JP2012047657A - Automatic measurement apparatus for aluminum - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an automatic measurement apparatus for aluminum for measuring high-concentration aluminum containing a solid component and a soluble component in order to manage the aluminum concentration in a water purification process.SOLUTION: An automatic measurement apparatus for aluminum includes: a sample water pump 51 for sampling sample water; an ECR solution pump 57 for adding an Eriochrome Cyanine Red (ECR) solution; an ECR solution tank 56 for collecting the ECR solution; a first stirring tub 52 to which the sample water and the ECR solution are supplied; a buffer liquid pump 59 for adding a buffer liquid; a buffer liquid tank 58 for collecting the buffer liquid; a second stirring tub 53 to which a liquid stirred and mixed in the first stirring tub 52 and the buffer liquid are supplied; and an absorbance measuring device 54 to which a liquid stirred and mixed in the second stirring tub 53 is supplied.

Description

  The present invention relates to an aluminum automatic measuring apparatus capable of automatically measuring aluminum contained in water during a water purification process.

In the water purification plant, a flocculant is injected into the raw water taken to aggregate the turbid components in the raw water to form flocs, and the flocs formed are settled and separated in a sedimentation basin. Precipitated water from which flocs have been settled and separated is introduced into a filtration basin, which is the next water purification facility, and filtered.
In this coagulation sedimentation treatment, the coagulant injection rate determined according to the raw water quality is important.

In the coagulation sedimentation treatment, the coagulant injection rate is generally calculated from the measurement results of raw water quality (turbidity, alkalinity, pH, etc.) according to a preset coagulant injection model formula, and the coagulant is added based on the coagulant injection rate. Feed forward feedback control that combines feed forward control for injection and feedback control for correcting the flocculant injection rate based on the measurement result of turbidity at the sedimentation tank outlet is employed. However, due to the nature of the coagulation sedimentation treatment, there is a large time delay of about 3 to 4 hours from the time when the coagulant is injected until the turbidity at the final sedimentation tank outlet is determined.
For this reason, it is difficult to correct the flocculant injection rate by feedback.

  Since the time delay is large in feeding back the measurement result of the turbidity at the sedimentation basin outlet, a flocculant injection control method using the micro flocs after the flocculant injection as an index is described in, for example, [Patent Document 1]. Has been proposed. This control method reduces the time delay of feedback correction by sampling the raw water injected with the flocculant at an earlier stage than the outlet of the sedimentation site. Correction is possible.

  If a lot of micro flocs are formed in the raw water into which the flocculant has been injected, the subsequent floc growth slows down, resulting in high turbidity at the sedimentation tank outlet. Therefore, the flocculant injection rate can be corrected with high accuracy by classifying minute flocs by a classifying means such as a filter and measuring the amount thereof. Here, the minute floc can be quantified by measuring the aluminum concentration of the solid component.

  In order to realize this coagulant injection control method, a measuring device that can easily and automatically measure the aluminum concentration of the solid component is required, and it is desirable that the measuring device be inexpensive.

Examples of the method for measuring the aluminum concentration in the sample water include atomic absorption spectrophotometry, ICP emission spectroscopic analysis, ICP mass spectrometry, and spectrophotometry. Among these, as a spectrophotometric method, there is a method of using Eriochrome Cyanine Red (C ₂₃ H ₁₅ Na ₃ O ₉ S, hereinafter referred to as ECR) as a color reagent. This is one in which a soluble aluminum causes a color reaction with an ECR reagent in the region of pH 4.6 to 5.6 to form a complex, and its absorbance is determined and quantified.

  As a method for measuring the aluminum concentration using an ECR reagent, for example, [Patent Document 2] discloses a metal ion concentration measuring device capable of adjusting the temperature of sample water.

