 10 correspond to the four-way valves (A) and (B) shown in FIGS. 3 to 8A, respectively. <SP7-8> Next, measurement by a timer is started (SP7), and the pressure in the path 30d and the path 31 during the warm-up operation, the temperature in the reactor 3, and the respective storage units 15, 60, 57, 18, and 21 are stored. Storage volume, sample liquid
It is determined whether the pH is appropriate (SP8). Specifically, as shown by “SP8A to SP8B” in FIG. 6, SP8 is based on the detection signal of the pressure sensor 6A,
The concentration pressure (P ₁ ) by the pre-set pressure (P ₀₁ ~
P ′ ₀₁ ) and whether the pressure sensor 17A
Whether the elution pressure (P ₂ ) by the pressure pump 17 is within a preset pressure range (P _{02 to} P ′ ₀₂ ), based on the detection signal of the sensor, the reactor 3 of the temperature (T) is preset set temperature _{(T 0 ± 2~T '0 ±} 2) is in the range whether the detected judgment respectively, the pressure ( If the temperature P (P ₁ · P ₂ ) and the temperature (T) continue outside the above-mentioned range for a predetermined time, it is regarded as abnormal, and the details of the abnormality are displayed on the graphic display B. 17 ・ 20 ・ 58.5
9. Turn off the heater of the reactor 3 and turn on the cooling fans 49 and 62 appropriately. As shown by “SP8C” in FIGS. 6 and 7, based on detection data from liquid level sensors (not shown) provided in each of the storage units 15, 60, 57, 18, and 21, The storage amount of hydrochloric acid (H ₂ ) stored as a reaction solution, the storage amount of ascorbic acid (H ₃ ) stored as a reducing agent, the storage amount of neutralizing solution (H ₄ ), the storage amount of eluent ( H ₆ ), the storage amount of the coloring liquid (H ₇ ) is the storage amount (H ₂₀ , H ₃₀ ,
H ₄₀ , H ₆₀ , H ₇₀ ) is determined, and if the number is smaller, the content of the abnormality is displayed on the graphic display B as an abnormality. Further, as shown by “SP8D” in FIG. 7, based on the output data from the pH sensor 61, when the pH is lower than the set value (pH ₁ ), the supply amount of the neutralizing solution is increased, and Set value (pH
₂ ) When higher, the supply amount of the neutralizing solution is set to be small. During the SP8A, when the pressurizing pump 17 is not driven, the determination relating to “P ₂ ” is not performed, and the next SP8B
Proceed to. <SP9 to 12> In the above SP8, the supply pressure of the pressurizing pumps 6 and 17, the temperature in the reactor 3, the storage amounts of the storage units 15, 60, 57, 18, and 21, and the pH of the sample liquid are appropriate. If it is determined that the temperature of the reactor 3 is 100 ° C. or more (SP9), as shown in FIG.
49, Drive the pressure pump 17 and the liquid feed pump 20 (SP1
0). As a result, the eluent is supplied to the concentration column 9 to be washed. In SP9, measurement of a preset time (T ₀ ) is started by the timer (the timing at this time is set to the eighth time).
(Indicated by T in FIG. (A)). Thereafter, it is determined whether or not 1/2 of a preset time (T ₀ ) has elapsed (SP11), and in the case of YES, both the four-way valves 7 and 10 are set to the R side (in FIG. 1 by a dotted line). At the same time, the three-way valve 5 is turned off (the state shown by the solid line in FIG. 1), and the pressurizing pump 6 is turned off (SP12) (the timing at this time is indicated by T in FIG. 8 (A)). ). As a result, the sample is not supplied into the concentration column 9 and the state of washing with the eluent is maintained, and the metal ions adsorbed on the concentration column 8 are pumped to the detection means 32 by the eluent. And the absorbance is detected. However, at this time, the detection data is not transmitted to the control unit C because of the warm-up state. After the end of SP12, after repeating the flow of SP8A to SP8D shown in FIGS.
