JP3662095B2 - Ozone water concentration meter - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ozone water concentration measuring device, and more particularly to an ozone water concentration measuring device that can measure a response speed quickly and can perform so-called in-line continuous measurement.
[0002]
Conventionally, ozone water concentration detection methods can be broadly divided into chemical reaction methods that use chemicals, ultraviolet absorption methods that compare and measure ultraviolet absorption, and electrical detection methods that detect changes in electromotive force and electrolyte conductivity. Are representative, but both are known to have advantages and disadvantages.
[0003]
First, a typical method using chemicals is a method using potassium iodide, which is known as the most accurate method, but requires a titration operation by sampling a certain amount of ozone water. Therefore, there is a problem that continuous measurement is impossible. In addition, the mechanization method of this method has been put to practical use, but this is also a digital display of the concentration measurement value, and batch operation that requires a certain amount of sampling and a reagent such as potassium iodide solution. Is still necessary. In addition, a color-changing reagent method using a dye such as indigo has been proposed, but it is still a batch method that requires a reagent.
[0004]
The following ultraviolet absorption method utilizes the phenomenon that ozone has a strong absorption spectrum in the ultraviolet region near 253.7 nm, and is the most popular method for measuring gas phase ozone. However, the measurement of ozone water requires a large amount of passing ozone water, and unlike gas, the measurement value causes a significant error due to slime that adheres to the ultraviolet column due to the measurement ozone water, so the washing operation is frequently performed. There was a problem that required.
[0005]
In the last electrical detection method, the membrane electrolyte method is currently best known. In this method, ozone flows into the electrolyte through a Teflon ( registered trademark ) thin film (membrane) having a thickness of several microns, This method reads changes in the conductivity of the electrolyte. The disadvantages of this method are that the response speed is slow, especially when it takes a considerable amount of time to start up from the stop, and replenishment of consumable electrolyte and periodic contamination of the membrane. There is a problem that requires complicated maintenance and management such as replacement.
[0006]
Compared to the various methods described above, the most convenient and rapid method of response speed, bare electrode method (expressed in English Bare Electrode Method) is usually an anode of gold or platinum (Pt), copper (Cu) This is a phenomenon that uses a phenomenon in which a voltage that follows a change in the concentration of ozone water is generated when a cathode made of ozone is inserted into ozone water. However, this method has a problem that a mechanism for constantly polishing the surface of the cathode electrode is necessary because copper (Cu) of the cathode electrode is oxidized by ozone (0 ₃ ).
[0007]
[Problems to be solved by the invention]
The present invention has been made in view of the above problems, and it is an object of the present invention to provide an ozone water concentration measuring instrument that can measure ozone concentration with a simple apparatus, easy maintenance and management, and quick response speed. .
[0008]
[Means for Solving the Problems]
In order to achieve the above object, the configuration of the present invention includes a first electrode S1 made of platinum (Pt) or gold (Au) in a measurement chamber 10 having an inlet 11a and an outlet 11b of ozone water, A second electrode S2 made of silver (Ag) is stored opposite to each other with a predetermined interval, and the first electrode S1 and the second electrode S2 measure the amount of electrical change between them. Lead wires L1 and L2 connected to the device M are extended outside the measurement chamber 10, and either or both of the first electrode S1 and the second electrode S2 are electrically insulated. attaching one end of the rod 4, the other end of the actuating rod 4 are extended to the outside from the through hole 31 of the measuring chamber 1 0, connecting the actuating rod 4 to the driving source 2 for reciprocating, the through hole 31 and the working rod 4 are secured to ensure the airtightness of the measuring chamber 10 and bendable to guarantee the movement of the working rod 4. In which it took technical means formed by providing a film 3.
[0009]
In the present invention, the first electrode S1 is made of platinum or gold (Au), which is chemically very low in reactivity, so that the first electrode S1 exhibits an action that is difficult to be altered by ozone water. Further, since the second electrode S2 composed of silver (Ag), the second electrode S2 is immediately oxidized silver (Ag) is in ozone water, the surface of silver oxide (Ag 2 ₀₎ will be next to blackening, This ozone-oxidized silver oxide (Ag ₂ 0) is chemically very stable and exhibits the action of preventing the subsequent oxidation.