JP 2010-137115 A JP 2008-96396 A

  The atomic absorption spectrophotometry, ICP emission spectroscopy, ICP mass spectrometry, and the method described in [Patent Document 2], which are methods for measuring the aluminum concentration in sample water, are difficult to measure when the sample water contains solid components. Yes, when it is desired to measure the solid component aluminum, it is necessary to inject an acid in advance to dissolve the solid component. Therefore, in order to automate, it is necessary to provide an acid injection pump, an acid tank, and a dissolution tank, and there is a problem that the measuring apparatus is complicated and expensive.

  An object of the present invention is to provide a simple and inexpensive aluminum automatic measuring apparatus capable of measuring aluminum in flocs.

  In order to achieve the above object, an aluminum automatic measurement apparatus of the present invention includes a sample water pump for collecting sample water, an ECR solution pump for adding an ECR solution, and an ECR for storing the ECR solution. A solution tank; a first agitation tank to which the sample water and the ECR solution are supplied; a buffer pump for adding a buffer; a buffer tank for storing the buffer; and the first agitation And a second agitation tank to which the liquid stirred and mixed in the tank and the buffer solution are supplied, and an absorbance measuring apparatus to which the liquid agitated and mixed in the second agitation tank is supplied.

  A sample water pump for collecting sample water; an ECR solution pump for adding an ECR solution; an ECR solution tank for storing the ECR solution; a buffer pump for adding a buffer; A buffer tank for storing the buffer solution, a supplied sample water, the ECR solution, an agitation tank for agitating and mixing the buffer solution, and a liquid agitated and mixed in the agitation tank are supplied. And an absorbance measuring device to which the liquid stirred and mixed in the stirring tank is supplied.

  According to the present invention, an acidic ECR reagent is added to sample water prior to a pH adjustment buffer solution, so that an aluminum automatic measuring device that is simple and inexpensive for measuring the aluminum concentration of a solid component can be obtained. It becomes possible to provide.

It is a figure explaining the automatic measuring apparatus of aluminum which is Example 1 of this invention. It is a figure which shows the test flow of an absorbance measurement. It is a figure which shows the relationship between the measurement wavelength of sample water which carried out the color reaction, and the light absorbency. It is a figure which shows the test flow of the continuous measurement test of the light absorbency which is Example 1 of this invention. It is a figure which shows the continuous measurement result of the light absorbency which is Example 1 of this invention. It is a figure which shows the relationship between aluminum concentration and a light absorbency. It is a figure explaining the automatic measuring apparatus of aluminum which is Example 2 of this invention. It is a figure explaining the automatic measuring apparatus of aluminum which is Example 3 of this invention. It is a figure explaining the automatic measuring apparatus of aluminum which is Example 4 of this invention. It is a figure which shows the processing flow until the measurement of the aluminum concentration which is Example 5 of this invention.

  Embodiments of the automatic aluminum measuring apparatus of the present invention will be described below with reference to the drawings.

  In order to solve the above-described problems, the present inventors paid attention to the pH of the ECR reagent. In general, the ECR reagent is acidic at pH 2 or lower in order to prevent its deterioration. The sample water and the acidic ECR reagent are mixed to dissolve the solid component aluminum first. Thereafter, a buffer solution for pH adjustment is added, and the absorbance is measured. Thereby, an inexpensive and simple automatic measuring device for aluminum can be realized.

  That is, by adding an acidic ECR reagent to the sample water prior to the pH adjustment buffer solution, the solid component aluminum is dissolved, and the dissolved component and the solid component aluminum can be measured together.

  A first embodiment of the present invention will be described with reference to FIGS. FIG. 1 is a diagram showing an automatic measuring apparatus for aluminum in Embodiment 1 of the present invention.

  The aluminum automatic measuring apparatus of the present embodiment is configured as follows. A pipe for supplying sample water is connected to the first stirring tank 52, and a sample water pump 51 is provided in the middle thereof. The ECR solution tank 56 is provided with a pipe for supplying the ECR solution to the pipe on the downstream side of the sample water pump 51, and an ECR solution pump 57 is provided in the middle of the pipe.

