JP3377733B2 - Method and apparatus for treating contaminated water containing harmful substances - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to various harmful components (CO
Method and apparatus for treating contaminated water such as pool water and bath water containing organic pollutants such as component D, malodorous components, bacteria, etc., especially contaminated water with improved efficiency of detoxification by the action of ozone The present invention relates to a processing method and device.

[0002]

2. Description of the Related Art Contaminated water containing harmful substances such as C
The basic operation in the treatment of wastewater containing OD components is to oxidize the oxidizable components generally called chemical oxygen demand (COD) contained in the wastewater with an oxidant to highly oxidize to the final form of oxidation. It is common to decompose or aggregate as a hardly soluble component. As the oxidizer for this purpose, the cheapest and most easily available air (oxygen contained in this) is aerated to the waste water to oxidize the COD component. By this method, a considerable amount of COD components can be oxidatively decomposed, but oxidation by dissolved oxygen may inevitably leave insufficient components. For this reason, more powerful oxidizing agents such as hydrogen peroxide, sodium hypochlorite, ozone, etc. are used, but these are quite expensive and hydrogen peroxide has been pointed out to have a carcinogenicity. As for sodium hypochlorite, it has been pointed out that the carcinogenicity of trihalomethane, which is a by-product of the reaction with organic substances, is high. Ozone is inferior to sodium hypochlorite in oxidizing power, and its self-decomposition progresses, so its safety is currently evaluated, but the change from hydrogen peroxide and sodium hypochlorite is completely Not done. In addition, when ozone is added to the waste water to oxidize and decompose the COD component, the collision of the ozone with the third substance other than the COD component in the liquid phase increases the frequency of decomposition without contributing to oxidative decomposition. Therefore, there is a problem that the oxidative decomposition efficiency is low.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above problems in the prior art, and efficiently uses polluted water containing harmful substances such as COD components by using ozone, which is a highly safe oxidant. An object of the present invention is to provide a contaminated water treatment method that can be well treated and an apparatus for the same.

[0004]

The present invention has the following constitutions (1) to (5) as means for solving the above problems.

(1) Ozone in polluted water containing harmful substances
After adding and mixing, adsorb ozone and remove harmful substances.
SiO ₂ / Al ₂ O ₃ ratio of 70 or more
Intasil zeolite, SiO ₂ / Al ₂ O ₃ ratio 20 or more
Dealuminized faujasite, SiO ₂ / Al ₂
Mesoporous silicates having an O ₃ ratio of 20 or more or these
Filled with a high silica adsorbent that is a mixture of two or more of these
By passing the adsorbent layer through the
Co-adsorb the substance and ozone to the high silica adsorbent,
Characterized by detoxifying harmful substances by the action of ozone
A method for treating contaminated water containing harmful substances.

(2) It is characterized in that the treated water after detoxifying harmful substances in the adsorbent layer is contacted with an ozone decomposing agent to decompose residual ozone and prevent leakage of ozone to the downstream. The method for treating contaminated water containing harmful substances according to (1 ) above.

(3) A high silica pen having an SiO ₂ / Al ₂ O ₃ ratio of 70 or more that adsorbs ozone and adsorbs harmful substances.
Tasil zeolite, SiO ₂ / Al ₂ O ₃ ratio of 20 or more
Aluminum-free faujasite, SiO ₂ / Al ₂ O
₃ or more of 20 or more mesoporous silicates or these
The adsorbent packed column provided with an adsorbent layer of a high silica adsorbent that is a mixture of two or more of the following , a supply pipe for supplying contaminated water containing a harmful substance to the adsorbent packed column, and a connection to the supply pipe An apparatus for treating polluted water containing harmful substances, comprising: an ozone generator for adding ozone to polluted water; and a discharge pipe for discharging treated water that has been treated from the adsorbent packed tower.

[0008]

(4) An apparatus for treating polluted water containing harmful substances according to (3) , wherein an ozone decomposing agent layer that decomposes leaking ozone is provided on the downstream side of the adsorbent packed tower. .

[0010] (5) the said prior stream side and / or rear flow side of the ozone injection point of the adsorbent packed column, characterized by comprising filtration material layer is provided for removing suspended solids (3 )or
Is a treatment device for polluted water containing harmful substances of (4) .