[0010]
The combination of the first electrode S1 composed of platinum and the second electrode S2 composed of silver (Ag) (more precisely, silver oxide (Ag ₂ 0)) corresponds to the change in ozone water concentration as a result of experiments. It exhibited an electromotive action.
[0011]
Either one or both of the first electrode S1 and the second electrode S2 is reciprocated by a driving source 2 that reciprocates either one or both of the operating rod 4 to the first electrode S1 and the second electrode S2. Since it vibrates (vibrates), the response speed of the large electromotive force with respect to the ozone concentration is high and the action can be taken out stably. The mechanism of this action is not always clear, but the amount of electrical change at the surface of this bare electrode occurs in a very narrow range in a static atmosphere, but the phenomenon of electromotive force saturation occurs, but both electrodes move (vibrate). Thus, it can be estimated that a large electromotive force can be stably obtained by continuing the electromotive action.
[0012]
Next, the invention of “Claim 2” divides the measuring instrument main body 1 into a measuring chamber 10 and a driving device storage chamber 20 by a partition 30, and the measuring chamber 10 has an inlet port 11 a and an outlet port for ozone water. 11b, and in the measurement chamber 10, a substantially straight rod-shaped first electrode S1 made of platinum (Pt) or gold (Au) and silver (Ag), most of which is the first electrode. The second electrode S2 located at a position surrounding S1 at an equal distance is housed, and the first electrode S1 and the second electrode S2 are connected to a measuring device M for measuring an electrical change amount between them. the line L1, L2 is extended to the outside of the measuring chamber 1 0, also the first electrode S1 to the either one or both of the second electrode S2, the first electrode with electrically insulated One end of the operating rod 4 facing the axial direction of S1 is attached, and the other end of the operating rod 4 is connected to the partition 30. It extends into the drive device storage chamber 20 from the through hole 31 and is stored in the drive device storage chamber 20, and is connected to a drive source 2 for reciprocating the operating rod 4 in the axial direction of the first electrode S1. Technical means is provided in which a bendable partition film 3 is provided between the through hole 31 and the operating rod 4 to ensure the airtightness of the measuring chamber 10 and to ensure the movement of the operating rod 4.
[0013]
Therefore, in the present invention, in addition to the above-described operation, most of the first electrode S1 and the second electrode S2 are located at the same distance, and it goes without saying that both move (vibrate). Even if only one of the two electrodes moves, the effect of suppressing the change in electromotive force due to the change in the electrode interval is exhibited.
[0014]
Next, the invention of "Claim 3" divides the measuring instrument main body 1 into an upper measurement chamber 10 and a lower drive device storage chamber 20 by a partition body 30 provided at the upper and lower intermediate portions thereof. A through-hole 31 is provided in the center of 30, and a bendable partition film 3 made up of a bellows cylinder that closes the through-hole 31 is erected in the through-hole 31, and the upper end opening of the bendable partition film 3 is insulated. The first electrode S1 in the form of a substantially straight bar in which a wire S1a made of platinum (Pt) or gold (Au) is wound in a coil shape is erected on the insulating lid 3a. Further, a second electrode S2 in which silver (Ag) wire is formed in a mesh tube shape is attached concentrically with the first electrode S1 with a predetermined gap, and further, on the lower surface side of the insulating lid 3a. The upper end of the operating rod 4 that is loosely inserted in the through hole 31 is connected, and the lower end of the operating rod 4 is stored in the drive device storage chamber 20 so that the operating rod 4 can be Connected to a drive source 2 that reciprocates in the direction, from the first electrode S1 and the second electrode S2, lead wires L1 and L2 connected to a measuring device M that measures the amount of electrical change between them are measured. to extend to the outside of the chamber 1 0, in which took technical means formed by providing the outlet port 11b and the inlet 11a of the ozone water in the measuring chamber 10.