  A pipe for supplying the mixed liquid a is connected to the second stirring tank 53 in the first stirring tank 52, and a pipe for supplying the mixed liquid b is connected to the absorbance measuring device 54 in the second stirring tank 53. Is provided with an electromagnetic valve 62. The buffer tank 58 is connected to a pipe for supplying the mixed solution a by a pipe, and a buffer pump 59 is provided in the middle of the pipe. The pure water tank 60 is connected to an electromagnetic valve 62 by piping, and a pure water pump 61 is provided in the middle of the piping. The absorbance measuring device 54 is connected to a waste liquid tank 55 by piping. The absorbance measuring device 54 is connected to the data recording means 63 by a signal line.

  The sample water is supplied to the first stirring tank 52 at a constant flow rate by the sample water pump 51. Here, as the sample water pump 51, a means that can be continuously supplied at a constant flow rate such as a tubing pump or a plunger pump is applied. In order to reduce the amount of reagent used, a flow rate of 5 to 100 mL / min, preferably 10 to 40 mL / min is supplied.

  The ECR solution is supplied from the ECR solution tank 56 to the first stirring tank 52 using the ECR solution pump 57. Here, as with the sample water pump 51, the ECR solution pump 57 may be any means that can continuously supply at a constant flow rate.

  The ECR solution is adjusted by adding a predetermined amount of ECR reagent to the solvent. Here, in the ECR solution, the constituent material changes to a reduced chemical species over time, and discolors, so it is necessary to adjust the pH to 2.0 or less to prevent discoloration. Therefore, an acidic liquid such as hydrochloric acid can be used as the solvent.

  In addition to forming a complex with aluminum in the sample water, the ECR solution has a role of dissolving solid aluminum. Therefore, when the ECR solution is added to the sample water, it is necessary to determine the pH and the addition rate of the ECR solution so that the pH is such that the solid component aluminum can be dissolved.

  The concentration of the ECR reagent is set so that the absorbance is within the measurement range of the absorptiometer when the required aluminum concentration is reached. The concentration of the ECR reagent is 0.005 to 0.20 mg / mL, preferably 0.01 to 0.10 mg / mL after addition to the sample water.

  The ECR solution has a pH of 1.9, and the pH of the sample water becomes about 3 by adding 10% to the amount of the sample water. If the pH is 4 or less, the aluminum compound in the floc can be dissolved. The pH of the ECR solution is 2 or less, preferably 1 to 2 in terms of preventing deterioration and dissolving the aluminum compound.

  The concentration of the acetate buffer is 0.2 to 5 mol / L, preferably 0.5 to 5 mol / L in order to make the pH range in which aluminum reacts with ECR and forms a complex. After the addition of this acetate buffer, the amount added is adjusted so that the pH of the sample water is 4.6 to 5.6. For example, the molar amount of acetate buffer (concentration of acetate buffer × addition amount) is 0.5 to 4 mol / L, preferably 1 to 3.5 mol / L, relative to the addition amount of ECR solution at pH 1.9. .

  The sample water and the ECR solution are stirred and mixed in the first stirring tank 52. Here, the stirring means may be any means capable of obtaining good stirring, and examples thereof include a means using a stirrer and a magnetic stirrer. The residence time of the sample water in the first stirring tank 52 is within 5 minutes, preferably 1 to 3 minutes.

  The mixed solution a obtained by mixing the sample water and the ECR solution is supplied to the second stirring tank 53. A buffer solution is supplied from the buffer solution tank 58 to the second agitation tank 53 using a buffer solution pump 59. Here, as with the sample water pump 51 and the ECR solution pump 57, the buffer pump 59 may be any means that can be continuously supplied at a constant flow rate.

