JP2591770Y2 - Dissolved ozone concentration measurement device - Google Patents

Description

[Detailed description of the invention]

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a gas sensor for a semiconductor element structure or the like by dissolving dissolved ozone in a sample water sampled from tap water or industrial water into a gas phase through a microporous polymer membrane. The present invention relates to a dissolved ozone concentration measuring device for measuring the dissolved ozone concentration in sample water based on the measured value.

[0002]

2. Description of the Related Art In general, in the field of use of ozone such as clean water and industrial water, the solubility of ozone in water greatly changes depending on the water temperature and the ozone concentration in the gas phase. Due to its unstable properties such as decomposition at the time of generation, continuous measurement of ozone concentration is required.

[0003] Conventionally, the concentration measuring apparatus of dissolved ozone is extremely high in accuracy compared with, for example, concentration measurement using a reagent, and is also excellent in automation and the like. 2. Description of the Related Art A concentration measuring device using an absorption method is known. This ultraviolet absorption method utilizes the fact that ozone has an absorption spectrum (Hartley band) having a peak around 254 nm in the ultraviolet region, and a strong emission line at 253.7 nm is applied to the sample water in the ultraviolet-permeable flow cell. UV light is directly radiated from a low-pressure mercury lamp having a spectrum and the like, and the Lambert. The concentration is measured based on Beer's law.

[0004]

However, the conventional general concentration measuring apparatus of the absorption spectrophotometric method has many advantages such as that the components contained in the sample water can be selectively measured by the difference in wavelength. Since inorganic ions, amino acids, proteins, ammonia, amine chloride, microluocyan, etc., which are coexisting substances other than ozone, adversely affect the measured values, special equipment must be provided to remove these coexisting substances other than ozone. Must.

On the other hand, similarly to the concentration measuring apparatus using the ultraviolet absorption method, there has been proposed a measuring apparatus which measures liquid phase ozone using a membrane separation method as a method without using a reagent. An apparatus employing this kind of membrane separation method is, for example, a double tube in which an outer tube such as glass is disposed around the outer periphery of a small-diameter inner tube made of PTFE or the like, which is a microporous polymer membrane, into a gas phase. It was used as a separator and a flow cell for transferring dissolved ozone.

In the apparatus having the above structure, the ozone in the sample water flowing into the inner tube passes through the inner tube of the microporous polymer film, and enters the space provided between the inner tube and the outer tube. Since it moves, the ozone-containing gas can be guided to appropriate measurement means such as a chemiluminescence method by flowing clean air into the space, and according to this method, the measured value of the coexisting substance in the sample water can be measured. The effect can be avoided.

However, none of these concentration measuring devices are suitable for measuring the concentration of low-concentration ozone, which requires time and effort for maintenance, and the structure of the device is complicated, so that the size and cost are inevitable. And so on.

[0008]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention employs a thin film separation method using a microporous polymer membrane, and further attempts to provide a concentration measuring device having a simple structure by devising the device configuration. It is a thing. That is, the dissolved ozone in the sample water moves into the gas phase through the microporous polymer membrane provided in the closed container,
By measuring the ozone with a gas sensor having a semiconductor element structure or the like, the device configuration can be simplified and the cost can be reduced. In the dissolved ozone concentration measuring device disclosed in claim 1, a contact pipe is connected to the sample water inlet. With this arrangement, it is possible to smoothly transfer ozone to the gas phase, thereby further improving the functionality and reliability. In the dissolved ozone concentration measuring device disclosed in claim 2, a gas sensor is provided as a specific structure. While the measurement chamber to be installed is formed by a cylindrical joint, a cap body with a microporous polymer membrane wall formed at the tip surface is formed, and this is configured to be detachably attached to the cylindrical joint for maintenance. It is the one with improved performance.