[0015]
Therefore, in the present invention, in addition to the effect of the “claim 2”, the first electrode S1 is formed by winding a wire S1a made of platinum or gold in a coil shape, so that the amount of use of platinum or the like can be reduced. It exhibits the effect of setting a large surface area for performing a chemical reaction.
[0016]
Further, since the present invention the second electrode S2 has no silver (Ag) wire and mesh tubular, also be size rather set the electrical reactive surface area usage less of silver (Ag) and the first electrode S1, and Since the ozone water can pass through the mesh, the ozone water shielding by the second electrode S2 is prevented.
[0017]
BEST MODE FOR CARRYING OUT THE INVENTION
Next, embodiments of the present invention will be described with reference to the accompanying drawings. In the figure, reference numeral 10 denotes a measurement chamber, which has an ozone water inlet 11a and an outlet 11b, and ozone water to be measured flows in from the inlet 11a and flows out from the outlet 11b.
[0018]
Specifically, as shown in FIG. 2, a branch bypass passage 51 is branched in the middle of the ozone water supply pipe 50, and the measurement chamber 10 and the pump 52 are interposed in the branch bypass passage 51. However, of course, the measurement chamber 10 may be interposed directly in the middle of the ozone water supply pipe 50, and further, the measurement chamber 10 is provided completely separately from the ozone water supply pipe 50. Separately, ozone water such as the ozone water supply pipe 50 may be supplied into the measurement chamber 10. Although the present invention is premised on continuous measurement in running water, the batch measurement may be performed by retaining ozone water in the measurement chamber 10 for a predetermined time.
[0019]
Of course, the measurement chamber 10 is made of a material having ozone water resistance. In this embodiment, the measurement chamber 10 is made of a vinyl chloride resin material, but a Teflon ( registered trademark ) resin or a stainless steel material may be used. Furthermore, in the case of using a material that does not have ozone water resistance, an ozone water resistant film may be coated on the inner surface.
[0020]
The measurement chamber 10 may be formed in a sealed state except for the ozone water inlet 11a and the outlet 11b. In the illustrated example and the invention of claim 2, the partition 30 is used to drive the measurement chamber 10. It is partitioned into a device storage chamber 20. That is, a part of the measurement chamber 10 is constituted by the partition body 30, and a through hole 31 is provided in the partition body 30. The invention of "Claim 3" is also the same, and the measuring device main body 1 is divided into an upper measuring chamber 10 and a lower driving device housing chamber 20 by a partition body 30 provided at the upper and lower intermediate portions thereof. A through hole 31 is provided in the center of the partition 30.
[0021]
The partition 30 is made of a material having ozone water resistance, and is formed by providing a flange 33 at the lower part of a screw cylinder 32 having a thread on the outer periphery, and the measurement chamber 10 is formed in a covered cylinder. The lower part is screwed into the screw cylinder part 32 and sealed with a packing 34.
[0022]
The partition body 30 is provided with a through hole 31 at the center thereof and communicates with the drive device storage chamber 20 (however, it is partitioned by a bendable partition film 3 described later). The drive device storage chamber 20 is formed in a cylindrical shape, and the partition body 30 is fitted to the upper end and the bottom plate 35 is fitted to the lower end. Since the sealing of the drive device storage chamber 20 is not required, the partition body 30 and the bottom plate 35 may be fitted by press-fitting, screwing, or the like. What is necessary is just to integrate with a tightening degree.
[0023]
In addition, in the “claim 2” and “claim 3”, the measurement chamber 10 and the drive device storage chamber 20 are partitioned by the partition body 30 as described above, and the ozone water concentration measuring device of the present invention is simply compact. This is to make a single integrated structure and to maintain maintenance.
[0024]
In the measurement chamber 10, the first electrode S1 made of platinum metal such as platinum (Pt) and the second electrode S2 made of silver (Ag) are stored facing each other with a predetermined interval. is there.
