JPH08182994A - Removal of fluorescent material and device therefor - Google Patents

Abstract

PURPOSE: To economically remove a fluorescent material contained in water without using ion exchange treatment or active carbon treatment. CONSTITUTION: An ozonized oxygen containing 0.1-50mg ozone per 1l service water is blown into service water and mixed. By producing the ozonized oxygen having thigh ozone content by passing a concentrated oxygen through an ozonizer 2 using a PSA oxygen concentration device and blowing the ozonized oxygen into the service water 8, the ozone content in the service water is increased and the fluorescent material is easily decomposed and removed. The utilization efficiency is further increased by using a rotary atomizer 5 as the blowing means of the ozonized oxygen and the mixing means of the service water with the ozonized oxygen.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for removing fluorescent substances contained in water.

[0002]

2. Description of the Related Art In recent years, a large amount of fluorescent whitening agents have been used in the textile industry and paper industry, and have also been incorporated into household detergents. Many of these phosphors have run into rivers and lakes, and as a result, water from these rivers has become contaminated with phosphors. Generally, water is subjected to coagulation, precipitation, filtration, ion exchange treatment, activated carbon treatment, or the like alone or in combination depending on the purpose of use. However, the fluorescent substance remains in the water in spite of these treatments,
It can be a problem.

Hygiene materials such as gauze and bandages, fluorescent materials,
Its use in medical materials is prohibited and water containing fluorescent substances cannot be used in the manufacture of these materials. Conventionally, the water used for the production has been subjected to ion exchange treatment, activated carbon treatment or the like to remove the fluorescent substance, but these treatments involve excessive regeneration and desorption operation, and the water cost in the production cost becomes excessive.

[0004]

The present invention has been completed with the object of providing an effective and economical method for removing a fluorescent substance, which does not rely on ion exchange treatment, activated carbon treatment or the like.

[0005]

[Means for Solving the Problems] Ozone has a strong oxidizing power, so it has been conventionally used for decolorization of factory wastewater and deodorization of purified water, but it is toxic and may be dangerous during treatment. , Generally was not widely used. The present inventor paid attention to the strong oxidizing power of ozone, and as a result of vigorous research, established appropriate means and conditions for efficiently utilizing ozone, and easily and economically using fluorescent substances in water. I found that it can be removed. That is, a method for removing a fluorescent substance was completed, in which ozonized oxygen containing 0.1 to 50 mg of ozone was blown in and mixed with 1 liter of water to oxidize and remove the fluorescent substance contained in the water.

Further, an ozone generator for supplying concentrated oxygen to generate ozonized oxygen, and a blowing means for blowing the generated ozonized oxygen containing relatively high concentration ozone into the water containing the fluorescent substance, An efficient fluorescent substance removing device comprising a mixing means for bringing blown ozonized oxygen into contact with water has been completed. In particular, it is preferable to use a rotary atomizer for the blowing / mixing means for contacting the ozonized oxygen with the water, while also blowing the ozonized oxygen, because the use efficiency of ozone can be improved. FIG. 1 is a flow sheet showing an embodiment of the fluorescent substance removing apparatus of the present invention, in which 1 is a concentrated oxygen supply apparatus,
2 is an ozone generator, 3 is a gas-liquid contact device, 4 is water supply piping, 5 is a rotary atomizer, 6 is treated water derivation piping, 7 is a device for decomposing residual ozone, 8 is water, and 9 is ozonization. It is an oxygen pipe.

