JP2003211159A - Photooxidizer, water treatment apparatus and measuring apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photooxidizer which can efficiently and safely oxidize object components in fluid such as liquid with a simple structure. <P>SOLUTION: An inner tube 1a and an outer tube 1b are sealed at their both ends, and a substance radiating ultraviolet rays by electric discharge is enclosed, thereby forming a ring discharge tube 1. The inside of the inner tube 1a is used as a reaction space 2, into which the liquid is introduced. A reflective membrane 3 is coated around the outer tube 1b. A coil 5 connected to a high-frequency power source 4 is wound around the discharge tube 1. The discharge tube 1 is discharged by an induced magnetic field obtained by supplying a high-frequency current to the coil 5. The liquid is irradiated with the ultraviolet rays radiated from the discharge tube 1 to the inside reaction space 2 to be oxidized. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photo-oxidizer for oxidizing a fluid such as a liquid, a water treatment device, and a measuring device. More specifically, photooxidation that can be suitably used for a water treatment device that sterilizes sewage and the like by oxidizing microorganisms in water and a measuring device for measuring total organic carbon content (TOC) of ultrapure water and the like. And a water treatment device and a measuring device using this photo-oxidizer.

[0002]

2. Description of the Related Art In sewage treatment, water before being discharged into the environment is sterilized. Conventionally, the most commonly used sterilization method is chlorination. However, chlorination tends to generate harmful by-products. Also, discharged water containing chlorine may affect aquatic organisms and plants such as Nori. Therefore, ozone treatment using ozone instead of chlorine is also performed.

In recent years, a water treatment method using ultraviolet rays has been attracting attention as a treatment method having a smaller environmental load than ozone treatment. The treatment with ultraviolet rays is a highly reliable sterilization method because DNA of microorganisms in water can be directly destroyed by a photochemical reaction and inactivated in a few seconds.

As a photo-oxidizer for such water treatment,
For example, a photo-oxidizer having a structure in which a UV lamp is directly infiltrated into a water tank for irradiation, or a structure in which water is circulated in a full-filled state in a casing having a closed structure including the UV lamp is used.

On the other hand, in today's advanced industrial manufacturing processes and the like, highly purified "ultra pure water" is often used in large quantities. For example, in the case of cleaning semiconductors, manufacturing medical chemicals and injection solutions, chemical analysis, etc., impurities,
For example, pure water that is substantially free of fine particles, various ions, microorganisms such as bacteria, and dissolved substances such as organic compounds is essential. A system for producing such pure water usually uses a combination of various filtration means including a reverse osmosis method, a distillation method, an ion exchange method, an adsorption method, a vacuum degassing method, an ultraviolet oxidation method and an ultrafiltration method. Especially in the semiconductor manufacturing field, for example,
As the circuit integration becomes narrower as the degree of integration of LSI increases, it is necessary to make the semiconductor cleaning water of higher purity in order to prevent a circuit short circuit.
Bacteria and organic substances should be removed as much as possible.

As one of the methods of expressing the cleanliness of pure water, the total organic carbon (TO
C) There is a value. As a means for measuring the TOC value of pure water,
An ultraviolet (UV) oxidation type TOC meter is widely used. In such a TOC meter, the sample solution is introduced into the photo-oxidizer,
Here, the sample solution is irradiated with ultraviolet rays to change the organic carbon in the sample solution into an organic acid or carbon dioxide. Then, the TOC of the sample liquid is obtained based on the change in the conductivity of the sample liquid obtained by the above.
Seeking a value.

The photo-oxidizer is not limited to the TOC described above,
It is widely demanded for the purpose of analyzing a sample solution after oxidizing it. For example, the measurement of total phosphorus and total nitrogen can be performed by colorimetric analysis by oxidizing a sample solution and causing it to color with a reagent.

As a photo-oxidizer for such analysis,
For example, a photo-oxidizer having a structure as shown in FIG. 8 is known. This photo-oxidizer is configured by winding a small-diameter spiral-shaped reaction tube 122 around a straight tube-shaped ultraviolet lamp 121. Then, a fixed amount of the sample water S is transferred to the reaction tube 122 by the pump 124 via the pipe 125, and the fixed amount of the sample water S is irradiated with ultraviolet rays from the ultraviolet lamp 121 and then sent to the analyzer 126 for analysis. I am supposed to do it.

A photo-oxidizer having a structure as shown in FIG. 9 is also known. In FIG. 9, reference numeral 101 denotes a thick straight tube-shaped reaction tube, and an ultraviolet lamp 102 is spirally wound along the longitudinal direction of the reaction tube 101. 1
Reference numeral 03 is a sample water inlet of the reaction tube 101. A fixed amount of sample water S is introduced into the sample water introducing port 103 by a liquid feeding means 104 such as a pump through a pipe 105 provided with a valve 120. Reference numeral 106 is a sample water outlet of the reaction tube 101. The sample water S that has been oxidatively decomposed by the irradiation of ultraviolet rays from the ultraviolet lamp 102 is sent from the sample water outlet 106 through the pipe 107 to the analyzer 108. In addition, 109 is an electrode part of the ultraviolet lamp 102, and E is a power supply connected to the electrode part 109.