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The method of the present invention contains oil and fat contaminants in pool water and bath water, protein-based contaminants, COD components in domestic and industrial wastewater, bacteria such as Escherichia coli, and harmful substances such as malodorous components. It is characterized in that after ozone is added to and mixed with the contaminated water, the adsorbent layer filled with the adsorbent is caused to flow through the adsorbent layer so that detoxification due to the action of ozone is advanced with high efficiency. The detoxification mentioned here includes oxidative decomposition of organic pollutants and malodorous components due to oxidation reaction, sterilization of bacteria and the like. The adsorbent used in the present invention must be one that adsorbs ozone and adsorbs harmful substances. Examples of such adsorbents are silica gel, high silica pentasil zeolite (silicalite or ZS with high SiO ₂ / Al ₂ O ₃ ratio).
M-5), dealuminated faujasite (super stable Y
Type zeolite: USY), mesoporous silicates (MCM-41, FSM-16, low temperature acidic synthetic mesoporous silicate using tetraethoxysilane as silica source, low temperature acidic synthetic mesoporous silicate using low molecular silicic acid as silica source, etc.) The high silica adsorbents can be mentioned. Among these high silica adsorbents, silica gel has a slightly low ozone and harmful substance adsorption capacity and low resistance to water, but other high silica pentasil zeolites, dealuminated faujasites and mesoporous silicates all have ozone High adsorption capacity,
Moreover, it has a low decomposition rate of the adsorbed ozone, has a property of adsorbing harmful substances, and has resistance to water, and is suitable for water treatment.

Among the high silica adsorbents, the high silica pentasil zeolite uses sodium silicate or fumed silica as a silica source and tetrapropylammonium bromide as an organic template.
SiO ₂ / obtained by performing hydrothermal synthesis at about 180 ° C
It is a pentasil zeolite having an Al ₂ O ₃ ratio of about 10 to 1000. Aluminum-free faujasite is SiO
A SiO ₂ / Al ₂ O ₃ ratio of 10 to 10 obtained by removing most of the Al in the zeolite skeleton by treating Na-Y type zeolite with a ₂ / Al ₂ O ₃ ratio of about 5 with ammonia water.
400 ultra stable Y zeolite (USY).

Mesoporous silicate is 10 to 1000
Silica-based porous material with angstrom mesopores
There are various manufacturing methods, and depending on the manufacturing conditions, etc.
O₂/ Al₂O₃Ratio 10 to substantially SiO₂Only
Has been obtained. For example, MCM-41 is a mobile
Temperature 140 ℃, pH 13.5, Siri developed by the company
Water source, sodium silicate, organic template
Use a cationic surfactant (more than 8 carbon atoms)
Specific surface area of 1600m²/ G, SiO
₂/ Al₂O₃It is a silica-based porous body with a ratio of about 1000.
It FMS-16 was also developed by Kuroda, Inagaki, etc.
Intercalation with cationic surfactant in kanemite
Of SiO 2 having a structure similar to MCM-41
₂/ Al ₂O₃It is a silica-based porous body with a ratio of about 1000.
It Also, low temperature mesoporous silicate is stuck
The method proposed by Y. et al., ie, as a silica source
Tetraethoxysilane (TEOS) is used as an organic template.
PH at room temperature using a cationic surfactant
Synthesized at 1 or less, low temperature mesoporous siliqu
Is a method developed by the present inventors, namely silica.
As a source, polycondensed silica-free silicic acid was used as an organic solvent.
At room temperature using cationic surfactant as template
It is synthesized at a pH of 1 or less. These low temperature mesopo
-Silica may be SiO depending on manufacturing conditions.₂/ Al₂
O₃Ratio 10 to substantially SiO₂You can get only things
You can

[0014] According to the experimental results of the present inventors, SiO Among these high-silica adsorbents ₂ / Al ₂ O ₃ ratio of 70 or more high-silica pentasil zeolite, SiO ₂ /
Al ₂ O ₃ ratio of 20 or more dealumination faujasite, SiO ₂ / Al ₂ O ₃ ratio of 20 or more mesoporous silicate, high ozone adsorbing capability, more preferable adsorbents der since lower decomposition rate of the adsorbed ozone , In the present invention this
3 kinds of adsorbents are used. Among these, high-silica pentasil zeolite tends to have a slightly higher ozone decomposition rate. Considering ozone adsorption capacity and decomposition rate, SiO ₂ /
A mesoporous silicate having an Al ₂ O ₃ ratio of 20 or more shows the best performance, and then has a SiO ₂ / Al ₂ O ₃ ratio of 20.
The above dealuminated faujasite, SiO ₂ / A
The order is high silica pentasil zeolite having an l ₂ O ₃ ratio of 70 or more.