[0009]

The main object of the present invention is, as described above, a thin film separation method using a microporous polymer membrane as this type of concentration measuring apparatus, and furthermore, ozone transferred to the gas phase is used as a semiconductor. An object of the present invention is to provide a dissolved ozone concentration having a simple structure by measuring with a gas sensor having an element structure or the like.

[0010]

According to a first aspect of the present invention, a sealed container having a sample water inlet and a sample water outlet is formed, and the sealed container is provided with a highly porous material. Forming the wall surface of the molecular film and forming a measurement chamber outside the polymer film, disposing a gas sensor in the measurement room, and discharging the sample water toward the wall surface of the polymer film to the sample water inlet. The configuration according to claim 2 of the utility model registration claim is a configuration in which a pipe is provided, and in the dissolved ozone concentration measurement device according to the claim 1 of the utility model registration claim, the measurement chamber is disposed outside the closed container. A cylindrical joint disposed in a penetrating state to the middle side, and detachably fixed to a distal end portion on the inner side of the sealed container of the cylindrical joint, and a wall surface of a microporous polymer film is provided on the distal end surface. This is a configuration formed with a cap body.

[0011]

[Embodiment of the Invention] The present invention that has achieved the object will be described below with reference to the drawings of the embodiments. FIG. 1 is a schematic diagram of a dissolved ozone concentration measuring device according to claim 1 of the present invention, and FIG. 2 is a first diagram of claim 2 of the present invention.
FIG. 3 is a schematic sectional view showing a dissolved ozone concentration measuring device according to an embodiment, and FIG.
It is a schematic sectional drawing which shows the dissolved ozone concentration measuring apparatus of the 2nd Example.

The dissolved ozone concentration measuring device of the present invention is shown in FIG.
As shown in FIG. 2, dissolved ozone in sample water A collected from tap water, industrial water, or the like is injected into the gas phase of the measurement chamber 3 through the microporous polymer membrane 2 provided in the closed container 1. And the ozone in the gaseous phase is measured by a gas sensor 4 such as a semiconductor device structure disposed in the measurement chamber 3, and the concentration of dissolved ozone in the sample water A is measured based on the measured value. It is an ozone concentration measuring device.

A dissolved ozone concentration measuring device according to claim 1 of the present invention is a sealed container provided with a sample water inlet 1a and a sample water outlet 1b as shown in the schematic diagram of FIG. 1, a wall of a microporous polymer film 2 is formed on the closed container 1 and a measurement chamber 3 is formed outside the polymer membrane 2, and a gas sensor 4 is provided in the measurement chamber 3. Let
The gist is that a contact tube 5 for discharging the sample water A toward the wall surface of the polymer film 2 is provided at the sample water inlet 1a.

That is, in the dissolved ozone concentration measuring apparatus 1 according to the present invention, a sample water inlet 1a is provided on a lower side such as a bottom surface and a upper side such as a side surface is provided on a lower side such as a bottom surface, as a function of a flow cell for measurement. An appropriately shaped hermetically sealed container 1 provided with a sample water outlet 1b is formed.

The sample water inlet 1a of the sealed container 1 is connected to a sample water A inlet piping (not shown) provided with a pump device and the like, and the sample water outlet 1b is connected to the sample water A. The sample water A is connected to a discharge-side pipe line (not shown).
The concentration of dissolved ozone in the sample is measured by a gas sensor 4 disposed in a measurement chamber 3 described later while continuously flowing sample water A from the sample water inlet 1a toward the sample water outlet 1b.
It is performed by

The measuring chamber 3 is formed, for example, as an airtight space in which the upper surface of the sealed container 1 is bulged inward, and a liquid such as water does not pass through the bottom of the measuring chamber 3. A gas sensor, such as a semiconductor element structure, having a wall surface of a polymer film 2 made of a microporous thin film made of PTFE or the like that allows gas such as ozone to pass therethrough, and having a space in the measurement chamber 3 connected to a display device 6 or the like. 4 is provided.