Further, the outside of the ultraviolet lamp 102 is enclosed and sealed by a casing 111 having a reflection plate 110 provided on the inner surface thereof. Then, the casing 111 is filled with an inert gas to prevent ozone from being generated in the air atmosphere by ultraviolet rays.

[0011]

In the above-mentioned conventional photooxidizer for water treatment, when an ultraviolet lamp is directly immersed in a water tank for irradiation, the irradiated light cannot be retained only in water. The oxidation efficiency was not sufficient. Further, there is a problem that ultraviolet rays deteriorate surrounding facilities and the like, and the health of workers' eyes and the like is adversely affected.

When water is circulated in a casing having a closed structure containing an ultraviolet lamp, the casing is made of a material that does not allow light to pass through, so that the emitted light can be used only in water. Is possible. However, in this case, it is necessary to provide a dedicated casing for the ultraviolet ray treatment, and the treatment equipment becomes large in size.

Further, in the photo-oxidizer for analysis shown in FIG. 8, in the case of the batch system in which the flow of sample water is stopped and decomposed, the reaction tube 122 is thin, so that when bubbles are generated in the pipe 125, the reaction occurs. The sample water S in the tube 122 moves from the ultraviolet irradiation position. Therefore, there is a problem that the sample water S is not sufficiently decomposed and the reproducibility of analysis is impaired. Further, for example, the bent portion 122a of the reaction tube 122
At that time, the expanded bubbles may stop moving and stop moving, and the bubbles may accumulate. Further, in the case of the continuous decomposition method in which the sample water S is continuously transferred by the pump 124 and introduced into the analyzer 126 before the decomposition is completely completed, the flow rate is likely to change when bubbles are generated. Therefore, the sample water S sent to the analyzer 126
There was a problem that the reproducibility of the analysis was impaired in this case as well, since the degree of decomposition was different.

Further, in the photooxidizer for analytical use shown in FIG. 9, since the ultraviolet lamp 102 has a spiral shape, a gap is formed and the entire circumference of the reaction tube 101 cannot be covered. Therefore, it is necessary to surround the ultraviolet lamp 102 with the casing 111 and to provide the reflector 110 inside thereof. Therefore, the size of the entire photo-oxidizer must be increased. Even if the reflection plate 110 is provided in this way, there is a problem that the oxidation efficiency is low because the light directly irradiated to the reaction tube 101 is small. Further, since a space is created in the casing 111, it is necessary to prevent ozone from being generated in the space. Therefore, the inert gas has to be filled, resulting in an increase in manufacturing cost.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a photo-oxidizer having a simpler structure, capable of efficiently and safely oxidizing a target component in a fluid such as a liquid. To do. In addition, sewage, etc. efficiently and safely,
An object of the present invention is to provide a water treatment device that can perform sterilization treatment without requiring large equipment. Further, it is another object of the present invention to provide a measuring device capable of accurately measuring the total organic carbon content and the like in a sample solution and without increasing the size of the entire device.

[0016]

In order to solve the above-mentioned problems, the present invention comprises a tubular reaction space and an annular ultraviolet light source disposed around the reaction space, wherein the ultraviolet light source is an inner tube. Provided is a photo-oxidizer, which is a discharge tube in which a substance that emits ultraviolet rays by discharge is sealed in an annular space formed by sealing an outer tube and an outer tube at both ends.

According to the present invention, since the entire reaction space can be surrounded by the ultraviolet light source without a gap, the entire reaction space can be directly irradiated with ultraviolet rays. Therefore, it is possible to efficiently photooxidize a fluid such as a liquid. Further, since the reaction space is arranged inside the ultraviolet light source, the reaction space itself does not need to have a complicated shape such as a spiral shape. Therefore, bubbles or the like are not generated and stay in the reaction space. Further, since the ultraviolet light source is composed of a discharge tube in which a substance that emits ultraviolet rays by discharge is sealed in an annular space formed by sealing an inner tube and an outer tube at both ends, an annular light source can be formed by one discharge tube. It can be formed, and the configuration can be simplified.

When the ultraviolet light source is a discharge tube in which a gas is sealed in an annular space formed by sealing an inner tube and an outer tube at both ends, the peripheral wall of the reaction space is defined by the inner tube of the ultraviolet light source. It is preferably configured. In this way, the inner tube of the ultraviolet light source also serves as the peripheral wall of the reaction space, so that the configuration can be further simplified.

In the present invention, the discharge tube is preferably an electrodeless, high frequency discharge tube which discharges by high frequency induction. In this case, since the entire reaction space can be made to uniformly emit light by high frequency induction, it is possible to efficiently photooxidize a fluid such as a liquid. Moreover, since an electrode for discharging is not required, the structure is simplified and
The life of the discharge tube can be extended.