For high silica pentasil zeolites, dealuminated faujasites and mesoporous silicates having different SiO ₂ / Al ₂ O ₃ ratios, SiO ₂ / A
FIG. 7 shows the result of investigation of the relationship between the l ₂ O ₃ ratio and the ozone decomposition rate.
Shown in. The decomposition rate was determined by passing water of 25 ° C. in which 10 ppm of ozone was dissolved through a packed column filled with 80 liters of an adsorbent, and measuring the ozone concentration (C ₁ pp in the effluent at the outlet of the packed column).
m) was measured and the decomposition rate was calculated by the following formula. Decomposition rate (%) = [(10−C ₁ ) / 10] × 100 In FIG. 7, a decomposition rate of 20% or less is a practical range, and for high silica pentasil zeolite, SiO ₂ / Al.
₂ O ₃ ratio is about 70 or more, and dealumination faujasite and mesoporous silicate (low temperature mesoporous silicate) have SiO ₂ / Al ₂ O ₃ ratio of about 20.
If it is above, it falls into this range, and further, in the case of high silica pentasil zeolite, the SiO ₂ / Al ₂ O ₃ ratio is about 200.
As described above, in the dealuminated faujasite and mesoporous silicate, when the SiO ₂ / Al ₂ O ₃ ratio is about 50 or more, the decomposition rate is 10% or less, which is particularly preferable. Main points in the figure (SiO ₂ / Al ₂
The ratio of O _{3 to} ozone decomposition is (15:90), (20:50), (10) for the high silica pentasil zeolite.
0:12), (1000: 10), (15:55), (30:15) for dealumination faujasite,
(100: 8), (400: 8), (15:50), (30:12), (100: in mesoporous silicate).
6) and (1000: 6). Although not shown , MC with an SiO ₂ / Al ₂ O ₃ ratio of about 1000
The decomposition rate of M-41 and FSM-16 was about 6%, and that of silica gel was about 60%.

These adsorbents may be used alone or in the form of a mixture depending on the purpose of use by molding them into any desired shape such as granular, Raschig ring-shaped or honeycomb-shaped. In addition, the adsorbent-filled tower has a two-layer structure in which the treated water inlet side is filled with mesoporous silicate with high adsorption performance for high-concentration ozone, and the treated water outlet side is filled with dealuminated faujasite with high adsorption performance for low-concentration ozone. It is also possible to increase the use efficiency of ozone as the adsorbent layer of the structure.

In the present invention, ozone is added to and mixed with polluted water containing harmful substances, and then the adsorbent packed column provided with the adsorbent layer is passed through to carry out an oxidation reaction in the adsorbent phase to cause harmful substances. Disassemble and sterilize. This makes it possible to proceed with detoxification with a much higher efficiency than in the case where ozone is simply added to the contaminated water containing a harmful substance to react. In addition, sterilization is performed along with decomposition of harmful substances due to oxidation reaction. The amount of ozone added may be appropriately set depending on the type and concentration of harmful substances in the wastewater, but in normal wastewater treatment, it is 0.1-10 pp.
It is about m.

As an ozone generator (ozonizer) for supplying ozone into the contaminated water, any method known per se, such as a silent discharge method, an ultraviolet lamp method, and a water electrolysis method can be applied. Among them, in the water electrolysis method, a specially treated ion exchange membrane is sandwiched between a gas permeable electrode (hydrogen electrode) made of carbon and fluororesin and a lead dioxide electrode (ozone electrode), and ion exchange water is supplied to the ozone electrode as raw material water. Electrolysis to generate ozone and oxygen at the ozone electrode, and hydrogen at the hydrogen electrode, and a high-concentration and clean ozone gas can be obtained, and the generated ozone is in the form of gas as well as for water treatment. It can be easily supplied in the form of a suitable ozone water, and is suitable when applied to water treatment as in the present invention.