Proceed to SP13. <SP13> The measurement time of the timer is a preset time (T ₀ -5 (mi
n)), when the value of 0 of the absorptiometer 12 of the detection means 32 is reached.
A pulse signal for turning ON the point is output, and the detection unit 32 is calibrated. As a result, the base line (0 line) of the output value of the detection means 32 becomes a constant base regardless of the concentration of the sample liquid flowing from the separation column 11 side. <SP14> After the timer measures the set time (T ₀ ),
After the warm-up operation of the device has been completed, the four-way valve
Side (the side shown by a solid line in FIG. 1), and further, a three-way valve 5
Is turned ON (the side indicated by the dotted line in FIG. 1), and the pressurizing pump 6 is driven. As a result, the sample liquid is supplied to the concentration column 8 and the eluent is supplied to the concentration column 9, and the analysis operation of the sample liquid is started (the timing at this time is indicated by T in FIG. 8A).
). At the same time, the liquid feed pump 58 for adjusting the PH is driven. The preset T ₀ is the concentration column 8.9
This is the time for performing the initial cleaning. The driving of the liquid feed pump 58 is controlled based on the detection data of the PH sensor 61 so that the sample liquid becomes neutral. Hereinafter, the analysis flow of the metal component by the concentration column 8 will be described by SP15 to SP28, and the concentration column 9 will be described by SP29 to SP38.
The analysis flow of the metal component will be described. <SP15 to 19> On condition that the temperature of the heater is within the above-mentioned set value (SP15), the concentration column 8 or 9 is
The pH adjusting pump 58 is operated to adsorb metal ions with high efficiency (SP16). Here, the timer is started to measure the set time (T ₁ ) so that the pH in the apparatus becomes uniform (SP17). At this time, the pH of the sample solution is
Detected at 61. During the set time (T ₁ ), the sample solution is supplied to the concentration column 8 so that the metal component in the sample solution is adsorbed on the concentration column 8 and the concentration column 9 is washed with the eluent. The set time (T ₁ ) is defined as the “replacement time” in column 8 and the “wash time” in column 9 (see FIG. 8 (B)). When the timer measures the set time (T ₁ ) SP18), as shown in the flow of FIG. 4, the three-way valve 5 is turned off (the side shown by the solid line in FIG. 1), the pressurizing pump 6 is turned off, and at the same time, only the four-way valve 7 is turned to the R side (first side). (SP19) (the timing at this time is indicated by the dotted line in the figure).
(Indicated by T in FIG. (A)). The <SP20~22> timer, to start measuring the predetermined set time (T ₂₎ (SP20). During this time, the metal component adsorbed on the concentration column 8 is eluted and discharged to the drain 34 through the line 35. At this time, the three-way valve 5 is on the OFF solid line side and the pressurizing pump 6 is stopped.
Will be maintained as it is. The set time (T ₂ ) of the SP 20 is defined as “washing time” of the concentration column 8 and “stop time” of the concentration column 9 (see FIG. 8 (B)). When the timer measures the set time (T ₂ ) (SP2
1), the three-way valve 5 is set to NO (the side shown by the dotted line in FIG. 1), only the four-way valve 7 is set to the L side (the side shown by the solid line in FIG. 1), and the pump 6 is turned ON, and the pumps 17, 20 (SP22) (the timing at this time is set to 8th.
(Indicated by T in FIG. (A)). The <SP23~25> timer to start the measurement or the like preset enriched time (T ₃₎ (SP23). During this time, the sample solution is pressure-fed into the concentration column 8, and the metal component of the sample solution is adsorbed in the concentration column 8, and then discharged to the drain 34 through the line 35. At this time, since the pressurizing pump 17 is stopped, the stopped state of the concentration column 9 is maintained. The concentration time (T ₃ ) set in SP23 is referred to as “concentration time” in column 8 and “stop time” in column 9 (see FIG. 8 (B)). When the timer measures the set concentration time (T ₃ ) (SP24), the sampling valve 1 is switched to the next flow path (switched from the inflow path 1A to 1B, and the concentration is different from that of the inflow path 1B to 1A). The sample liquid is supplied), and the pump 2 is turned off only at this switching timing. At the same time, when measuring the absorbance of the metal ions adsorbed by the concentration column 8, a pulse signal for turning on the zero point of the absorptiometer 12 is output and calibration is performed again. Here, the four-way valves 7 and 10 are both connected to the R side (the side indicated by the dotted line in FIG. 1).