In the present invention, as the discharge tube, an electroded discharge tube having a straight tubular inner tube, an outer tube, and a pair of electrodes and discharging by an AC voltage applied between the pair of electrodes may be used. It is possible. In this case, it is preferable that the discharge is performed in the presence of an alternating magnetic field oriented substantially in the longitudinal direction of the discharge tube. As a result, the discharge path can be formed in a spiral shape instead of the shortest path between the electrodes. Therefore, even if the straight line distance between the electrodes is short, the entire annular space can be made to uniformly emit light, so that the fluid such as a liquid can be efficiently photooxidized.

In the present invention, around the ultraviolet light source,
It is preferable to provide a light reflecting means for reflecting light toward the inner surface. This allows the energy of the ultraviolet light source to
It can be utilized for photo-oxidation without waste. In addition, in the case of the present invention, the shape of the ultraviolet light source is annular, and is not complicated like a spiral shape. Therefore, the light reflecting means can also reflect light toward the reaction space on the inner surface only by covering the periphery of the ultraviolet light source, and it is easy to have a simple configuration.

It is preferable that the light reflecting means reflects substantially only ultraviolet rays. That is, it is preferable to use a so-called cold type reflective film that transmits visible light or the like that does not contribute to photooxidation. This can prevent the internal fluid from being heated by the light energy that does not contribute to photooxidation. Therefore, particularly when used for analytical purposes, it is easy to control reaction conditions and data with good reproducibility can be obtained.

The light reflecting means is preferably provided in close contact with the periphery of the ultraviolet light source. Thereby, it is possible to prevent the oxygen in the atmosphere from being oxidized by the ultraviolet light and generating the ozone gas. Further, the energy of the ultraviolet light source can be utilized for photooxidation without waste.

The light reflection means is preferably a reflection film coated around the ultraviolet light source. In this case, the entire ultraviolet light source can be easily covered in a surely adhered state. Therefore, generation of ozone gas can be reliably eliminated, and the energy of the ultraviolet light source can be utilized for photooxidation without waste. It should be noted that the light reflecting means which is almost in close contact with the ultraviolet light source can also be obtained by winding a light-reflecting metal foil around the ultraviolet light source.

When the reflective film coating the periphery of the ultraviolet light source is made of a conductive material, it is preferable to coat the periphery of the ultraviolet light source while leaving a conduction cut-off band for cutting off the induced current. Thereby, especially when the ultraviolet light source is a discharge tube, it is possible to prevent an induced current from flowing through the reflective film due to the influence of the magnetic field. If an induced current flows through the reflective film, the effect of the spiral discharge due to the AC magnetic field disappears, which is not preferable.

When the photooxidizer of the present invention is used for analytical purposes, it is preferable to insert a sensor for measuring the properties of the fluid introduced into the reaction space. In this case, since the photo-oxidizer and the sensor unit can be integrated, the entire device can be downsized. In addition, the configuration of the entire device is simplified and manufacturing is easy. Further, since it is not necessary to introduce the fluid into the separately provided sensor section, the consumption amount of the fluid can be further reduced. The type of sensor is not particularly limited, and a conductivity detector, a photodetector, a pH detector, a redox potential detector, etc. can be appropriately adopted depending on the measurement target.

In the present invention, it is preferable that a photocatalyst for promoting photooxidation of the fluid is present in the reaction space. In this case, photooxidation of the fluid can be performed more efficiently. The photocatalyst may be packed directly into the reaction space with its own powder or granules, but if the photooxidizer of the present invention is used for analytical applications, any insert or packing that reduces the void volume in the reaction space. It is preferable to coat the article. As a result, the contact area between the catalyst and the fluid can be increased, and the oxidation reaction occurring at the fluid interface in contact with the catalyst can be efficiently promoted with a small amount of the catalyst. When used for analytical applications, it is most preferred to coat the photocatalyst on a sensor that measures the properties of the fluid. As a result, the reaction space containing the photocatalyst and the sensor inserted,
It can be constructed very simply.

The present invention provides a water treatment device characterized by sterilizing water using the photo-oxidizer according to any one of the above. According to the present invention, sewage or the like can be sterilized efficiently and safely, and without requiring large equipment.

The present invention also provides a measuring device characterized by measuring the properties of the sample liquid by oxidizing the sample liquid using the photooxidizer according to any one of the above. For example, it can be configured as a total organic carbon content measuring device by oxidizing a sample and measuring a change in conductivity.
Further, it can be configured as a measuring device for total phosphorus and total nitrogen by colorimetric analysis in which a sample is oxidized and colored with a reagent. According to the present invention, the total organic carbon content in the sample solution,
It is possible to measure accurately and without increasing the size of the entire device.