The present invention is based on the fact that the present inventors
During the adsorption test, a high silica-based adsorbent (high silica penta
Sil zeolite, dealuminated faujasite,
Sodium silicate, etc.) absorbs dissolved ozone and
COD components co-adsorbed (alcohol, ketone, S
Tellur, ether, amine, mercaptan, etc.)
Oxidizing harmful substances such as odorous components with ozone with high efficiency
Based on the finding that zon is converted to oxygen
Of. By coexisting an adsorbent in this way,
Detoxification of harmful substances in water, eg COD component ozone
Oxidation proceeds efficiently because ozone detoxifying the solution
The concentration of ozone in the solution [O₃]_aqAnd COD component concentration
[COD]_aqProduct of [O₃]_aq・ [COD]_aqIn proportion to
Although it progresses, in the adsorbent, the azo of the adsorbent phase
Concentration [O₃]_adsAnd COD component concentration [COD]_ads
Can reach 10 to 100 times,
[O ₃]_ads・ [COD]_adsIs 10 to 10 in the liquid phase
It is thought that this will be 000 times.

Further, in the liquid phase, ozone collides with a third substance other than a harmful substance and is decomposed more often without contributing to detoxification, and the detoxification efficiency is not so large. On the other hand, in detoxifying harmful substances by ozone in the adsorbent phase as in the present invention, since ozone and harmful substances are selectively adsorbed in the adsorbent phase, ozone decomposition by collision with the third substance The probability of is greatly reduced, and ozone is efficiently consumed for detoxifying harmful substances.

In the present invention, most of the unreacted ozone stays in the silica-based adsorbent, so there is almost no leakage to the downstream, but ozone that slightly leaks is contacted with ozone and oxidized to CO ₂ . It can be completely decomposed using an ozone decomposing agent such as activated carbon or an alumina-based compound which is a consumable adsorbent. That is, unreacted ozone can be decomposed by providing a decomposing agent layer that decomposes leaking ozone at the drainage outlet portion of the adsorbent-packed tower that performs ozone oxidation treatment. The decomposing agent layer may be provided inside the outlet portion of the adsorbent packed tower, or may be separately provided outside the packed tower. Although activated carbon has been used for the treatment of leaked ozone, the concentration of leaked ozone is high because the reaction is slow in conventional treatment of harmful substances in the liquid phase, and therefore the consumption of activated carbon by ozone is also high. It was quite large, and there was a strong need for improvement in terms of economy and maintainability due to the high frequency of replacement. In this respect, according to the method of the present invention, the concentration of leaked ozone becomes 1/10 or less of that in the conventional case, and therefore the frequency of use of activated carbon can be significantly extended to about 10 times that in the conventional case.

As a preferred embodiment of the present invention, there is an embodiment in which a filter material layer for removing suspended matter is provided on the upstream side and / or the downstream side of the ozone injection point into the contaminated water. Different effects can be expected depending on the installation position of the filter material layer, and the installation position may be appropriately determined depending on the condition of the apparatus, the property of the contaminated water, the material of the filter material, and the like. For example, if it is installed on the upstream side of the ozone injection point, it will have the effect of removing ozone decomposing substances and the reduction of the amount of suspended solids adsorbed on the adsorbent packed bed. And protein-based sludge-like substances aggregate due to condensation polymerization, decomposition, etc., and change into a property that facilitates filtration and separation, improving the filterability and easily peeling off even when attached to a filtering material, In addition to facilitating filtration and washing of the filter material, there is an effect that clear treated water can be obtained. In addition, there is an advantage that it is not necessary to select a material that withstands ozone when it is installed on the upstream side of the ozone injection point or on the downstream side of the ozone decomposer layer.

INDUSTRIAL APPLICABILITY The method and apparatus of the present invention have a high detoxification performance for harmful substances, are safe without fear of ozone outflow into treated water, and are capable of sufficiently decomposing and sterilizing organic substances possessed by ozone with relatively simple equipment. It is possible to construct a purification system for polluted water containing high-performance harmful substances that has been utilized for purification of pool water and bath water, sterilization, COD reduction of various wastewater, decolorization, sterilization treatment, and lakes and marshes. It can be applied to a wide range of purposes, such as water purification (purification of water-bloom etc.) and rainwater purification.

Embodiments of the present invention will now be described in detail with reference to the drawings. FIG. 1 shows an example of a method of adding ozone to polluted water containing harmful substances and a method of introducing ozone-added polluted water into an adsorbent packed tower according to the present invention. Figure 1
In (a), ozone is added to the polluted water 1 containing harmful substances from the ozone generator 3 in the ejector 2 and mixed by the static mixer 4, and then the high silica adsorbent layer 5 is added.
Is supplied from below the adsorbent packed tower 6 in which the adsorbent layer 5 is provided.
To decompose the harmful substances, and discharge the treated water 7 from above the adsorbent packed tower 6. If necessary, by providing an ozone decomposing agent layer 8 such as activated carbon on the adsorbent layer 5, it is possible to completely prevent leakage of ozone into the treated water 7. In the figure, 9 is an air vent. Further, instead of the ejector 2 and the static mixer 4, FIG.
You may provide the cascade pump 10 shown in FIG.