The gas sensor 4 is electrically connected to an analysis circuit using a resistor or the like, a control circuit, or the like.
The gas sensor 4 is made of a metal oxide semiconductor such as nO ₂ , ZnO, and Fe ₂ O _2, and its electric resistance (electric conductivity) changes when ozone comes into contact with the surface of the gas sensor 4.

The dissolved ozone concentration measuring apparatus of the present invention converts ozone dissolved in the sample water A inside the closed container 1 into a gas phase in the measuring chamber 3 through the microporous polymer film 2. The dissolved ozone concentration is measured based on the electric resistance value of the gas sensor 4 changed by the contact of the ozone gas. When the bubbles accumulate on the surface of the polymer film 2, the dissolved ozone in the sample water A is dissolved. Is measuring room 3
It does not move smoothly into the gas phase inside, resulting in a decrease in accuracy such as a variation in measured values.

For this reason, in the dissolved ozone concentration measuring apparatus of the present invention, a contact tube 5 having a discharge port disposed in the vicinity of the polymer membrane 2 is provided at the sample water inlet 1a, and the closed container 1 for the sample water A is provided. At the time of introduction into the inside, the sample water A is discharged toward the wall surface of the polymer film 2 to prevent generation of bubbles on the polymer film 2.

Next, claim 2 of the utility model registration claim
As shown in the schematic cross-sectional views of FIGS. 2 and 3, the dissolved ozone concentration measuring device forms a closed container 1 provided with a sample water inlet 1a and a sample water outlet 1b. In addition, a wall of the microporous polymer membrane 2 is formed and a measurement chamber 3 is formed outside the polymer membrane 2, a gas sensor 4 is disposed in the measurement chamber 3, and the sample water inlet 1a is 2. The dissolved ozone concentration measuring apparatus according to claim 1, further comprising a contact tube for discharging the sample water toward the wall surface of the polymer film. A tubular joint 3a disposed in this state, and a tubular joint 3a detachably fixed to a tube end inside the sealed container 1 and a wall surface of a microporous polymer film 2 provided at a distal end surface. The gist is that the cap body 3b is formed with the cap body 3b.

That is, Claim 2 of the utility model registration claim.
The dissolved ozone concentration measuring device described in (1) further discloses a specific device structure in the dissolved ozone concentration measuring device disclosed in claim 1, and mainly includes a closed container 1
And a general-purpose cylindrical joint 3 a and a cap body 3 b for forming the wall surface of the polymer film 2 and the measurement chamber 3.

The hermetically sealed container 1 is composed of, for example, a cylindrical container main body and a lid or the like fitted to the upper opening and the lower opening of the container main body via appropriate sealing means such as an annular ring. A substantially circular through-hole is formed in a part of the lid on the upper surface, and the cylindrical joint 3a is inserted into the through-hole through a suitable sealing means.
2 and 3, a screw portion is formed in the through hole, and a cylindrical joint 3a is formed in the screw portion.
Are screwed and fixed.

The cylindrical joint 3a is formed of a general-purpose synthetic resin pipe joint or the like having a threaded portion on the outer peripheral surface of one end of the tube which forms the inner side of the sealed container 1. Fitting 3
The cylindrical joint 3a and the cap body 3b are detachably fixed to each other by forming a cap body 3b that can be screwed to the threaded portion a.

A display means 6 provided outside is provided from the other end of the tube on the outside of the sealed container 1 to the space in the body.
And a gas sensor 4 having a semiconductor element structure connected thereto, and the other end of the tube is sealed by appropriate means,
A space surrounded by the body of the cap body 3b and the cylindrical joint 3a is used as the measurement chamber 3.

An opening is formed in the tip surface of the cap body 3b, and the cap body 3b is connected to the cylindrical joint 3a.
At the time of screwing, the sheet-like microporous polymer film 2 is sandwiched between the cap 3b and the cylindrical joint 3a, and the opening of the cap 3b is closed with the polymer film 2. Thereby, the wall surface of the polymer film 2 is formed in the measurement chamber 3.