[0030]

Embodiments of the present invention will be described below with reference to the drawings, but the present invention is not limited to the following embodiments. FIG. 1 is a photo-oxidizer according to the first embodiment, FIG. 1A is a horizontal sectional view, and FIG. 1B is a vertical sectional view. Figure 1
As shown in A and B, the photo-oxidizer according to the present embodiment is provided with an annular discharge tube 1 in which an inner tube 1a and an outer tube 1b are sealed by sealing parts 1c and 1d at both ends thereof. There is. Inner tube 1
Each of the a, the outer tube 1b, and the sealing portions 1c and 1d is made of a material such as quartz glass that can transmit ultraviolet rays and has the same coefficient of thermal expansion. Inside the discharge tube 1, which is surrounded by the inner tube 1a, the outer tube 1b, and the sealing portions 1c and 1d, a small amount of mercury particles and hundreds of mercury particles are contained.
Pa argon, krypton, xenon, etc. are enclosed.

Inside the inner tube 1a is a tubular reaction space 2 into which a liquid is introduced, and the opening surrounded by the sealing portion 1c is surrounded by the liquid inlet 2a and the sealing portion 1d. The opened opening forms the discharge port 2b. That is, the inner tube 1a constitutes a reaction tube having the inlet 2a and the outlet 2b.

A reflection film 3 is coated on the outer side of the outer tube 1b. As the material of the reflective film 3, for example,
Gold, aluminum, etc. can be adopted. In addition, it is preferable to use a so-called cold type reflective film material such as a silica film that transmits visible light other than ultraviolet rays as the reflective film 3 because the internal temperature is not increased. The reflective film 3 is, for example,
The outer tube 1b can be coated by means such as vapor deposition, plating, coating and the like.

When the material of the reflective film 3 is conductive, the coating is applied to the outer tube 1b leaving the slit 3a in the axial direction, as shown in the developed view of FIG.
The slit 3a serves as a conduction cut-off band that cuts off the conduction of electricity, and the presence of the slit 3a prevents the induction current from flowing through the reflective film 3.

A coil 5 connected to a high frequency power source 4 is wound around the outer tube 1b. As the high frequency power supply 4, an alternating current capable of generating a high frequency induction current is used. The preferred frequency of the high frequency power source 4 is several MH.
It is z to several tens of MHz.

Further, an annular magnetic body 6 is arranged outside the coil 5. This is provided as an inductance for stably generating a high frequency induction current. Therefore, the frequency of the high frequency power source 4 is 10
It can be omitted if it is higher than MHz.

When oxidizing the liquid with the photo-oxidizer of this embodiment, the liquid is made to flow from the inlet 2a to the outlet 2b to fill the reaction space 2 with the liquid. Then, the high frequency power supply 4 is operated to supply a high frequency current to the coil 5. Then, a high-frequency induction magnetic field is generated along the longitudinal direction of the discharge tube 1, which causes a high-frequency induction current to flow in the circumferential direction of the discharge tube 1. As a result, discharge is generated in the discharge tube 1, and ultraviolet rays are emitted from the entire discharge tube 1. The ultraviolet rays thus radiated are reflected directly or inward by the reflection film 3,
The liquid in the reaction space 2 is irradiated. As a result, microorganisms and the like in the liquid are oxidized.

According to this embodiment, by high frequency induction,
Since the entire discharge tube 1 can be made to uniformly emit light and the entire reaction space 2 can be irradiated with ultraviolet rays, it is possible to efficiently photooxidize a fluid such as a liquid. Further, since no electrode for discharging is required, the structure is simplified and the life of the discharge tube 1 can be extended. Further, since the reflection film 3 is coated around the outer tube 1b, the energy of the emitted ultraviolet rays can be utilized for photooxidation without waste. Also, the reflective film 3
Covers the discharge tube 1 while being in close contact with the outer tube 1b, so that the emitted ultraviolet rays do not come into contact with the atmospheric gas,
Ozone gas generation can be reliably eliminated. Furthermore, the magnetic body 6
Is disposed, it is possible to stably generate a high frequency induction current and obtain a stable ultraviolet ray.

In this embodiment, the coil 5 is wound directly around the discharge tube 1 to generate a high frequency induction current. However, the means for generating the high frequency induction current is not particularly limited, and for example, the coil 5 can be built in the casing accommodating the discharge tube 1.

FIG. 3 shows a photo-oxidizer according to the second embodiment.
3A is a horizontal sectional view, and FIG. 3B is a vertical sectional view. 3A,
As shown in B, the photooxidizer according to the present embodiment has an inner tube 1
The outer tube 1a and the outer tube 1b are provided with the annular discharge tube 1 sealed by the sealing portions 1c and 1d at both ends thereof. Inside the discharge tube 1, which is surrounded by the inner tube 1a, the outer tube 1b, and the sealing portions 1c and 1d, a small amount of mercury particles that radiate 253.7 nm ultraviolet rays and the like by discharge and argon or krypton of several hundred Pa,
Xenon etc. are enclosed.

