JPS58213233A - Method and device for continuously measuring nickel ion concentration - Google Patents

Abstract

PURPOSE:To measure Ni<++> concn. continuously in an instant from both light transmittance values, by measuring the light transmittances of the Ni<++> absorption peak and at the same time, the light of the wavelength of the sample water contg. Ni<++> continuously flowing at the bottom of the absorption near said peak of Ni<++> as the background. CONSTITUTION:The sample water contg. Ni<++> is passed through a deaerator 8 and a filter 7 to the sample inlet 3a of an absorption cell 3 made changeable in cell length in accorance with Ni<++> concn. by controlling plastic bellows provided in the middle of the cell. The water is passed through the cell 3 and the outlet 3b. The transmittance of Ni<++> is measured at 400nm or 720nm absorption peak by using 250-900nm light emitted by a light source 1a, a semireflective mirror 2b, and a photoelectric element 2b, and that of the water sample is measured at the same time at a wavelength where Ni<++> is not absorbed, and near said peak, e.g., 500nm, with a photoelectric element 2c. The Ni<++> concn. is recorded with a record control signal generating circuit 12 by eliminating the background value of the water from the peak absorbance value through an amplifying computing circuit 11, and control of an Ni recovery device, etc. are carried out with the circuit 12, thus permitting continuous and instantaneous measurement of Ni<++> concn.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method and apparatus for measuring nickel ions in water, particularly a method and apparatus for continuously measuring nickel ions in flowing water.

The conventional method for measuring the concentration of nickel in secondary nickel electrolytic washing water is to take the collected sample water to the laboratory and quantify it using a standard chemical analysis method (for example, JISKOlol or JISKO).
102) Alternatively, there are methods such as timely on-site analysis using a simple water quality analyzer, but the former provides high accuracy of analysis results, but requires a long time for analysis operations and is extremely slow, so it is not recommended to use a nickel recovery device. This method is not suitable for continuously controlling nickel m*□ in introduced water, and although the latter method is faster than the former, it is not suitable for continuously controlling fluctuations in nickel concentration. Ta. In addition, both methods add reagents to sample water and measure the early color reaction of nickel or the atomic absorption of nickel.
The waste liquid after measurement had to be treated separately.

The present invention solves the troublesome and inefficient measurement of nickel ion concentration as described above, and reduces the amount of nickel ions to be measured into three
The present invention provides a method and a measuring device that can continuously measure water while it is in a fluid state.

That is, the gist of the first invention is that among the light transmitted through the test water in a flowing state, wavelengths of 250 to 900 n1
The amount of light transmitted through water containing nickel ions and substances other than nickel ions is determined using light with a nickel ion absorption peak wavelength within the range of A continuous measurement method for nickel ion concentration characterized by determining the amount of light transmitted through water containing substances other than ions, and determining the nickel ion concentration from the amount of transmission of both, and the second gist of the invention. The sample water in the cell is irradiated with light from a light source installed at one end of the absorption cell, and the intensity of the transmitted light in A is measured by the transmitted light detector installed at the other end of the cell. In this device, the concentration of a substance S in the sample water is measured by a theoretical circuit based on the intensity of the absorption cell. The photodetecting section is composed of a measuring part for measuring light with a nickel ion absorption peak wavelength in the wavelength range of 250 to 900 nm and a measuring part for light having a wavelength at the absorption bottom near the absorption peak wavelength. A continuous nickel concentration measuring device is characterized in that it is configured to extract the concentration of nickel ions based on the measured intensity of transmitted light.

The above invention was made based on the following new findings from research by the inventors. As shown in FIG. 1, the absorption spectrum of nickel ions (IT value) remains unchanged at a temperature of 5 to 50° C. and a pH of 2.5 to 5, and the first absorption peak wavelength is 400 nm.