And the pumps 17 and 20 are turned on. Next, preparation for concentration processing by the concentration column 9 is performed (SP25) (the timing at this time is indicated by T in FIG. 8A). The <SP26~29> timer, to start measuring the predetermined set time (T ₄₎ (SP26). During this time, the eluent is supplied to the concentration column 8 and the metal component adsorbed on the concentration column 8 is eluted by the analysis means 32, and the sample solution supplied from the inflow path 1B is supplied to the other concentration column 9. Supplied. Then, the concentration of the metal component is measured in the analysis means 32 (SP27), and the sample liquid having passed through the concentration column 9 is discharged to the drain 34 via the line 35. The set time (T ₄ ) of the SP 26 is defined as the “analysis time” of the concentration column 8 and the “replacement time” of the concentration column 9 (see FIG. 8B). When the timer finishes measuring the set concentration time (T ₄ ) (SP28), the three-way valve 5 is set to OFF (the side indicated by the solid line in FIG. 1), and the pressurizing pump 6 is turned OFF. .
At the same time, only the four-way valve 7 is switched to the L side (the side indicated by the solid line in FIG. 1) (SP29) (the timing at this time is indicated by T in FIG. 8A). SP28A is located between SP28 and SP29.
In P28A, “displacement-washing-concentration-
It is determined whether or not to repeat the "analysis" process. The <SP30~32> timer to start the measurement or the like preset time (T ₂₎ (SP30). During this time, the concentration column 9
And the metal components in the concentration column 9 eluted by the eluent are discharged to the drain 34 through the line 35. Further, since the three-way valve 5 and the pressure pump 6 are both set to OFF, the concentration column 8 is in a stopped state. The set time (T ₂ ) of the SP 30 is defined as the “stop time” of the concentration column 8 and the “wash time” of the concentration column 9 (see FIG. 8 (B)). When the timer finishes measuring the set concentration time (T ₂ ) (SP31), the three-way valve 5 is set to ON (the side indicated by the dotted line in FIG. 1), the pump 6 is turned ON, and the pump 17 20 to
Set to OFF. At the same time, processing such as switching only the four-way valve 7 to the R side (the side shown by the dotted line in FIG. 1) is performed (SP32) (the timing at this time is indicated by T in FIG. 8A).
). The <SP33~36> timer, to start measuring the predetermined concentration time (T ₃₎ (SP33). During this time, the sample liquid supplied from the inflow passage 1B is supplied to the concentration column 9, and the metal component in the sample solution is adsorbed on the concentration column 9, and thereafter, the metal component passes through the concentration column 9 and the metal component passes therethrough. Removed sample liquid is line
After passing through 35, it is discharged to a drain 34. At this time, since the pressurizing pump 17 has stopped, the stopped state of the concentration column 8 is maintained. The concentration time (T ₃ ) set in SP33 is referred to as “stop time” of the concentration column 8 and “concentration time” of the concentration column 9 (see FIG. 8 (B)). When the timer finishes measuring the set concentration time (T ₃ ) (SP34), the sampling valve 1 is switched to the next flow path, and the pump 2 is switched only at this switching timing.
Is OFF. At the same time, in preparation for the measurement of the absorbance of the metal component adsorbed by the concentration column 9, a pulse signal for turning on the zero point of the 32 absorptiometers 12 is output and calibration is performed again. At this time, the four-way valves 7 and 10 are both switched to the L side (the side shown by the solid line in FIG. 1) and the pump
Turn on both 17 and 20 to prepare for the enrichment process by the next enrichment column 8 (SP35).