The discharge tube 1 of this embodiment is composed of the sealing parts 1c, 1
In the vicinity of d, electrode encapsulation portions 1e and 1f, which communicate with the inside surrounded by the inner tube 1a, the outer tube 1b, and the sealing portions 1c and 1d, are provided, and the electrodes 8a and 8b are enclosed. Electrode 8a,
8b is connected to an AC power supply (not shown), for example, the number 1
An alternating voltage of 0 KHz to several hundred KHz is applied.

A reflective film (not shown) is coated on the outer side of the outer tube 1b as in the first embodiment. The reflection film in this case is also coated, leaving a conduction cutoff band.

In this embodiment, the AC power source 9 and the coil 10 are used.
Thereby, the AC magnetic field H substantially oriented in the longitudinal direction (axial direction) of the discharge tube 1 is applied.

When oxidizing the liquid with the photo-oxidizer of this embodiment, the liquid is made to flow from the inlet 2a to the outlet 2b to fill the reaction space 2 with the liquid. Then, in the presence of the alternating magnetic field H, an alternating current is passed between the electrodes 8a and 8b. Then,
Discharge occurs between the electrodes 8a and 8b, but the discharge current at this time does not short-circuit between the electrodes 8a and 8b, and is spirally swirled under the influence of the AC magnetic field H. As a result, the discharge path extends inside the discharge tube 1, and ultraviolet rays are emitted from the entire discharge tube 1. The ultraviolet rays thus radiated are directly or reflected inward by the reflection film 3 and applied to the liquid in the reaction space 2. As a result, microorganisms and the like in the liquid are oxidized.

According to the present embodiment, the reaction space 2 can be made to uniformly emit light under the influence of the AC magnetic field H, so that the fluid such as a liquid can be efficiently photooxidized. Moreover, since the outer tube 1b is coated with a reflective film, the energy of the emitted ultraviolet rays can be utilized for photooxidation without waste. Moreover, since the reflective film covers the discharge tube 1 in a state of being in close contact with the outer tube 1b, the emitted ultraviolet rays do not come into contact with the atmospheric gas, and the generation of ozone gas can be reliably eliminated.

FIG. 4 shows a water treatment device according to the third embodiment. The water treatment device according to this embodiment includes a discharge tube 1 configured similarly to the discharge tube 1 of the first embodiment. Further, similarly to the first embodiment, the reflective film 3 is provided on the outer side of the discharge tube 1.
And a coil 5 connected to the high frequency power source 4 is wound.

In this embodiment, the inner diameter of the inner tube 1a of the discharge tube 1 is configured to be substantially the same as the inner diameter of the pipe 11 (11a, 11b) for transferring the treated water. And the discharge tube 1 is
It is attached in the middle of the pipe 11 for transferring the treated water. In FIG. 4, 11a is an inlet side pipe, and the inlet side pipe 11a and the discharge tube 1 are a connecting portion 12a and a seal ring 1.
3a is used for connection. Similarly, 11b is an outlet side pipe, and the outlet side pipe 11b and the discharge tube 1 are connected to each other by a connecting portion 12
b, the seal ring 13b is used for connection.

Although the material of the pipe 11 is not particularly limited, the connecting portions 12a and 12b are made of a non-conductive magnetic material. This is to prevent the induced current from spreading to the side of the pipe 11 and reducing the processing efficiency in the reaction space 2.

In this embodiment, the catalyst rod 15 is attached to the reaction space 2 inside the inner pipe 1a (not shown).
It is placed in a state of being held in. This catalyst rod 1
Reference numeral 5 is, for example, a surface of a non-conductive magnetic material coated with a photocatalyst. As the photocatalyst, for example, titanium oxide, zinc oxide, phosphorus oxide or the like can be used. The photocatalyst oxidizes the surface of the material forming the catalyst rod 15,
Coating can be performed by means such as coating, baking, vapor deposition, and chemical modification.

When sterilizing water with the water treatment apparatus of this embodiment, water such as sewage is caused to flow from the inlet side pipe 11a toward the outlet side pipe 11b to fill the reaction space 2 with water. And
The high frequency power supply 4 is operated to supply a high frequency current to the coil 5. As a result, discharge is generated in the discharge tube 1, and ultraviolet rays are radiated from the entire discharge tube 1. The ultraviolet light thus radiated is directly or reflected inward by the reflection film 3 and is applied to the water in the reaction space 2. As a result, microorganisms in water are oxidized and sterilized.

According to this embodiment, by high frequency induction,
Since the entire discharge tube 1 can be made to uniformly emit light and the entire reaction space 2 can be irradiated with ultraviolet rays, the water can be sterilized efficiently. Further, since no electrode for discharging is required, the structure is simplified and the life of the discharge tube 1 can be extended. Further, since the reflection film 3 is coated around the outer tube 1b, the energy of the emitted ultraviolet rays can be utilized for photooxidation without waste. Further, since the reflective film 3 covers the discharge tube 1 in a state of being in close contact with the outer tube 1b,
The emitted ultraviolet rays do not come into contact with the atmospheric gas, and ozone gas generation can be reliably eliminated. In addition, since the discharge tube 1 is simply attached to the pipe 11, the treatment can be performed without providing a reaction space for water treatment. Therefore, the size of the entire device can be reduced. Further, since the catalyst rod 15 is arranged, the reaction is promoted and the oxidation treatment can be efficiently performed.