  The purpose of adding the buffer solution is to make the pH range from 4.6 to 5.6, where aluminum reacts with the ECR reagent to form a complex. Therefore, the pH of the buffer solution is determined in the range of 4.6 to 5.6. Further, the concentration and addition rate of the buffer solution must be determined so that the pH of the sample water after the addition of the ECR solution falls within the range of 4.6 to 5.6. Although it is important that the buffer solution is within the set pH range, it is desirable that the buffer solution is not subject to the PRTR target substance from the viewpoint of the environment. For example, an acetic acid buffer solution in which acetic acid and sodium acetate solution are mixed may be used.

  The mixed solution a and the buffer solution are stirred and mixed in the second stirring tank 53. Here, the stirring means may be any means that can obtain good stirring as in the first stirring tank 52. In the second agitation tank 53, the dwell time of the sample water is within 5 min, preferably 1 to 3 min, like the first agitation tank 52.

  The mixed solution b obtained by mixing the mixed solution a and the buffer solution is supplied to the absorbance measuring device 54. The absorbance measuring device 54 measures the absorbance of the mixed solution b. Here, although the cell used for measuring the absorbance is influenced by the flow rate of the mixed solution b and the measurement accuracy, it is preferably a commercially available cell of 1 to 5 cm. The measurement wavelength needs to be determined from the range showing high absorbance.

  The absorbance measuring device 54 is periodically supplied with pure water from a pure water tank 60 by a pure water pump 61 to adjust the zero point of absorbance. When adjusting the zero point, the pure water pump 61 and the electromagnetic valve 62 are controlled by control means (not shown). Further, while a drain port (not shown) is attached to the second stirring tank 53 and the zero point is adjusted, the mixed solution b does not pass through the absorbance measuring device 54 but is directly drained to the waste liquid tank 55. ing.

  FIG. 2 shows a test flow for measuring absorbance according to the method of this example. In S1, 5 mL of an aluminum standard solution having an aluminum concentration of 0.15 mg / L is taken as sample water. In S2, 0.5 mL of 0.05 wt.% ECR solution is added to the sample water. In S3, immediately after adding the ECR solution, stir for 3 minutes. In S4, 0.8 mL of 2 mol / L acetate buffer adjusted to pH 5.0 is added. In S5, immediately after adding the acetate buffer, stir for 4 min. In S6, the absorbance is finally measured in the measurement wavelength range of 200 to 600 nm. Here, the absorptiometer adjusts the absorbance to zero with pure water.

  FIG. 3 shows the relationship between the measurement wavelength of the sample water subjected to color reaction and the absorbance. As can be seen from FIG. 3, the absorbance resulted in a peak at a measurement wavelength near 530 nm. Therefore, the measurement wavelength is 490 to 550 nm, preferably 515 to 535 nm.

  FIG. 4 shows a flow of continuous measurement of absorbance in this example. In S7, the absorbance measurement device 54 is activated. In S8, the electromagnetic valve 62 is operated, and in S9, pure water is supplied to adjust the absorbance to zero. In S10, the solenoid valve 62 is operated, and in S11, the sample water pump 51 is operated at a flow rate of 25 mL / min. In S12, the ECR solution pump 57 is operated at a flow rate of 2.5 mL / min. Here, the ECR solution is 0.05 wt%, and the capacity of the first stirring tank 52 is 50 mL. In S13, the buffer pump 59 is operated at a flow rate of 4 mL / min. Here, a 2 mol / L acetate buffer adjusted to pH 5.0 by mixing acetic acid and sodium acetate solution is used as the buffer. Moreover, the capacity | capacitance of the 2nd stirring tank 53 is 50 mL.

  FIG. 5 shows the results of continuous measurement of absorbance in this example. After the absorbance is stabilized after the measurement is started, the absorbance increases when the aluminum concentration of the sample water is switched from 0.01 mg / L to 0.05 mg / L, and the absorbance becomes stable 10 minutes after switching. It became constant. Even when the aluminum concentration was sequentially switched to 0.15, 0.30, and 0.50 mg / L at intervals of 20 min, the absorbance was stable and constant at 10 min. From this result, it can be seen that the aluminum automatic measuring apparatus of this example can cope with the change in the aluminum concentration in about 10 minutes.