[0007]

FUNCTION AND EXAMPLE OF EMBODIMENT The present invention will be described in detail with reference to FIG. First, the ozone generating means 2 suitable for the present invention will be described. One feature of the present invention is that concentrated oxygen is supplied to the ozone generator 2 to generate ozonized oxygen containing a relatively high concentration of ozone, and the ozonized oxygen is brought into contact with a fluorescent substance to be oxidatively decomposed. There is. Therefore, the oxygen supply device 1 to be used has a PSA (Pre
Sure Swing Adsorption) Oxygen concentrated using an oxygen generator, high-concentration oxygen filled in a high-pressure container, or the like is used. Among them, the PSA oxygen generator is convenient because it is easy to operate and economically obtains a high concentration of oxygen. The concentration of concentrated oxygen is usually 5
It may be about 0% by volume or more, and more preferably 80% by volume or more. The ozone generator 2 is not particularly limited, and silent discharge or ultraviolet irradiation can be used.
When air is supplied to the ozone generator to generate ozone, the ozone concentration in the ozonized oxygen is usually 3000 p
It is about pm. When this ozonized oxygen is blown into the water using an ejector, the ozone concentration in the water is about 5p.
It will be pm. On the other hand, when oxygen having a concentration of 90% is supplied to the ozone generator 2, the ozone concentration in the ozonized oxygen obtained usually reaches 10,000 to 50,000 ppm. If a PSA oxygen generator using a zeolite molecular sieve or a carbon molecular sieve as an adsorbent is used, concentrated oxygen having a concentration of 30 to 99% can be easily obtained.
If this concentrated oxygen is supplied and ozonized, 4000-5
Ozonized oxygen containing ozone of about 0000 ppm can be easily and economically produced.

The generated ozonized oxygen is ejected by the ejector,
It is necessary to blow gas into the water by using a gas blowing means such as a nozzle, and efficiently contact the water by using a mixing means such as a static mixer or a gas-liquid mixing pump. In the present invention, as shown, the rotary atomizer 5
However, it can be used particularly preferably as a means for simultaneously performing the blowing and mixing of ozonized oxygen. The basic principle of the rotary atomizer will be briefly described with reference to FIG.
FIG. 2 is a schematic view of the mounting of the rotary atomizer.
The rotary atomizer 21 mounts the cup-shaped rotor 23 on the bottom of the water 22 and rotates at high speed with the central shaft 24 as the rotation shaft, while the ozonized oxygen inlet pipe 29
Through this, ozonized oxygen is supplied into the rotor 23, and the ozonized oxygen is made to overflow into the water 22 through the opening 25 at the lower end. The overflowed ozonized oxygen forms an ozonized oxygen film 26 on the rotor surface, and the water 22 and the gas film 26 are formed.
Due to the shear stress between
It is divided into 7 and dispersed in the water 22. Treated water is pipe 3
Discharge from 0 to the outside of the system. 28 is a water supply pipe. Although details are omitted, it is of course possible to use a rotor whose shape is modified. The rotary atomizer has a gas-liquid contact efficiency several times higher than that when a line mixer is used as a mixing means, for example. Normal,
The rotation speed of the rotor of the rotary atomizer is 1000.
~ 3000 rpm.

The amount of ozone blown is 0.1 to 50 mg, preferably 0.5 to 20 mg, per liter of water to be treated.
Is. If it is less than 0.1 mg, it is not sufficient for the oxidative decomposition of the fluorescent substance, and if it exceeds 50 mg, it will not be dissolved in the water, so that an effect commensurate with the amount of injection cannot be obtained. The time required for the oxidation treatment is usually 0.5 minutes to 3 hours.

The fluorescent substance removing device of the present invention may be provided with an exhaust ozone decomposing device 7 for detoxifying unreacted ozone. There is no limitation on the type of the exhaust ozone decomposing device, and catalytic decomposition or thermal decomposition can be used.

The present invention can be used to remove most types of fluorescent materials. Examples thereof include diaminostilbene-disulfonic acid derivative, imidazole derivative, coumarin derivative, pyrazoline derivative, oxazole-based naphthalimide derivative, bisbenzoxazolyl derivative, and bisstilbiphenyl derivative. Among these, it is effective in removing the diaminostilbene-disulfonic acid derivative, the coumarin derivative and the bisbenzoxazolyl derivative.

[0012]

EXAMPLES The present invention will be specifically described with reference to examples.
The fluorescence in water was measured as follows.