FIG. 5 is a sectional view of the detecting portion of the TOC meter (total organic carbon content measuring device) according to the fourth embodiment, and FIG. 6 is FIG.
5 is a sectional view taken along line AA of FIG. 7, and FIG. 7 is a sectional view taken along line BB of FIG. The detector 20 of the TOC meter according to this embodiment includes the discharge tube 1 configured similarly to the discharge tube 1 of the first embodiment.
A reflective film (not shown) is coated on the outside of the discharge tube 1 as in the first embodiment. Further, the discharge tube 1 is adapted to radiate ultraviolet rays by a high frequency induction magnetic field generating means (not shown). The high frequency induction magnetic field generating means is not particularly limited, and for example, as in the first embodiment, a high frequency induction magnetic field may be applied to a coil directly wound around the discharge tube 1, a coil built in a casing accommodating the discharge tube 1, or the like. A configuration in which a current is passed can be adopted.

In this embodiment, the discharge tube 1 is incorporated in the recess 22 in the upper portion of the substantially block-shaped base material 21.
An electrode insertion opening 23 is formed on one end side (right side in the drawing) of the recess 22 of the base material 21 so as to be coaxial with the discharge tube 1. The electrode insertion port 23 is substantially the same as the outer diameter of the discharge tube 1 and the discharge tube receiving portion 23 a, and the inner diameter of the discharge tube 1, that is, the diameter of the reaction space 2 is substantially the same as the electrode insertion port 23 so as to be continuous with the reaction space 2. The connecting portion 23b provided and the electrode receiving portion 2 having a small diameter
3c, an electrode seal portion 23d having a diameter slightly larger than that of the electrode receiving portion 23c, and an enlarged diameter portion 23e.

A retaining hole 24 having a diameter larger than the outer diameter of the discharge tube 1 is formed on the other end side (left side in the drawing) of the concave portion 22 of the base material 21 so as to be coaxial with the discharge tube 1. The fastener 25 is fitted into the fastening hole 24 by using fastening screws 27, 27. An electrode insertion opening 26 is bored inside the fastener 25 so as to be coaxial with the discharge tube 1. The electrode insertion port 26 is provided with a discharge tube receiving portion 26a that is substantially the same as the outer diameter of the discharge tube 1 and an inner diameter of the discharge tube 1, that is, a diameter slightly smaller than the diameter of the reaction space 2, and that is continuous with the reaction space 2. The connecting portion 26b has a small diameter, the electrode receiving portion 26c has a small diameter, the electrode sealing portion 26d has a diameter slightly expanded from the electrode receiving portion 26c, and the diameter expanding portion 26e. The fastener 25 includes a collar portion 25a and a body portion 25b, and the body portion 25b is provided with annular grooves 25c and 25d. Further, a flow passage 28 penetrating between the connecting portion 26b and the outer peripheral surface of the body portion 25b is bored at approximately the center of the annular grooves 25c and 25d.

The discharge tube 1 is incorporated in the recess 22 in the upper portion of the base material 21 by the fastener 25. That is, in order to assemble the discharge tube 1, first, the base material 2
The discharge tube 1 is arranged in the recessed portion 22 of No. 1 with the seal rings 31 and 32 at both ends. Then, the annular grooves 25c, 25
In the fastener 25 with the seal rings 33 and 34 fitted in d,
The discharge tube 1 is pressed against the electrode insertion port 23 side. Thereby, the discharge tube 1 is kept watertight between the discharge tube receiving portion 23a and the discharge tube receiving portion 26a.

Then, in the reaction space 2 inside the discharge tube 1,
The conductivity electrodes 41 and 42 are inserted, and the tips of these conductivity electrodes 41 and 42 are arranged to face each other with an interval in consideration of detection sensitivity. The conductivity electrode 4
Both ends of Nos. 1 and 42 are connected to an instruction conversion unit (not shown) of the TOC meter. The conductivity electrode 41 is inserted into the reaction space 2 through the electrode insertion port 23. The outer diameter of the conductivity electrode 41 is slightly smaller than that of the electrode receiving portion 23c of the electrode insertion port 23, and is watertightly inserted by using the seal ring 43 in the electrode sealing portion 23d. An annular retaining rubber 44 is fitted on the enlarged diameter portion 23e of the electrode insertion opening 23. On the other hand, the conductivity electrode 42 is inserted into the reaction space 2 through the electrode insertion port 26. The outer diameter of the conductivity electrode 42 is equal to the electrode receiving portion 26c of the electrode insertion port 26.
It has a slightly smaller diameter and is watertightly inserted by using the seal ring 45 in the electrode seal portion 26d. An annular retaining rubber 46 is fitted on the enlarged diameter portion 26e of the electrode insertion opening 26.