[0025]
As the platinum metal constituting the first electrode S1, platinum (Pt), palladium (Pd), iridium (Ir) or the like can be used. In particular, the use of platinum (Pt) can be used for the second electrode S2. It was particularly effective for using (Ag). The silver (Ag) constituting the second electrode S2 is preferably one in which silver (Ag) is immobilized. However, when ozone water is supplied in practical use, the surface is immediately oxidized with ozone and silver oxide (Ag ₂ 0). ) And thus immobilization, it was substantially the same if silver (Ag) was used as it was.
[0026]
The first electrode S1 and the second electrode S2 are opposed to each other with a predetermined interval since a difference in electromotive force occurs when the gap is changed. The first electrode S1 and the second electrode S2 may be plate-shaped or rod-shaped, respectively, but the larger the surface area, the greater the electromotive force that can be obtained.
[0027]
Therefore, in the invention according to claim 2, the second electrode S2 is formed in a substantially straight bar shape, and the second electrode S2 is mostly located at a position surrounding the first electrode S1 at an equal distance. Accordingly, the entire circumferential surface of the first electrode S1 is opposed to the second electrode S2 under the same distance condition, and an efficient electromotive force can be obtained.
[0028]
The substantially straight rod-shaped first electrode S1 and the second electrode S2 surrounding the first electrode S1 are configured such that the first electrode S1 is a column or pipe having a circular cross section, and the second electrode S2 is the first electrode. A cylindrical body having an inner diameter larger than the outer diameter of S1 may be used. However, when the first electrode S1 is surrounded by the cylindrical body, the ozone water that flows as a kind of shielding plate is evenly distributed to the first electrode S1. In some cases, the cylindrical body may be divided into a plurality of parts and arranged on the circumference with intervals. Alternatively, the second electrode S2 may be a straight bar having a space on the same circumference and parallel to the second electrode S2. Needless to say, the second electrode S2 may be in the form of a wire mesh tube as in "claim 3".
[0029]
In the invention of "Claim 3", the first electrode S1 is obtained by winding a wire S1a made of platinum (Pt) or gold in a coil shape so as to obtain a large surface area with a small amount of platinum metal used. Then, since the second electrode S2, a large electromotive force can be obtained by setting wide surface area, and, since the first electrode S1 to the coil shape to face the entire circumference effective, silver ( Ag) A wire having a net-like shape is used.
[0030]
From the first electrode S1 and the second electrode S2, lead wires L1 and L2 connected to a measuring device M for measuring an electrical change amount between them are extended to the outside of the measuring chamber 10. As the measuring device M (see “FIG. 2”), an ammeter or a voltmeter can be used. In this embodiment, a voltmeter is used. It goes without saying that an amplifier circuit, a temperature correction circuit, and the like are added to the measuring apparatus M as necessary.
[0031]
In addition, one or both of the first electrode S1 and the second electrode S2 is attached with one end of an electrically insulated working rod 4, and the other end of the working rod 4 is a through hole of the measurement chamber 10. It extends outside 31 and is connected to a drive source 2 that reciprocally moves the operating rod 4.
[0032]
That is, one or both of the first electrode S1 and the second electrode S2 is reciprocated by the drive source 2, in other words, vibrates. In the illustrated example, the drive source 2 that obtains vibration by electromagnetic force is used. However, another known vibration generator using a motor and a link may be used.
[0033]
In order to reciprocate either the first electrode S1 or the second electrode S2 by the drive source 2, unlike the illustrated example, either the first electrode S1 or the second electrode S2 is moved by the operating rod 4. Of course, it is possible to connect to the drive source 2 via the other, and to fix the other to the fixed part as appropriate.
[0034]
There is no particular problem when both the first electrode S1 and the second electrode S2 are reciprocated simultaneously in synchronism with the driving source 2, but when only one of them is moved, the first electrode S1 and the second electrode S2 are moved. When the gap with S2 is changed with movement, the electromotive force may be wave-shaped. Therefore, in the invention of "Claim 2", the second electrode S2 is positioned at a position surrounding the first electrode S1 at an equal distance, and one or both of the first electrode S1 and the second electrode S2 are One end of the operating rod 4 which is electrically insulated and faces the axial direction of the first electrode S1 is attached, and the other end side of the operating rod 4 is in the drive device storage chamber 20 through the through hole 31 of the partition 30. The distance between the first electrode S1 and the second electrode S2 is such that the operating rod 4 accommodated in the drive device storage chamber 20 is reciprocated in the axial direction of the first electrode S1. There is no change.