(Indicated by T in FIG. (A)). Then, in the next SP36, the inflow path of the sampling valve 1 to be set is switched to the next set flow path (inflow path 1C) if the previous (one previous) analysis result is appropriate. If the result is incorrect and inappropriate due to the control threshold, etc.
The flow returns to the inflow path (inflow path 1A) analyzed above, and is suctioned from the pump 2 to perform reanalysis. In the re-analysis, the concentration time of the metal ions is varied. <SP37-40> As shown in FIG. 5, a preset time (T ₄ )
Measurement is started by a timer (SP37). During this time,
The eluent is supplied to the concentration column 9 and the metal component adsorbed on the concentration column 9 is eluted by the analysis means 32, and the sample liquid supplied from the inflow channel 1A or 1C is supplied to the other concentration column 8. Supplied. And the analysis means 32
Then, the concentration of the metal component is measured (SP38), and the sample solution that has passed through the concentration column 8 is discharged to the drain 34 via the line 35. The set time (T ₄ ) of SP37 is defined as “analysis time” of the concentration column 9 and “replacement time” of the concentration column 8 (see FIG. 8B). When the timer completes the measurement of the set concentration time (T ₄ ) (SP39), each column 8 determines whether to repeat the “replacement-washing-concentration-analysis” process by the above-described concentration columns 8.9. -Judgment is made every 9 and as a result, the concentration column 8
When the process of the above cycle is performed, the process returns to SP19 (indicated by an arrow (a) in FIG. 8 (B)), and when the process of the above cycle is performed for the concentration column 9, the process returns to SP29. When a predetermined number of processes are completed in each of the concentration columns 8 and 9, the process proceeds to the next SP41 (SP40).
(The timing at this time is indicated by T in FIG. 8 (A)). Such determination of SP40 is also made in the above-described SP28A. <SP41-44> When the analysis is completed (at the timing shown in FIG. 8A), first, the heater of the reactor 3 is turned off, and further, the pumps 6, 16, 17, 20, 58, and 59 are turned off. Thereafter, the cooling fan 62 is turned on to cool the reactor 3 (SP41). After that, the absorptiometer 12, the flow meter 19 and the data recording section D
After turning OFF, and setting the four-way valves 7 and 10 to the L side (the side indicated by the solid line in FIG. 1), the one sampling valve is connected to the flow path 1A.
Switch to. Then, only during the time when the sampling valve 1 is switched, the pump 2 is temporarily turned off and set to NO again (SP42). Thereafter, based on the output data from the temperature sensor provided in the reactor 3, if the temperature of the heater of the reactor 3 drops to 80 ° C., the pump 2 is turned off, and the cooling fans 49 and 62 are turned off. (SP43) (the timing at this time is indicated by T in FIG. 8 (A)), and this flow is terminated (SP43).
44). Although not described in each SP of the above flow, the pressure in the path detected in SP1 to SP44, the temperature of the reactor 3, and the remaining amount of the reagent are always motorized. Display on graphic display and external computer display. In addition, the graphic display B displays an indication such as "analyzing", "concentrating", "analysis completed", and the like. According to the metal component analyzer shown in the present embodiment described in detail above, FIG. 8 (B) which summarizes the main parts of the flowcharts of FIGS. 3 to 7 and the time chart of FIG. 8 (A).
As can be seen by referring to the table in each of the columns 8 and 9,
Steps such as “replace” → “wash” are performed first,
After replacing each column 8.9 with the sample solution to be measured, the actual "concentration" → "analysis" of the metal ions is performed, so that the concentration efficiency in each column 8.9 is increased. This has the effect of improving the analysis accuracy. The processing such as “replacement—washing—concentration—analysis” is performed by the replacement function, cleaning function, concentration function, and analysis function of the control unit C. The stop shown in FIG. 8 (B) is due to the stop function of the control unit C. Also, in SP25 / 35, just before the measurement of the absorbance of the metal ions captured in each of the concentration columns 8.9, the zero-point adjustment of the absorptiometer 12 was performed, so that the analysis accuracy was increased,
In addition, since a fluid such as an eluent is not allowed to flow into the cell of the absorptiometer 12 at a stage before the zero point adjustment, a problem that the zero point level naturally rises during this period occurs. However, by outputting the signal for adjusting the O point immediately before the measurement of the absorbance of the metal ion as shown by the above-described SP25 / 35, the effect of eliminating the problem can be obtained. Further, according to the metal component analyzer shown in this embodiment,
Since the pH is adjusted by the adjusting unit 50 and the pH is monitored by the pH sensor 61 so as to maintain the neutrality,
In the concentration columns 8 and 9, metal ions, which are metal components of the sample solution, can be efficiently captured. As a result, the concentration efficiency is increased and the effect of improving the analysis accuracy is obtained. Note that such pH adjustment is performed by controlling the pH of the control unit C.