The relationship between the nickel ion concentration and its absorbance is linear regardless of which of the second absorption peak wavelengths of 720 nm is used as the dominant wavelength, and by utilizing this absorption characteristic, the low 11 degree nickel This can be measured using a long absorption cell. The absorbance graph shown in FIG. 1 is the result of measurement using nickel ions (Niz+) at 1 degree 110 l11/m and an absorption cell length of 10 III l.

The transmitted light used in the first invention is white light, but the wavelength actually measured is 400 nm or 720 r.
Since this is the wavelength of the in part and the wavelength of the absorption bottom part near a, only the 400 nm or 720nl11 part and the light at its absorption bottom may be used. Of these, the light absorption amount of water containing nickel ions and substances other than nickel ions in the sample water is determined by the transmitted light of 400 nm or 720n111 part, for example 380 to 440 nm or 70 (1 to 750 nm), and the amount of light absorbed by water containing nickel ions and substances other than nickel ions is determined by or at the wavelength of the absorption bottom near 720 nm, e.g. 480-540 nm,
The light absorption of water itself, which contains substances other than nickel ions, is 3 m (
(hereinafter referred to as background absorption amount).

Generally, the Lambert-Beer law shown in equation (1) holds between transmitted light and 11 degrees.

log,, (io/I) = εcd... (1) In formula (1), Io is the intensity of transmitted light of the solvent, r is the intensity of transmitted light of the solution, ε is the molar extinction coefficient, and C is the molar 11i1 degree, d is the thickness of the absorbing layer. Said 4゜Qnm or 720
The intensity of the transmitted light in the nm part is △, 400nm or 720n
If the intensity of the wavelength transmitted light at the absorption bottom of the nickel ion in the vicinity of m is B, △ corresponds to 1 in formula (1), and B corresponds to formula (1).
It can be assumed that the value corresponding to 10 is 1, which can be expressed in the relationship of equation (2).

10g1゜ (B/A)=εcd−-・(2) Therefore,
If ε and d are known in addition to the values of A and B, the molar concentration C can be determined. Using the wavelength of the absorption bottom near the absorption peak of nickel ions mentioned above, where there is almost no absorption by nickel ions, the amount of background absorption can be calculated as follows:
By simultaneously measuring the absorbed amount of nickel ions, it is possible to continuously measure 8 degrees of nickel ions at each moment even in flowing sample water. This makes it possible to set an appropriate amount of water for washing or control the nickel recovery device. Moreover, it is extremely quick compared to conventional methods, and since no special reagents are used, the sample water can be discharged or reused as is.

Next, the continuous measuring device of the second invention, which is directly used in carrying out the first invention, will be explained based on the drawings.

FIG. 2 is a ten-piece diagram showing an embodiment of the second invention.

Here, 1 is a light source such as an arc lamp or an incandescent lamp and its accessories which receive electricity supply from a light source stabilizing voltage (10), and 2 is a recording/control signal valve 1 circuit 12, etc. The transmitted light detection unit 3 connected to the circuit 11 is an absorption cell (tubular or square shape) made of glass or acid-resistant and heat-resistant plastic, and the optical path planes at both ends are equipped with optical cells that do not absorb light in the visible range. The light source 1 is made by fusing or gluing an optical glass plate having a flat surface on the absorption cell 3.
- and at the other end, a transmitted light detection section 2 consisting of, for example, a diffraction grating and a phototube is provided, and after the light emitted from the light source 1 passes through the absorption cell 3, it is measured by the transmitted light detection section 2. It is configured to

In addition, the sample water collected by the water pump 9 is deaerated by entering an inclined deaerator 8 filled with glass tubes, and then passed through a filter 7 to remove solid matter from the water. Photodetector 2
It flows into the absorption cell 3 from the side, then flows inside the cell 3, and is discharged to the outside from the light source 1 side.

13a and 13b are electromagnetic valves, 14 is a cell cleaning water tank, 15 is a water level adjustment valve, and 16 is a tap water supply adjustment valve. When the pump 9 is stopped, the valve 13a is closed.
If you open −4, the absorption cell 3 will be absorbed by the tap water in the tank 14.
It is constructed in such a way that it can be used to clean the inside of the container. The valve 131) is used for rimbling water testing, discharging air, and injecting cleaning agent into the cell.