[0035]
A bendable partition film 3 is provided between the through hole 31 and the operating rod 4 to ensure the airtightness of the measuring chamber 10 and to ensure the movement of the operating rod 4. The bendable partition film 3 requires a material having ozone water resistance. In this embodiment, the bendable partition film 3 is made of Teflon ( registered trademark ) resin, but silicon resin or the like may be used.
[0036]
The bendable partition membrane 3 closes the through hole 31 without hindering the movement of the operating rod 4, and a single diaphragm may be used. However, the embodiment shown in FIG. In the present invention, a bellows tube is used. That is, the bendable partition film 3 made of a bellows cylinder that closes the through-hole 31 is erected in the through-hole 31, and the upper end opening of the bendable partition film 3 is closed with the insulating lid 3a (epoxy system). It is fixed with an adhesive and closed.)
[0037]
In the illustrated embodiment and the invention of claim 3, the first electrode S <b> 1 and the second electrode S <b> 2 are both erected on the insulating lid body 3 a, and an operating rod is provided on the lower surface side of the insulating lid body 3 a. Since the upper ends of 4 are connected, both the first electrode S1 and the second electrode S2 move in the same direction.
[0038]
In addition, the contact part of the bendable partition film 3 made of the bellows cylinder, the through hole 31 and the insulating lid 3a is glued in this embodiment in order to keep airtightness. In the figure, L3 and L4 indicate lead wires of the drive source 2.
[0039]
【The invention's effect】
Since the present invention is as described above, the first electrode S1 is chemically oxidized with platinum having a very low reactivity, and the second electrode S2 is also chemically oxidized with silver (Ag) having a very low reactivity. Since silver oxide (Ag ₂ 0) was used, an ozone water concentration measuring device capable of performing stable measurement even when used for a long time can be provided.
[0040]
The combination of the first electrode S1 composed of platinum and the second electrode S2 composed of silver (Ag) (more precisely, silver oxide (Ag ₂ 0)) has an ozone water selective electromotive action. An ozone water concentration measuring device that is less affected by other substances dissolved with ozone can be provided.
[0041]
In the present invention, either one or both of the first electrode S1 and the second electrode S2 are reciprocated (vibrated) by the drive source 2, so that the response speed is high and an amplifier circuit is actually required. It is possible to provide an ozone water concentration measuring device that can obtain a large electromotive force that is not generated.
[0042]
In the invention of "Claim 2", most of the first electrode S1 and the second electrode S2 are located at the same distance. Therefore, when both electrodes are moved (vibrated), of course, Even if only one of them moves, it is possible to provide an ozone water concentration measuring instrument that suppresses a change in electromotive force due to a change in the electrode interval and makes the measurement result stable and easy to read.
[0043]
In the invention of "Claim 3", the first electrode S1 is formed by winding a wire S1a composed of platinum or gold in a coil shape, so that the surface area for conducting an electrical reaction is reduced by reducing the amount of platinum used. Since the second electrode S2 has a silver (Ag) wire mesh shape, the amount of silver (Ag) used is the same as the first electrode S1, and the electrical reaction surface area can be set large, and the mesh is made of ozone. Since water can pass through, ozone water shielding by the second electrode S2 is prevented, and an ozone water concentration measuring device capable of more stable measurement can be provided.
[0044]
Further, since the present invention uses the bendable partition film 3 made of a bellows tube, there is no fear of damage to the bendable partition film 3 even if the movement range of the first electrode S1 and the second electrode S2 is increased. An ozone water concentration measuring device can be provided.
[Brief description of the drawings]
FIG. 1 is a longitudinal sectional view of an essential part showing an embodiment of an ozone water concentration measuring device of the present invention.