  FIG. 6 shows the relationship between the aluminum concentration and the absorbance. The aluminum concentration and absorbance are in a proportional relationship when the aluminum concentration is in the range of 0.01 to 0.50 mg / L. Therefore, the method of the present embodiment can cover the range necessary for measuring the aluminum concentration in the water purification plant.

  The measured absorbance is recorded by the data recording means 63. Here, the absorbance to aluminum concentration is converted using an absorbance-aluminum concentration calibration curve prepared in advance. However, the conversion may be performed in the data recording means 63 or by using a data conversion means (not shown). Also good. The calibration curve is updated when the zero point is adjusted in S9 shown in FIG.

  The mixed liquid b after measuring the absorbance is drained into the waste liquid tank 55. Since the waste liquid is a solution having a pH of about 5, neutralization is performed if necessary.

  In the present embodiment, an acidic ECR reagent is added to the sample water prior to the pH adjusting buffer, whereby the aluminum concentration reflecting the solid aluminum can be measured.

  A second embodiment of the present invention will be described with reference to FIG. FIG. 7 is a configuration diagram of an aluminum automatic measuring apparatus according to the second embodiment.

  While Example 1 is a continuous system that supplies sample water and a reagent, Example 2 is a batch system that periodically supplies sample water and a reagent.

  The aluminum automatic measuring apparatus of the present embodiment is configured as follows. A pipe for supplying sample water is connected to the stirring tank 64, and a sample water pump 51 is provided in the middle thereof.

  The ECR solution tank 56 is provided with piping for supplying the ECR solution to the stirring tank 64, and an ECR solution pump 57 is provided in the middle of the piping. The buffer solution tank 58 is provided with a pipe for supplying the buffer solution to the stirring tank 64, and a buffer solution pump 59 is provided in the middle of the pipe.

  The stirring tank 64 is provided with a pipe for supplying the mixed solution b, and is connected to the absorbance measuring device 54. A supply pump 65, an electromagnetic valve 62, and an electromagnetic valve 68 are provided in the middle of the piping. The pure water tank 60 is connected to an electromagnetic valve 62 by piping, and a pure water pump 61 is provided in the middle of the piping. The cleaning liquid tank 66 is connected to an electromagnetic valve 68 by piping, and a cleaning liquid pump 67 is provided in the middle of the piping.

  In the present embodiment, the stirring tank 64, the sample water pump 51, the ECR solution tank 56, the ECR solution pump 57, the buffer solution tank 58, the buffer solution pump 59, the absorbance measuring device 54, the supply pump 65, the electromagnetic valve 62, and the electromagnetic valve 68. The pure water tank 60, the pure water pump 61, the cleaning liquid tank 66, and the cleaning liquid pump 67 are installed in the temperature adjustment tank 110.

  The absorbance measuring device 54 is connected to a waste liquid tank 55 by piping. The absorbance measuring device 54 is connected to the data recording means 63 by a signal line.

  The aluminum automatic measuring apparatus in Example 2 will be described in detail.

A certain amount of sample water is supplied to the stirring tank 64 by the sample water pump 51. Here, as the sample water pump 51, a tubing pump or a plunger pump is used, but a predetermined amount of sample water is supplied to and stopped from the stirring tank 64 by a control means (not shown).
The required amount of sample water at this time is 5 to 100 mL, preferably 10 to 40 mL, in order to reduce the reagent amount.

  When the sample water is supplied to the stirring tank 64, the ECR solution is supplied from the ECR solution tank 56 to the stirring tank 64 by the ECR solution pump 57. Here, like the sample water pump 51, the ECR solution pump 57 supplies and stops a certain amount of sample water to the stirring tank 64 by a control means (not shown).