The conductivity electrodes 41 and 42 are formed by coating the peripheral surface of a conductive material with a photocatalyst layer.
In addition, since the conductivity of a normal photocatalyst is poor, the conductivity electrode 4
The end faces of Nos. 1 and 42 are not coated with photocatalyst. As the conductive material, a material having high corrosion resistance is preferable, and for example, titanium, nickel, platinum, gold, stainless steel, glassy carbon or the like can be used. Further, as the photocatalyst layer, for example, titanium oxide, zinc oxide, phosphorus oxide or the like can be used. The photocatalyst layer can be formed by means of oxidation of the surface of the conductive material, coating, baking, vapor deposition, chemical modification, or the like. In particular, it is preferable that the conductive material is titanium and the photocatalyst layer is titanium oxide. In this case, the peripheral side surface of the titanium rod is oxidized and then the conductivity electrodes 41, 42 are
A structure in which the peripheral side surface is coated with titanium oxide and titanium is exposed on the end surface can be easily obtained by simply cutting at the position to be the end surface.

Further, the base member 21 has a connecting portion 23 at one end side.
Inlet flow path 51 communicating with b, and one end side of the communication path 2
8 is provided with an outlet channel 52, and a bypass channel 53 having one end communicating with the other end of the inlet channel 51. Then, the other end of the inlet channel 51 and the bypass channel 53
A sample liquid inlet 61 is provided at the communication part with. A sample liquid outlet 63 is provided on the other end side of the outlet channel 52 via a manifold 62. A solenoid valve 64 is provided in the outlet passage 52. Further, the other end side of the bypass flow path 53 communicates with the manifold 62 via a differential pressure valve 65.

When the total organic carbon content is measured by the TOC meter detection unit of the present embodiment, the electromagnetic valve 64 is opened and the sample solution is flown from the sample solution inlet 61 toward the sample solution outlet 63, and the reaction space 2 Fill the sample solution. While the electromagnetic valve 64 is open, the differential pressure valve 65 is closed by the pressure from the manifold 62 side, and the sample liquid flow in the bypass channel 53 is blocked.

After the sample liquid is sufficiently circulated and all the liquid in the reaction space 2 is replaced with the sample liquid to be measured, the electromagnetic valve 64 is closed to stop the flow of the sample liquid. When the electromagnetic valve 64 is closed, the sample liquid introduced from the sample liquid inlet 61 pushes the differential pressure valve 65 open. Therefore, the sample liquid is used in the bypass channel 53, the differential pressure valve 65, the manifold 62.
And is discharged directly from the sample liquid outlet 63.

In this way, with the sample liquid to be measured introduced into the reaction space 2, the high-frequency induction magnetic field generating means (not shown) is activated to start the ultraviolet irradiation from the discharge tube 1. This ultraviolet ray is directly or reflected inward by the reflective film coated on the discharge tube 1 and is applied to the sample solution in the reaction space 2.

By irradiating the sample solution in the reaction space 2 with ultraviolet rays, the organic carbon in the sample solution can be oxidized and converted into organic acid or carbon dioxide. Then, the change in the conductivity of the sample liquid thus obtained is converted into the conductivity electrode 41,
42. Then, based on the obtained change in conductivity, the total organic carbon content (TO
C) The value can be determined.

The oxidation reaction of the sample solution may be performed until it is completely completed, but it takes a long time to complete it. Therefore, the TOC may be obtained by obtaining the change in conductivity after a lapse of a certain time after the start of light irradiation and comparing this with a standard solution oxidized under the same conditions. Alternatively, the TOC may be obtained by irradiating the sample solution with ultraviolet rays kept flowing at a constant flow rate and comparing it with the case where the standard solution is caused to flow at the same flow rate.

According to the TOC meter using the detector of the present embodiment, the entire discharge tube 1 can be made to uniformly emit light by the high frequency induction and the entire reaction space 2 can be irradiated with ultraviolet rays, so that the sample liquid can be efficiently supplied. Can be oxidized. Further, since no electrode for discharging is required, the structure is simplified and the life of the discharge tube 1 can be extended. Also, the discharge tube 1
Since the reflective film is coated around the, the energy of the emitted ultraviolet rays can be utilized for photooxidation without waste. Further, since the reflective film covers the discharge tube 1 in a close contact state, the emitted ultraviolet rays do not come into contact with the atmospheric gas, and the generation of ozone gas can be reliably eliminated.

In the reaction space 2, the conductivity electrodes 41, 4 are provided.
Since 2 is built in, the entire apparatus can be downsized. In addition, the configuration of the entire device is simplified and manufacturing is easy. Further, since it is not necessary to introduce the sample solution into the separately provided sensor section, the consumption of the sample solution can be reduced. Also, by coating the photocatalyst layer on the conductivity electrodes 41 and 42, the contact area between the catalyst and the sample solution is increased, and the oxidation reaction occurring at the interface of the sample solution in contact with the catalyst is efficiently promoted with a small amount of the catalyst. can do. Therefore, according to the present embodiment, TOC can be efficiently measured with a small amount of sample liquid.