Depends on the adjustment function. “Effects of the Invention” As described in detail above, according to the first invention, in each concentration column, a process such as “replacement” → “washing” is performed first, and then the inside of each concentration column is measured. After passing through the sample solution, the metal ions in the sample solution are subjected to “concentration” → “analysis”. Since the actual adsorption and elution of the metal ion are performed from the above, the metal ion of the previously measured sample liquid does not remain in the concentration column, thereby increasing the concentration efficiency of the concentration column, The effect of improving the analysis accuracy is obtained. According to the second invention, the sample liquid supply pump and the elution supply pump are appropriately turned ON / OFF, and the first and second four-way switching valves are appropriately switched, so that “replacement → wash →
Concentration → analysis → stop → stop → replacement ”,“ washing → stop → stop → replacement → wash → concentration → analysis ”for the second concentration column
Since the respective processes are performed correspondingly, each process can be efficiently performed in cooperation with the two columns, and the effect that the concentration efficiency shown in the first invention can be further improved can be obtained. According to the third invention, the pH is adjusted by the pH adjusting unit,
In addition, since the pH is monitored by a pH sensor so as to maintain neutrality, the metal component (metal ion) of the sample liquid can be efficiently captured in the concentration column,
As a result, the effect of increasing the concentration efficiency and improving the analysis accuracy is obtained as in the second and third inventions.

[Brief description of the drawings]

FIGS. 1 to 8B are views for explaining an embodiment of the metal component analyzer of the present invention. FIGS. 1 and 2 are schematic structural views of the metal component analyzer, and FIG. 7 to FIG. 7 are flowcharts showing the control contents of the control unit of the metal component analyzer, FIG. 8 (A) is a timing chart corresponding to the flowchart, and FIG. 8 (B) is a diagram showing a main part of the timing chart. FIG. 9 is a schematic configuration diagram illustrating the configuration of a conventional metal component analyzer. 6 ... pressurizing pump (sample liquid supply pump), 7 ... 4-way automatic switching valve (first 4-way switching valve), 8 ... concentration column (first concentration column), 8a / 9a ... inflow path ( Parallel supply path),
8b ・ 9b… Outflow path (parallel supply path), 9… Concentration column (second concentration column), 10… Four-way automatic switching valve (second four-way switching valve), 17… Liquid feeding pump (elution) Liquid supply pump), 30 (30a-30d) ... sample liquid supply path, 31 ... eluent supply path, 32 ... analysis means, 33 ... line (sample liquid supply path), 34 ... discharge path, 50 … PH adjustment unit, 58… Solution pump, 61… pH sensor, C… Control unit (replacement function, washing function, concentration function, analysis function, stop function, pH adjustment function).