Next, a mode in which the method and apparatus of the present invention are applied to purification of pool water will be described. FIG. 2 is a schematic flow chart showing an example of the case of applying to an existing pool.
In a normal pool, it is common to extract water, purify it through a sand filter tank, add a chlorine-based bactericide and circulate the pool. In the flow of FIG. 2,
Part of the water extracted from the pool 30 and having suspended solids removed through the existing sand filtration tank 31 (about 10% in the example in the figure)
Is injected with ozone from an ozone generator 32, purified through an adsorbent packed tower 35 provided with a high silica adsorbent layer 33 and an ozone decomposing agent layer 34 such as activated carbon, and circulated as clean water in the pool 30. According to this flow, harmful substances in the water are decomposed and removed by the oxidative action of ozone and sterilized, and the remaining ozone is completely decomposed by the decomposer, and ozone remains in the circulating water to the pool. There is no fear. Moreover, unlike a chlorine-based germicide that is widely used at present, it does not remain in circulating water to cause an unpleasant odor or the like, and a comfortable pool environment can be provided.

FIG. 3 shows a second example when applied to an existing pool.
It is a schematic flow diagram showing an example of. In the example of FIG. 3, ozone is injected from the ozone generator 32 into the water extracted from the pool 30, the existing sand filtration tank is modified, and the high silica adsorbent layer 33, the filter medium layer 36, and the ozone decomposing agent layer 34 are used. The adsorbent packed column 35 having a layered structure is passed through for purification. In this case, since the existing sand filter tank is simply modified in addition to the addition of the ozone generator, the cost is lower than that of the example of FIG.

FIG. 4 is a schematic flow chart showing an example of application to a new pool. In this case, the high silica adsorbent layer 33 and the ozone decomposing agent layer 34 are provided in the circulation path of the pool water.
The filter material layer 36 may be provided, and ozone may be added from the ozone generator 32 upstream of the high silica adsorbent layer 33. The high silica adsorbent layer 33, the ozone decomposing agent layer 34, and the filter medium layer 36 may be provided individually, or two or three of these may be provided in the same container. When the method of the present invention is applied to the treatment of pool water, in addition to the oxidative decomposition of organic pollutants and malodorous components, there is a sterilizing effect.According to the test results of the present inventors, E. coli in pool water is Was reduced to about 1/100 to 1/10 ⁶ . Further, it was found that the transparency of water is improved due to the aggregation effect of oils and fats and protein-based suspended matter due to the addition of ozone.

FIG. 5 is a schematic flow chart showing an example of applying the method and apparatus of the present invention to the purification of bath water.
In the example of FIG. 5, ozone is injected from the ozone generator 41 into the bath water extracted from the bath 40, and the high silica adsorbent layer 4 is discharged.
3 and an ozone decomposing agent layer 44 such as activated carbon are provided for purification through the adsorbent reactor 42, and the cartridge filter 4
It is circulated to the bathtub through the filter material layer such as 5.

[0029]

The present invention will be described in more detail with reference to the following examples. (Embodiment 1) FIG. 6 is a flow chart showing an outline of a wastewater treatment test apparatus to which the present invention is applied. A wastewater treatment test according to the method of the present invention was performed according to the flow of FIG. 10 tons of industrial wastewater containing 5 ppm of ethanol as a COD component
/ H from the drainage port 51 to the high silica porous material packed tower (high silica adsorbent packed tower) 53 through the flow path (supply pipe) 52, the ozone from the ozone generator 54 to the ozone flow channel 52 of 0. 1 kg / h was added so that ozone and wastewater were completely mixed at the inlet of the packed tower 53. The packed column 53 has a diameter of 30 cm and a height of 30 cm, and is filled with 80 liters of the high silica adsorbent 55. Here, the superficial velocity was 45 m / h and the SV value was 150 h ⁻¹ . Since the wastewater after detoxifying ozone flows through the flow path (discharge pipe) 56, the wastewater was collected from the sampling line 57 and COD measurement was performed to verify the effectiveness of the present invention.
Table 1 shows the test conditions of the present invention and the results of evaluating the ozone oxidative decomposition characteristics of various porous silica materials at the outlet COD component concentration.