Although the present embodiment is shown as a TOC meter, it is possible to use various sensors such as optical sensors instead of the conductivity electrodes 41 and 42 to analyze various kinds of samples after oxidizing the sample liquid. It can be applied. For example, the measurement of total phosphorus and total nitrogen can be performed by colorimetric analysis by oxidizing a sample solution and causing it to color with a reagent.

[0066]

According to the photo-oxidizer of the present invention, the target component in the sample liquid can be efficiently and safely oxidized with a simple structure. Further, according to the water treatment device of the present embodiment,
It is possible to sterilize sewage and the like without requiring large equipment. Further, according to the total organic carbon content measuring apparatus of the present embodiment, it is possible to accurately measure the total organic carbon content in the sample liquid without increasing the size of the entire analyzer.

[Brief description of drawings]

FIG. 1 is a photo-oxidizer according to a first embodiment of the present invention,
1A is a horizontal sectional view, and FIG. 1B is a vertical sectional view.

FIG. 2 is a development view showing a state of a reflective film of the photo-oxidizer according to the first embodiment of the present invention.

FIG. 3 is a photo-oxidizer according to a second embodiment of the present invention,
3A is a horizontal sectional view, and FIG. 3B is a vertical sectional view.

FIG. 4 is a water treatment device according to a third embodiment of the present invention.

FIG. 5 is a total organic carbon content measuring device according to a fourth embodiment of the present invention.

6 is a cross-sectional view taken along the line AA of FIG.

7 is a sectional view taken along line BB of FIG.

FIG. 8 is a prior art photo-oxidizer.

FIG. 9 is a photo-oxidizer according to another prior art.

[Explanation of symbols]

1 ... Discharge tube, 1a ... Inner tube, 1b ... Outer tube, 2 ... Reaction space, 3 ... Reflective film, 4 ... High frequency power source, 5 ... Coil, 6 ... Magnetic material, 8a ... Electrode, 8b ... Electrode, 9 ...
… High current power supply, 10… Coil

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G01N 33/18 G01N 33/18 B H01J 65/04 H01J 65/04 A F term (reference) 2G042 AA01 BA03 CA02 CB03 DA03 DA07 DA09 FA08 FB05 GA10 HA07 4D037 AA03 AA11 AB02 AB03 BA18 BB02 4D050 AA05 AA15 AB07 BC06 BC09 BD08 4G075 AA15 AA65 BA06 CA33 CA54 EB31 EB33 EC21 FB02 FB06 5C039 NN04

Claims (12)

[Claims] 1. A tubular reaction space, and an annular ultraviolet light source arranged around the reaction space, the ultraviolet light source comprising:
A photo-oxidizer, which is a discharge tube in which an annular space formed by sealing an inner tube and an outer tube at both ends is filled with a substance that emits ultraviolet rays by electric discharge. 2. The photo-oxidizer according to claim 1, wherein a peripheral wall of the reaction space is constituted by an inner tube of the ultraviolet light source. 3. The photo-oxidizer according to claim 1, wherein the discharge tube is an electrodeless electrode and is a high-frequency discharge tube that discharges by high-frequency induction. 4. The discharge tube is an electrode discharge tube having a straight tubular inner tube, an outer tube, and a pair of electrodes, and is discharged by an AC voltage applied between the pair of electrodes. ,
The photo-oxidizer according to claim 1 or 2, wherein the photo-oxidizer is made in the presence of an alternating magnetic field oriented substantially in the longitudinal direction of the discharge tube. 5. The photo-oxidizer according to claim 1, further comprising a light-reflecting means that reflects light toward the inner surface around the ultraviolet light source. 6. The photo-oxidizer according to claim 5, wherein the light-reflecting means substantially reflects only ultraviolet rays. 7. The photo-oxidizer according to claim 5, wherein the light reflection means is a reflection film coated around the ultraviolet light source. 8. The reflective film is made of a conductive material,
The photo-oxidizer according to claim 7, wherein the ultraviolet light source is coated around the ultraviolet light source leaving a conduction cut-off band for cutting off an induced current. 9. The light according to claim 1, wherein a sensor for measuring a property of a fluid introduced into the reaction space is inserted inside the reaction space. Oxidizer. 10. The photooxidation according to claim 1, wherein a photocatalyst for promoting photooxidation of the fluid introduced into the reaction space is internally present in the reaction space. vessel. 11. A water treatment device, characterized in that water is sterilized by using the photo-oxidizer according to any one of claims 1 to 10. 12. A sample liquid is oxidized by using the photo-oxidizer according to claim 1.
A measuring device characterized by measuring the properties of a sample liquid.