FIG. 2 is a side view showing an example of use of the ozone water concentration measuring device of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Measuring device main body 2 Drive source 3 Bendable partition film 3a Insulating lid 4 Actuation rod 10 Measurement chamber 11a Inlet 11b Outlet 20 Drive device storage chamber 30 Partition 31 Through-hole S1 1st electrode S1a line S2 L1 Lead wire L2 Lead wire

Claims (3)

In a measurement chamber (10) having an inlet (11a) and an outlet (11b) of ozone water, a first electrode (S1) made of platinum (Pt) or gold (Au) and silver (Ag) The configured second electrode (S2) is stored with a predetermined interval facing each other,
From the first electrode (S1) and the second electrode (S2), lead wires (L1, L2) connected to a measuring device (M) for measuring the electrical change between them are connected to the measuring chamber (10). Extending outside the
Further, one or both of the first electrode (S1) and the second electrode (S2) is attached with one end of an electrically insulated operating rod (4), and the other end of the operating rod (4). The side extends outside the through hole (31) of the measurement chamber ( 10 ) and is connected to a drive source (2) for reciprocating the operating rod (4).
A bendable partition film (3) is provided between the through hole (31) and the operating rod (4) to ensure the airtightness of the measuring chamber (10) and to ensure the movement of the operating rod (4). Ozone water concentration measuring instrument. The measuring device main body (1) is divided into a measurement chamber (10) and a drive device storage chamber (20) by a partition (30),
The measurement chamber (10) is provided with an inlet ( 11a ) and an outlet ( 11b ) of ozone water, and the measurement chamber (10) is made of platinum (Pt) or gold (Au). A substantially straight rod-shaped first electrode (S1) and a second electrode (S2), which is made of silver (Ag) and is located at a position that mostly surrounds the first electrode (S1) at an equal distance,
From said 1st electrode (S1) and 2nd electrode (S2), lead wire L1, L2 connected to the measuring apparatus (M) which measures the electrical variation | change_quantity between both is carried out of the said measurement chamber ( 10 ). It extends outside, and one or both of the first electrode (S1) and the second electrode (S2) are electrically insulated and the axial direction of the first electrode (S1) is One end of the facing operating rod (4) is attached, and the other end of the operating rod (4) is extended from the through hole (31) of the partition (30) into the drive device storage chamber (20 to drive the driving rod. Connected to a drive source (2) housed in the device storage chamber (20) and reciprocatingly moving the operating rod (4) in the axial direction of the first electrode (S1);
A bendable partition film (3) is provided between the through hole (31) and the operating rod (4) to ensure the airtightness of the measuring chamber ( 10 ) and to ensure the movement of the operating rod (4). Ozone water concentration measuring instrument. The measuring device main body (1) is divided into an upper measurement chamber (10) and a lower drive device storage chamber (20) by a partition (30) provided at the upper and lower intermediate portions, and the partition (30). A through hole (31) is provided in the center of the
The through hole (31) is provided with a bendable partition film (3) made of a bellows cylinder that closes the through hole (31), and the upper end opening of the bendable partition film (3) is an insulating lid. (3a)
On the insulating lid (3a), a substantially straight rod-shaped first electrode (S1) in which a wire (S1a) made of platinum (Pt) or gold (Au) is wound in a coil shape is erected, and The second electrode (S2) in which the silver (Ag) wire is formed into a mesh tube shape is attached concentrically with the first electrode (S1) with a predetermined gap,
Further, an upper end of an operating rod (4) that is loosely inserted into the through hole (31) is connected to the lower surface side of the insulating lid (3a), and the lower end of the operating rod (4) is connected to the driving device. Connected to a drive source (2) stored in the storage chamber (20) and reciprocatingly moving the operating rod (4) vertically;
From said 1st electrode (S1) and 2nd electrode (S2), lead wire (L1, L2) connected with the measuring apparatus (M) which measures the electrical variation between both is said measurement chamber ( 10 ). Extending outside the
An ozone water concentration measuring device comprising an ozone water inlet (11a) and an outlet (11b) in the measurement chamber (10).

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