  The sample water and the ECR solution are stirred and mixed in the stirring tank 64. Any stirring means may be used as long as it can obtain good stirring as in the first embodiment. For example, there is a means using a stirring bar and a magnetic stirrer. At this time, the residence time is within 5 minutes, preferably 1 to 3 minutes.

  After the sample water and the ECR solution are stirred and mixed, a buffer solution is supplied to the stirring vessel 64 from the buffer solution tank 58 using the buffer solution pump 59. Similarly to the sample water pump 51 and the ECR solution pump 57, the buffer pump 59 supplies and stops a certain amount of sample water to the agitation tank 64 by control means (not shown). The stirring and mixing operations are the same as when stirring and mixing the sample water and the ECR solution.

  The mixed solution b in which the sample water, the ECR solution, and the buffer solution are stirred and mixed is supplied to the absorbance measurement device 54 by the supply pump 65. The absorbance measuring device 54 measures the absorbance of the mixed solution b.

  As in the first embodiment, pure water is periodically supplied from the pure water tank 60 by the pure water pump 61 to the absorbance measuring device 54, and the zero point of absorbance is adjusted. When adjusting the zero point, the pure water pump 61 and the electromagnetic valve 62 are controlled by control means (not shown). The mixed liquid b is drained directly to the waste liquid tank 55 without passing through the absorbance measuring device 54 while a drainage port (not shown) is attached to the stirring tank 64 and the zero point is adjusted.

  The measured absorbance is recorded by the data recording means 63. Here, the conversion from absorbance to aluminum concentration uses a previously prepared absorbance-aluminum concentration calibration curve, but the conversion may be performed in the data recording means 63 or using a data conversion means (not shown). Good. Similar to the first embodiment, the calibration curve is updated when the zero point is adjusted.

  The mixed liquid b after measuring the absorbance is drained into the waste liquid tank 55. In the case of the second embodiment, the cleaning liquid pump 67 and the electromagnetic valve 68 are periodically controlled by a control unit (not shown), and the cleaning liquid is supplied from the cleaning liquid tank 66 to the absorbance measuring device 54. Here, as the cleaning liquid, one that can clean the cell of the absorbance measuring device 54 such as pure water and acid is used. At this time, the mixed liquid b is drained directly into the waste liquid tank 55 in the same manner as when the zero point is adjusted.

  In the above-described cleaning operation, an acetate buffer may be used as the cleaning liquid, and the cleaning liquid pump 67 and the cleaning liquid tank 66 can be removed by cleaning the cell with the acetate buffer. Since the waste liquid is a solution having a pH of about 5, neutralization is performed if necessary.

  When moving to the next measurement of absorbance, the liquid remaining in the stirring vessel 64 is replaced with the sample water by operating the sample water pump 51, and thereafter the same operation is repeated.

  The above operation is performed in the temperature adjustment tank 110. The temperature in the temperature adjustment tank 110 is adjusted to 0 to 40 ° C, preferably 10 to 30 ° C.

  In Example 2, the aluminum concentration is measured at set intervals by a control means (not shown). The aluminum automatic measurement apparatus according to the second embodiment is more complicated in operation than the first embodiment, but the amount of reagent used can be reduced. Further, the cell is prevented from being contaminated by regular cleaning, and stable absorbance measurement is possible.

  A third embodiment of the present invention will be described with reference to FIG. FIG. 8 is a configuration diagram of an aluminum automatic measuring apparatus according to the third embodiment.

  The third embodiment is configured in the same manner as the first embodiment. However, in the aluminum automatic measuring apparatus according to the third embodiment, the heater 80 and the temperature measuring means 90 are attached to the first stirring tank 52, and the temperature is not shown. The control means is provided with temperature measuring means.

  The aluminum automatic measurement apparatus of Example 3 can promote dissolution of the solid component aluminum compound by the acid by heating the sample water in the first stirring tank 52. Here, as heating temperature, 40-80 degree | times higher than room temperature is good.