FIG. 3 is an explanatory diagram showing a more specific tKJm composition of the light mi, the transmitted light detector 2, and the absorption cell 3. In FIG.

The absorption hill has a structure in which the length can be varied in the range of 200 to 2500 mm depending on the nickel ion concentration of the sample water.For example, the middle part may be made of a plastic bellows, etc. It has a test water inlet 3a on the side and a ta outlet 3b on the light source side. The light source 1 includes a light emitter 1a and a convex lens 1b
The light from the light emitter 1a becomes parallel light by the lens 1b, passes through the cell 3, reaches the transmitted light detection side, and a part of the transmitted light passes through the reflector 2a and is handled at the peak wavelength light measurement site. C enters a certain photoelectric element 2b, and is also reflected by a reflecting mirror 2a. 1=Some of the transmitted light enters a photoelectric element 2G, which is the absorption bottom wavelength light measurement site. In the photoelectric element 2b, the wavelength is 400
The intensity of the light in the nm or 720 nm region is measured, and the amount of water that passes through the water containing nickel ions and substances other than nickel ions in the sample water is determined.
The amount of transmission at the wavelength of the absorption bottom in the vicinity of 0 nm or 720 nm, for example, 500 nm, is measured, and the amount of transmission of water containing substances other than nickel ions is determined. These two data signals are processed by the amplification/operation circuit 11, and the above formula (2
) As shown in (), nickel ion 11r!
I is launched. Next, the result of step (a) is recorded in the recording/control signal generation circuit 12, and a control signal is generated according to the concentration of nickel ions. It becomes possible to control the device automatically.

The configuration described above is controlled by automatic control using a computer, for example, according to a program according to the flowchart shown in FIG. 4. C is cut. Here, step 21 is to set the standard state of the absorption cell length.
Furthermore, the processing of initial setting of various device data such as standard state setting of the electromagnetic valve 13a and the nickel recovery device is shown. The next step 22 represents a process of measuring the state of background transparency and determining that the absorption cell length is insufficient if the amount of transmission exceeds 38111 in Bt. At step 23, the absorbent cell is stretched by a certain amount and returned to the smear tube 22 again. If it is determined in step 22 that it is 81 or more, and then in step 24 the amount of background transmission is less than the reference value 82, it is determined that the absorption cell length is too large, and in step 25 the absorption cell length is set to a constant value, Shrink,
Return to step 24 again. Here, 82<8+. If it is determined in step 24 that it is 82 or more, the process goes to step 2.
Move on to 6. In step 126, the measurement of the transmitted light of, for example, 400 nm is omitted, and then in step 27, from the data - (background transmission amount, transmission amount of 400 nm, and computer memory), the above formula (2 ) is performed to obtain nickel A > 14 degrees.

Next, in step 28, the data obtained by C1 is recorded or displayed. In step 29, it is determined whether the nickel ion concentration is equal to or greater than the reference value N. If it is equal to or greater than N, the process proceeds to step 30, where the nickel recovery equipment is
For example, the degree of nickel is adjusted to below the reference value by adding water, so that nickel can be recovered, and the process returns to step 22 to repeat the same process again.

The nickel ion concentration continuous measuring device of the second invention configured as described above has the effects of the first invention and also measures the nickel ion concentration continuously and automatically without the need to stop the Niracle processing line for measurement. It is possible to quickly take measures against changes in the nickel ion concentration (A), and it also has a relatively neutral mechanism (C), which is easy to maintain and can be made in-house.

Next, an example will be explained.