[0030]

[Table 1]

High silica adsorbent used in this example
Is as follows: Silica gel is a commercial product. US
Y is SiO₂/ Al₂O₃Na-Y type zeolite with a ratio of 5
Zeolite by contacting it with ammonia vapor at 250 ° C
SiO obtained by removing most of the skeleton Al₂/ Al₂
O₃It is an ultra stable Y-type zeolite with a ratio of 70. Silica Rye
Sodium silicate as a silica source, organic template
Using tetrapropylammonium bromide
SiO hydrothermally synthesized at 180 ℃₂/ Al ₂O₃ratio
It is 400 pentasil zeolite. Also, MCM-
41 is temperature 140 ° C., pH 13.5, water as silica source
Glass, sodium silicate, mosquito as organic template
Obtained using a thione-based surfactant (more than 8 carbon atoms)
Specific surface area 1600m²/ G of silica based porous material
It FMS-16 is a cationic surfactant for kanemite
MCM-41 obtained by intercalating
It is a silica-based porous material having a similar structure. Low temperature mesoporous
Silicate is a tetraethoxysilane as a silica source
(TEOS) as an organic template
Synthesized at room temperature using a surfactant at pH 1 or less
Is. Low temperature mesoporous silicate as a silica source
Silicic acid containing no condensation-polymerized silica is treated with an organic template.
Room temperature pH 1 using cationic surfactant
It is synthesized below. Each adsorbent is 1.6 mm
Filled with φ spheres. In addition, the ratio table of each adsorbent used
The area is as shown in Table 2.

[0032]

[Table 2]

As can be seen from the results shown in Table 1, the decomposition rate of ethanol remains about 40% under the condition (RUN0) in which the high silica porous body 5 is not filled, whereas the high silica porous body 5 is filled in the example. 70 with silica gel (RUN2)
%, USY (RUN4), silicalite (RUN6),
Mesoporous silicate (MCM-41, FSM-1
6, low temperature mesoporous silicate, RUN8, 1
0, 12, 14) showed a decomposition rate of 85% or more.

The oxidative decomposition efficiency of the adsorbent is low temperature mesoporous silicate, MCM-41, silicalite> US
The order of Y>FSM-16> silica gel is low temperature mesoporous silicate, as shown by the decomposition rate of ozone in wastewater containing no ethanol, and MCM-4.
It is considered that ozone is effectively adsorbed in the order of 1, silicalite>USY>FSM-16> silica gel without being decomposed by the adsorbent. The outlet ozone concentration increases in the order of low temperature mesoporous silicate, MCM-41, silicalite <USY <FSM-16 <silica gel, and the lower the concentration, the higher the reaction activity in the adsorbent phase. Was given.

(Embodiment 2) In Embodiment 1, even in the case of using low temperature mesoporous silicate, a value of 0.
About 15 ppm of ozone was detected. Regarding ozone toxicity, there is no specific regulation because it decomposes with long-term retention. However, in consideration of the oxidizing property of ozone, it is desirable that the residual ozone after treatment be completely decomposed.
Therefore, the bottom of the packed tower 3 was filled with cloth-like ACF (activated carbon fiber), which is one type of activated carbon, to a height of about 5 cm. As a result, no ozone was detected from the outlet channel 6. The ozone decomposition of this adsorbent is C + O ₃ → CO
This is due to the reaction of ₂ + O ₂ , and it has been confirmed that a filling amount of this degree can withstand continuous use for half a year. For comparison, when the cloth-like ACF and the unreacted ozone were directly contacted with each other without filling the adsorbent (low temperature mesoporous silicate), the ozone concentration at the outlet began to increase in about 2 weeks. From this, it can be seen that the ozone is effectively used by the reaction in the adsorbent phase, and the flow-through of ozone is 1/10 or less of that of the conventional case, so that the life of the adsorbent for leak prevention is extended by about 10 times.

[0036]

According to the method of the present invention, in the treatment of polluted water containing harmful substances with ozone, the effective use of ozone can be achieved by using an adsorbent that efficiently adsorbs ozone and adsorbs harmful substances. The rate is improved, and detoxification treatment such as oxidative decomposition and sterilization of highly efficient organic pollutants and malodorous components becomes possible. Also, since the utilization rate of ozone is improved,
The amount of leaked ozone to the treated wastewater discharged is small, and furthermore, the ozone leak can be completely prevented by providing an ozone decomposing agent layer such as activated carbon. Further, according to the apparatus of the present invention, the treatment of polluted water containing harmful substances with ozone can be efficiently performed.