Claims (3)

(57) [Claims] 1. A sample liquid supply path to which a sample liquid containing a metal component is supplied, and a pair of parallel supply paths branched in two and provided in parallel in the middle of the sample liquid supply path; A first and a second concentration column provided in each parallel supply path for adsorbing a metal component in a sample liquid; a first four-way switching valve provided at a branch of the parallel supply path located on the upstream side; A second four-way switching valve provided at a branch of the parallel supply path located on the side, and an eluent that is connected to the first four-way switching valve and elutes the metal component adsorbed on the concentration column. An eluent supply path, and a discharge path connected to the second four-way switching valve to discharge the solution via each of the parallel supply paths;
An analyzing means provided in a sample liquid supply passage located downstream of the second four-way switching valve and detecting a concentration of a metal component in the sample liquid eluted by the eluent; The four-way switching valves are respectively switched to selectively supply a sample solution or an eluent to the first and second columns, and
A controller configured to selectively supply a sample liquid and an eluent through the first and second concentration columns to a discharge path or a sample liquid supply path leading to an analysis unit, wherein the control unit comprises: A replacement function of supplying a sample solution to cause the metal component in the sample solution to be adsorbed to one of the concentration columns, and discharging the sample solution after the adsorption of the metal component to a discharge path; and supplying the eluent to the one of the concentration columns. A washing function that elutes the metal component adsorbed on the sample and discharges the eluate after the elution to a discharge path; and supplies a sample solution to adsorb the metal component in the sample solution to one of the concentration columns after the washing. A concentration function of discharging the sample solution after the adsorption to a discharge path, and supplying an eluent to elute the metal component adsorbed to the one of the concentration columns after the washing, and analyzing the eluate after the elution with an analyzing means. Function to guide the sample liquid supply path leading to Metal component analyzer, characterized in that a. 2. The sample liquid supply path is provided with a sample liquid supply pump for supplying a sample liquid, and the eluent supply path is provided with an eluent supply pump for supplying an eluent, respectively. The driving of the sample liquid supply pump and the elution supply pump is stopped, and the first and second four-way switching valves are respectively switched to selectively supply the sample liquid or the eluent to the first and second columns. And selectively supplying a sample liquid and an eluent through the first and second concentration columns to a discharge path or a sample liquid supply path leading to an analysis means. After the sample solution is supplied to the first concentration column to adsorb the metal component, the sample solution is guided to the discharge path, and the eluate is supplied to the second concentration column for washing. Substitution that guides the liquid to the sample liquid supply path leading to the analysis means A washing function, supplying an eluent to the first concentration column to elute the adsorbed metal component, guiding the eluent to a discharge path, and stopping the sample liquid supply pump. A washing / stopping function for stopping the second concentration column by supplying the sample solution to the first concentration column after the washing to adsorb the metal component, and then transferring the sample solution after the adsorption to the discharge path. A condensing / stopping function for further stopping the stopped second concentration column by guiding the eluent supply pump, and supplying the eluent to the concentrated first concentration column. To elute the adsorbed metal component, guide the eluent to a sample liquid supply path leading to the analysis means, and supply the sample liquid to the stopped second concentration column to supply the metal component. After the sample is adsorbed, drain the sample liquid. And analysis and replacement functions to guide the first enrichment column after the analysis process by stopping the sample liquid supply pump is stopped, and the second
Supplying an eluent to the concentration column to elute the adsorbed metal component, and then guiding the eluent to a discharge path; a stop / wash function; and stopping the eluent supply pump to stop the eluent. After further stopping the first concentration column therein, and supplying the sample solution to the washed second concentration column to adsorb the metal component, the adsorbed sample solution is guided to the discharge path. Stopping and concentrating functions, after supplying a sample liquid to the stopped first concentrating column to adsorb metal components, guiding the sample liquid to a discharge path, and performing the concentrating second condensing After supplying the eluent to the column to elute the adsorbed metal component, the eluent is guided to a sample liquid supply passage leading to the analysis means.
The metal component analyzer according to claim 1, further comprising an analysis function. 3. A sample pump for supplying a neutralizing solution for neutralizing a sample solution to a sample solution supply passage located upstream of the first four-way switching valve to adjust the pH of the sample solution. pH adjuster,
PH for monitoring the pH of the sample solution adjusted by this pH adjustment unit
And a sensor is sequentially provided, wherein the control unit has a pH adjusting function of adjusting a supply amount of the neutralizing solution by the liquid sending pump based on the detection data of the pH sensor. Item 3. The metal component analyzer according to Item 1 or 2.