  A fourth embodiment of the present invention will be described with reference to FIG. FIG. 9 is a configuration diagram of an aluminum automatic measuring apparatus according to the fourth embodiment.

  The fourth embodiment is configured in the same manner as the first embodiment. However, in the automatic measuring apparatus for aluminum of the fourth embodiment, the insoluble matter removing means 100 is attached between the second stirring tank 53 and the absorbance measuring apparatus 54. Yes.

  In the aluminum automatic measurement apparatus of Example 4, turbidity that is insoluble in acid is removed in front of the absorbance measurement apparatus 54. Thereby, contamination of the cell is prevented and stable absorbance measurement is possible. Here, the insoluble matter removing means 100 is a filter or the like, and a filter having an opening of 10 μm or less, preferably 0.45 to 5 μm is preferable. The insoluble matter removing means 100 may be attached singly or a plurality of insoluble matter removing means 100 may be attached in parallel. In order to maintain the performance of the filter for a long period of time, a backwash device may be attached.

  A fifth embodiment of the present invention will be described with reference to FIG. FIG. 10 is a processing flow up to the measurement of the aluminum concentration in Example 5.

  Example 5 is an automatic measurement apparatus for aluminum according to Example 1, in which the absorbance measurement apparatus 54 measures at a plurality of wavelengths instead of a single wavelength, and includes data conversion means for correcting the aluminum concentration. Yes.

If there are obstacles in the sample water, the measurement of absorbance is disturbed. For example, using an aluminum standard solution with an aluminum concentration of 0.15 mg / L and an aluminum standard solution with an aluminum concentration of 0.15 mg / L containing 0.25 cm ^{−1 of} UV absorbance of humic acid (organic matter) as an obstacle substance, When the absorbance measurement test shown in FIG. 2 is carried out (the absorbance is adjusted to zero with pure water), the absorbance at the measurement wavelength of 535 nm is 0.736 cm ⁻¹ when no organic matter is contained, When organic matter is contained, it becomes 0.776 cm ⁻¹ and the same absorbance is not obtained. Therefore, when an organic substance is included, it is necessary to correct the aluminum concentration.

  Next, a method for correcting the aluminum concentration will be described.

  In the processing flow for measuring the aluminum concentration shown in FIG. 10, the absorbance measuring device 54 is activated in S14. The absorbance measurement device 54 in Example 5 has two measurement systems with different wavelengths. Here, one of the different wavelengths is a measurement wavelength at which an obstacle substance can be quantified, for example, ultraviolet absorbance (260 nm), and the other is a wavelength at which aluminum can be measured. Here, the measurement system of the measurement wavelength capable of quantifying the obstacle substance is referred to as series 1, and the measurement system of the wavelength capable of measuring aluminum is referred to as series 2.

  In S15, the electromagnetic valve 62 is operated. In S16, the absorbance of series 1 and series 2 is adjusted to zero with pure water. In S17, the solenoid valve 62 is operated.

  In S18, the sample water pump 51 is operated. Here, in Example 1, the sample water is supplied to the first agitation tank 52, but in Example 5, a part of the sample water is supplied to the line 1 side through a separate pipe, and the rest is the same as in Example 1. It is supplied to the first stirring tank 52.

  In S19, the ECR solution pump 57 is operated. In S20, the buffer pump 59 is operated. In S21, the absorbance a is measured, and in S22, the absorbance b is measured.

  In S23, the aluminum concentration is corrected by the data correction means using the measured absorbance a and absorbance b. The data conversion means capable of correcting the aluminum concentration calculates a correction value of the aluminum concentration using the equation 1 from the received absorbance a data, for example.

[Equation 1]
(Correction value) = A × (absorbance a) (1) Here, A is a coefficient.

  The data conversion means capable of correcting the aluminum concentration calculates the aluminum concentration from the received absorbance b data using a calibration curve. Then, for example, the aluminum concentration is calculated using Equation 2.