Standard fluorescence: 100 mg of diaminostilbene-disulfonic acid derivative (type I compound) (fluorescent whitening agent: Hakkol BN Conc: Showa Kagaku Co., Ltd.) was added with purified water to prepare a 1 liter aqueous solution. did. Add 100 ml of this stock solution to water to dilute it to 1 liter,
A fluorescent standard solution was prepared. Add this fluorescent standard solution to 1, 3, 5,
7, 10, 30, 50, 70 and 100 ml each were separated, and water was added to each to make 100 ml. After soaking No. 2 filter paper in this solution for about 10 minutes in the dark,
Take it out and swiftly transfer it to the watch glass without squeezing.
It was dried at 0 ° C. for about 30 minutes. The fluorescence of the dried filter paper
In the order in which the amounts of the solutions are listed, 0.1 degree, 0.3 degree, 0.
It was set to 5 degrees, 0.7 degrees, 1 degree, 3 degrees, 5 degrees, 7 degrees and 10 degrees. The fluorescence of these filter papers was stable for at least January.

Measurement operation: 3000 ml of test water was poured into a Buchner funnel with No. 2 filter paper set, and gravity filtration was performed.
If the test water is cloudy, use a glass filter (3G
3) or the glass fiber filter paper (GS-25: manufactured by Toyo Roshi Kaisha, Ltd.) was used to filter the test water.After filtration, the filter paper was transferred to a watch glass and kept at 105 to 110 ° C for about 30 minutes. It was dried, irradiated with ultraviolet rays (366 nm) in the dark, and compared with the standard fluorescence to obtain the fluorescence having the same fluorescence.

Example 1 A PSA oxygen generator (S-05: manufactured by Sumitomo Seika Co., Ltd.) was used to concentrate the oxygen concentration in the air to 90% by volume, and the resulting concentrated oxygen was subjected to creeping discharge ozone. Generator (SA-10
0: Sumitomo Seika Co., Ltd.) was used to generate 60 liters / hour of ozonated oxygen containing 17,000 ppm of ozone. On the other hand, the rotary atomizer (OB-1
0: Sumitomo Seika Chemicals Co., Ltd. installed has a real internal volume of 0.5
the gas-liquid contact apparatus of m ^3, the industrial water fluorescence is 0.4 to 0.6 was supplied at a rate of 1 m ³ / time, mixing said ozonized oxygen through a rotary atomizer, industrial water, stirred While blowing. The average retention time of industrial water was 20 minutes, and the amount of ozone blown per liter of industrial water was about 2.2 mg. The fluorescence of the treated industrial water was measured and found to be 0.

Example 2 Using a PSA oxygen generator (S-05: Sumitomo Seika Chemicals Co., Ltd.), the oxygen concentration in the air was concentrated to 90% by volume, and the resulting concentrated oxygen was subjected to creeping discharge ozone. Generator (SA-10
0: Sumitomo Seika Co., Ltd.) was used to generate 60 liters / hour of ozonated oxygen containing 22000 ppm of ozone. On the other hand, in 20 liters of industrial water with a fluorescence of 0.6,
A diaminostilbene-disulfonic acid derivative fluorescent whitening agent (Hakkor BN Conc .: Showa Kagaku Co., Ltd.) was added,
Test water having a fluorescence of 2 was prepared. This test water is at the bottom with a rotary atomizer (OB-1: Sumitomo Seika Chemicals Ltd.)
Was put into a gas-liquid contactor having a substantial internal volume of 50 liters. Through the rotary atomizer, the above-mentioned ozonized oxygen was mixed with the test water that had been introduced, and the test water was blown with stirring to treat the test water in a batch system. When the fluorescence degree in the test water sampled 30 seconds after the start of the treatment was measured, it was already zero. The amount of ozone blown per liter of test water was about 1.2 mg.