In the dissolved ozone concentration measuring apparatus according to the second aspect of the present invention, since the cap body 3b provided with the polymer film 2 is detachable from the cylindrical joint 3a, the polymer film 2 can be used with time. When is deteriorated, it is only necessary to remove the cap body 3b and replace the polymer film 2, and maintenance is extremely easy.

In the illustrated dissolved ozone concentration measuring apparatus,
The sample water inlet 1a is provided on the bottom wall of the closed cylindrical container 1 having a bottom, and the sample water outlet 1b is formed on the side wall of the closed container 1. The sample water inlet 1a is provided at the bottom opening. Various design changes are possible, such as providing on the fitted lid or providing the sample water outlet 1b on the lid fitted on the upper surface opening.

[0029]

According to the present invention, the dissolved ozone in the sample water is moved into the gas phase through a microporous polymer film provided in a closed container, and the ozone is measured by a gas sensor such as a semiconductor element structure. Therefore, unlike the concentration measuring apparatus of the ultraviolet absorption method, there is no interference by coexisting substances in the sample water, and the apparatus configuration can be simplified to provide a low-cost apparatus. If you use
It is possible to provide a measuring device that can measure low-concentration dissolved ozone with high sensitivity and is suitable for leak management of residual ozone concentration. Further, in the dissolved ozone concentration measuring device disclosed in claim 1 of the present invention, since the contact tube is provided at the inlet of the sample water, the ozone moves into the gas phase without accumulating air bubbles on the polymer film. Is performed smoothly, so that the function and the reliability are excellent. In the dissolved ozone concentration measuring device disclosed in claim 2, a measuring chamber in which a gas sensor is disposed is further formed by a cylindrical joint, and the measuring chamber is formed on the distal end surface. Since the cap body with the microporous polymer membrane wall is detachably attached, it is an epoch-making and excellent maintenance in addition to the above-mentioned effects and simplification of membrane exchange. This is a very meaningful idea.

[0029]

[Brief description of the drawings]

FIG. 1 is a schematic view of a dissolved ozone concentration measuring apparatus according to claim 1 of the present invention;

FIG. 2 is a schematic sectional view showing a dissolved ozone concentration measuring apparatus according to a first embodiment of claim 2 of the present invention;

FIG. 3 is a schematic sectional view showing a dissolved ozone concentration measuring apparatus according to a second embodiment of claim 2 of the present invention;

[0030]

[Explanation of symbols]

 A sample water 1 sealed container 1a sample water inlet 1b sample water outlet 2 polymer membrane 3 measurement chamber 3a cylindrical joint 3b cap body 4 gas sensor 5 contact tube 6 display device

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-204242 (JP, A) JP-A-4-264229 (JP, A) JP-A-4-131756 (JP, A) JP-A-6-204 258269 (JP, A) JP-A-2-24039 (JP, A) JP-A-2-240538 (JP, A) JP-A-3-85564 (JP, U) JP-A-59-109954 (JP, U) (58) Fields surveyed (Int. Cl. ⁶ , DB name) G01N 27/12 G01N 1/22 G01N 33/18

Claims (2)

(57) [Scope of request for utility model registration] 1. A closed container provided with a sample water inlet and a sample water outlet is formed, and a wall of a microporous polymer film is formed on the closed container and measurement is performed outside the polymer film. A gas sensor is disposed in the measurement chamber, and a contact pipe for discharging sample water toward the wall surface of the polymer film is provided in the sample water inlet, the dissolved ozone concentration measuring device being characterized in that: . 2. The dissolved ozone concentration measuring device according to claim 1, wherein the measuring chamber is disposed so as to penetrate from the outside to the inside of the sealed container. Dissolved ozone concentration measurement characterized in that it is detachably fixed to the tube end inside the closed container of the tubular joint and is formed by a cap body provided with a microporous polymer membrane wall surface at the end surface apparatus.