Example 1 A tungsten filament incandescent lamp (special concentrating type incandescent lamp), 10V-24W, was used as a light source, and the length was 2'.
In a 50 mm glass absorption cell, nickel sulfate was converted into nickel ions in tap water and the water was absorbed from 0 to 1000 m (
] / vertical (with a transmitted light detector, measure the amount of transmission at the absorption peak of the aqueous solution of niracle sulfate using light with a wavelength of 700 nm, and the amount of transmission at the absorption bottom with light at a wavelength of 500 nm, Each measurement result is subjected to arithmetic processing according to equation (2) above, and the record of the output signal after the frame processing in section (a) is shown in FIG.

As a result, the output at each 11 degrees changes stepwise,
The output signal corresponds primarily to 1lillffl of the nickel ion, and the response is instantaneous, as the staircase rises almost vertically. It was found that this is expressed in

Example 2 Using a device similar to Example 1, nickel secondary electrolysis washing water was used in actual operation (Figure 6 shows the measurement results of flowing washing water at a rate of 5 m/1n through the absorption cell). Shown in 1.:.

As a result, it was found that -C self-supported and continuously expressed the instantaneous concentration in response to changes in nickel temperature.

[Brief explanation of drawings]

Fig. 1 is a graph showing the absorption peak of nickel ions, Fig. 2 is a block diagram showing an embodiment of the continuous measuring device of the second invention, and Fig. 3 shows the light source, transmitted light detection section, and absorption cell section. Fig. 1 is a schematic diagram, Fig. 4 is a flowchart showing the microcomputer control of the measuring device, and Fig. 5 shows the nickel ion concentration in a stepwise manner at each time. I change my degree! Graph 1 shows the change in the output of the transmitted light detector in this case, and Figure 6 shows an example of actual measurement of nickel secondary electrolysis water using this measuring device.
represents. 1...Light source 2...Transmitted light detection unit 3...Absorption U10...) Stabilized power source for source 11...Amplification and extraction circuit 12...Recording and control signal generation circuit Agent Ben Soku”] Tsutomu Adachi Figure 1 Figure 1, nm Figure 2 Figure 3

Claims (1)

[Scope of Claims] 1. Light of water containing nickel ions and substances other than nickel ions is generated by light having a wavelength of nickel ion absorption peak within the wavelength range of 250 to 900 nm out of the light transmitted through the sample water in a fluid state. At the same time, the amount of light transmitted through water containing substances other than nickel ions is determined using the wavelength light at the absorption bottom near the absorption peak wavelength described in -, and the degree of nickel ion is determined from the amount of transmission of both. A 111 degree continuous measurement method for nickel ions. 2 Nickel ion absorption peak wavelength light is 400 or 7
Claim 1, which is light with a peak wavelength of 20 nm
The nickel ion continuous measurement method described in Section 1. 3 The wavelength light at the absorption bottom near the absorption peak wavelength is 500
Claim 11, which is light with a wavelength at the absorption bottom in the nm portion
r4 or the method for one-time continuous measurement of nickel ions described in item 2. 4. A light source installed at one end of the absorption cell emits light onto the sample water in the cell, and a transmitted light detection section installed at the other end of the cell measures the intensity of the transmitted light, In a device that measures the temperature of a substance in test water based on its strength, it is sent to an arithmetic circuit (J).
l! ! The transmitted light detection section is configured to flow out from the end, and the transmitted light detection section is composed of a measurement site for light with a nickel ion absorption peak wavelength in the wavelength range of 250 to 90 Qnm, and a measurement site for light at the absorption bottom wavelength near the absorption peak wavelength, A nickel 11 degree continuous measuring device, characterized in that the operator circuit is configured to calculate the concentration of nickel ions based on the intensity of transmitted light measured simultaneously by both measuring parts. 5 Measurement site of nickel ion absorption peak wavelength light is 40
The nickel concentration continuous measuring device according to claim 4, which measures light having a peak wavelength of 0 nm or 720 nm. 6 Nickel I according to claim 4 or claim i, wherein the measurement site for the wavelength light at the absorption bottom near the absorption peak wavelength measures the wavelength light at the absorption bottom in the 500 nl+1 portion.
I Continuous slimming measurement device.