[Brief description of drawings]

FIG. 1 is an explanatory view showing an example of a method of adding ozone to polluted water containing a harmful substance and a method of introducing polluted water to which ozone is added into an adsorbent-packed tower according to the present invention.

FIG. 2 is a schematic flow chart showing an example in which the present invention is applied to purification of water in an existing pool.

FIG. 3 is a schematic flow chart showing another example of applying the present invention to water purification of an existing pool.

FIG. 4 is a schematic flow chart showing an example in which the present invention is applied to purification of water in a new pool.

FIG. 5 is a schematic flow chart showing an example when the present invention is applied to purification of bath water.

FIG. 6 is a flow chart showing an outline of a wastewater treatment test apparatus used in Examples.

FIG. 7 is a graph showing the relationship between the SiO ₂ / Al ₂ O ₃ ratio of a high silica adsorbent and the ozone decomposition rate.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI E04H 4/12 E04H 3/20 B (72) Inventor Hiroyuki Tsutaya 5-17-1 Fukahori-cho, Nagasaki-shi, Nagasaki Mitsubishi Heavy Industries, Ltd. Nagasaki Research Institute (72) Inventor Naruyuki Tomonaga 5-717-1, Fukahori-cho, Nagasaki City, Nagasaki Prefecture Mitsubishi Heavy Industries, Ltd. Nagasaki Research Institute (72) Inventor Ka Wada 3000, Tana, Sagamihara City, Kanagawa Mitsubishi Heavy Industries Ltd. Company Sagamihara Works (72) Inventor Tokuichi Mineo 3000 Tana, Sagamihara City, Kanagawa Mitsubishi Heavy Industries, Ltd. Sagamihara Works (56) References JP-A-8-24878 (JP, A) JP-A-64-4220 ( JP, A) JP 4-313320 (JP, A) JP 6-98357 (JP, B2)

Claims (5)

(57) [Claims] 1. A high-silica penta having a SiO ₂ / Al ₂ O ₃ ratio of 70 or more that adsorbs ozone and adsorbs harmful substances after ozone is added to and mixed with polluted water containing harmful substances.
Sil zeolite, desorption of SiO ₂ / Al ₂ O ₃ ratio of 20 or more
Aluminum faujasite, SiO ₂ / Al ₂ O ₃
A mesoporous silicate with a ratio of 20 or more or of these
Hazardous substances in contaminated water by passing through an adsorbent layer filled with a high silica adsorbent that is a mixture of two or more of
And ozone are co-adsorbed on the high silica adsorbent,
A method for treating polluted water containing harmful substances, characterized by detoxifying substances by the action of ozone. 2. The treated water after detoxifying harmful substances in the adsorbent layer is contacted with an ozone decomposing agent to decompose residual ozone, thereby preventing leakage of ozone to the downstream. The method for treating polluted water containing harmful substances according to claim 1 . 3. A high silica pentasil having an SiO ₂ / Al ₂ O ₃ ratio of 70 or more which adsorbs ozone and adsorbs harmful substances.
Zeolite, deaeration with SiO ₂ / Al ₂ O ₃ ratio of 20 or more
Luminium faujasite, SiO ₂ / Al ₂ O ₃ ratio
20 or more mesoporous silicates or of these
An adsorbent packed tower provided with an adsorbent layer of a high silica adsorbent that is a mixture of two or more kinds , a supply pipe for supplying contaminated water containing a harmful substance to the adsorbent packed tower, and connected to the supply pipe ,
A treatment device for polluted water containing harmful substances, comprising: an ozone generator for adding ozone to polluted water; and a discharge pipe for discharging treated water that has been treated from the adsorbent packed tower. 4. The treatment apparatus for polluted water containing harmful substances according to claim 3, wherein an ozone decomposing agent layer for decomposing leaking ozone is provided on the downstream side of the adsorbent packed tower. . 5. A front flow side and / or rear flow side of the ozone injection point of the adsorbent packed column, filtering material layer for removing suspended matter, characterized in that the thus provided according to claim 3 or 4. A treatment apparatus for polluted water containing harmful substances according to item 4 .