[Equation 2]
(Aluminum concentration) =
(Aluminum concentration calculated from absorbance b) − (correction value) (2) In S24, the aluminum concentration is stored in the data recording means.

  Although the data conversion means capable of correcting the aluminum concentration as described above has been shown, other mathematical expressions may be used as long as the aluminum concentration can be corrected.

  In the fifth embodiment, the absorbance measurement device 54 having two measurement systems has been described as an example. However, the absorbance measurement device 54 capable of changing the measurement wavelength may be used in one measurement system.

  In Example 5, the absorbance of the sample water itself is measured, and the correction value is calculated by the data conversion means. However, the absorbance is measured using the ECR solution and the solution after addition of the buffer solution, and the same processing is performed. A correction value may be calculated.

  The aluminum automatic measurement apparatus according to the fifth embodiment is configured such that the absorbance measurement device 54 measures a plurality of wavelengths instead of a single wavelength, and includes the absorbance measurement device 54 and data conversion means capable of correcting the aluminum concentration. Thus, it is possible to measure the aluminum concentration even if there are obstacles in the sample water.

51 Sample Water Pump 52 First Stirring Tank 53 Second Stirring Tank 54 Absorbance Measuring Device 55 Waste Liquid Tank 56 ECR Solution Tank 57 ECR Solution Pump 58 Buffer Liquid Tank 59 Buffer Liquid Pump 60 Pure Water Tank 61 Pure Water Pumps 62, 68 Solenoid Valve 63 Data recording means 64 Stirring tank 65 Supply pump 66 Cleaning liquid tank 67 Cleaning liquid pump 80 Heater 90 Temperature measuring means 100 Insoluble matter removing means 110 Temperature adjusting tank

Claims (8)

  A sample water pump for collecting sample water, an ECR solution tank for storing an ECR solution, an ECR solution pump for adding an ECR solution from the ECR solution tank, the sample water and the ECR solution are supplied. A first agitation tank, a buffer tank for storing the buffer, a buffer pump for adding the buffer from the buffer tank, a liquid stirred and mixed in the first agitation tank, and the buffer An aluminum automatic measuring apparatus comprising: a second stirring tank to which a liquid is supplied; and an absorbance measuring apparatus to which the liquid stirred and mixed in the second stirring tank is supplied.   A sample water pump for collecting sample water, an ECR solution tank for storing an ECR solution, an ECR solution pump for adding an ECR solution from the ECR solution tank, and a buffer solution tank for storing a buffer solution A buffer pump for adding a buffer from the buffer tank, a stirring tank for stirring and mixing the supplied sample water, the ECR solution, and the buffer, and stirring in the stirring tank. A batch-type automatic measurement of aluminum concentration, comprising: a supply pump for supplying the mixed liquid; and an absorbance measurement device supplied with the mixed liquid stirred and mixed in the stirring tank. apparatus.   The apparatus for automatically measuring aluminum according to claim 1 or 2, wherein the pH of the ECR solution is 1 to 2 and the pH of the sample water after the addition of the ECR solution is 4 or less.   4. The automatic aluminum measuring apparatus according to claim 3, wherein the addition amount of the ECR reagent is 0.005 to 0.20 mg / mL.   A heater for heating the sample water and the ECR solution supplied into the first stirring tank, and a temperature measuring means for measuring the temperature in the first stirring tank, The automatic measuring device for aluminum according to claim 1 or 2.   The absorbance measuring device measures a plurality of wavelengths, and measures the absorbance of the obstacle substance at the first wavelength, the absorbance of aluminum and the obstacle substance at the second wavelength, and calculates the aluminum concentration from the measurement result. The aluminum automatic measuring device according to claim 1 or 2, characterized in that:   The automatic measuring apparatus for aluminum according to claim 6, wherein the first wavelength is 254 to 260 nm.   The apparatus for automatically measuring aluminum according to claim 1 or 2, wherein a part or the whole of each device configuration is installed in a temperature control tank for carrying out in a temperature controlled environment.

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