Example 3 Using the same apparatus as used in Example 2, the test water was treated in a batch system while flowing ozonized oxygen in the same manner as in Example 2. The test water was adjusted to have a fluorescence of 10 by adding a fluorescent whitening agent of a diaminostilbene-disulfonic acid derivative (Tinopearl CBS-X: manufactured by Ciba Geigy) to 20 liters of industrial water having a fluorescence of 0.7. The ozonized oxygen was obtained by concentrating the oxygen concentration in the air to 90% by volume, and generating 3 liters / min of ozonized oxygen containing 15000 ppm of ozone in the ozone generator. The ozonized oxygen was mixed into the test water through the rotary atomizer and blown with stirring. When the fluorescence degree in the test water sampled 90 seconds after the start of the treatment was measured, it was already zero. The amount of ozone blown in per liter of test water was about 7.5 mg.

Example 4 Using the same apparatus as used in Example 2, the test water was treated in a batch system while flowing ozonized oxygen in the same manner as in Example 2. The test water was adjusted to a fluorescence level of 5 by adding a fluorescent whitening agent of a coumarin derivative (Illuminal WN: Showa Kako Co., Ltd.) to 20 liters of industrial water having a fluorescence level of 0.6. Ozonized oxygen concentrates the oxygen concentration in the air to 90% by volume, and is 16000 ppm in the ozone generator.
3 liters / minute of ozonized oxygen containing 1 oz of ozone was generated. The ozonized oxygen was mixed into the test water through the rotary atomizer and blown with stirring. When the fluorescence degree in the test water sampled 90 seconds after the start of the treatment was measured, it was already zero. The amount of ozone blown in per liter of test water was about 7.8 mg.

Example 5 Using the same apparatus as used in Example 2, test water was treated in a batch system while flowing ozonized oxygen in the same manner as in Example 2. The test water consisted of 20 liters of industrial water with a fluorescence of 0.7 and a fluorescent whitening agent of bisbenzoxazolyl derivative (Mika White KTN Conc: Nippon Kayaku Co., Ltd.).
Manufactured) was added to adjust the fluorescence to 7. Ozonized oxygen was generated and used in the same manner as in Example 4. When the fluorescence in the test water sampled 120 seconds after the start of treatment was measured, it was already zero. The amount of ozone blown in per liter of test water was about 8 mg.

[0020]

INDUSTRIAL APPLICABILITY The fluorescent substance removing method and the fluorescent substance removing apparatus of the present invention utilize the strong oxidizing power of ozone, and use concentrated oxygen to remove ozonized oxygen containing relatively high concentration of ozone. Since the fluorescent substance is continuously generated and blown into the water for oxidation to remove the fluorescent substance, the fluorescent substance in the water is easily and completely decomposed. Unlike conventional removal devices, operations such as regeneration and desorption are not required, and continuous processing can be performed in one series, which is simple and economical. Further, if a rotary atomizer is used for blowing ozonized oxygen, mixed contact of gas and liquid is significantly improved, and thus blown ozone is efficiently used.

[Brief description of drawings]

FIG. 1 is a flow sheet showing an embodiment of a fluorescent substance removing apparatus of the present invention.

FIG. 2 is a schematic view of the installation of a rotary atomizer.

[Explanation of symbols]

1: Oxygen supply device 2: Ozone generator 3: Gas-liquid contact device 4: Water supply pipe 5: Rotary atomizer 6: Treated water outlet pipe 7: Residual ozone decomposing device 8: Water 9: Ozonized oxygen pipe 21: Rotary atomizer 22: Water 2
3: Rotor 24: Central axis 25: Opening 26: Ozonized oxygen film 27: Micro bubbles 28: Water supply pipe 29: Ozonized oxygen inlet pipe 30: Treated water pipe

Claims (3)

[Claims] 1. A method for removing a fluorescent substance, characterized in that ozonated oxygen containing 0.1 to 50 mg of ozone is blown in and mixed with 1 liter of water to oxidize and remove the fluorescent substance contained in the water. 2. An ozone generator for supplying concentrated oxygen to generate ozonized oxygen, a blowing means for blowing the generated ozonized oxygen into water containing a fluorescent substance, blown ozonized oxygen and water. And a mixing means for contacting the fluorescent substance with the fluorescent substance removing device. 3. A fluorescent substance removing apparatus according to claim 2, wherein a rotary atomizer is used as a blowing means of ozonized oxygen and a mixing means of the ozonized oxygen and water.