JPH11347571A - Contact type water quality modifying agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject modifying agent capable of being charged in a small-sized water purifying apparatus, capable of preventing the generation of scale in a piping of treated water capable of being regenerated in water purifying function, usable for a long period of time and also effective even in the removal of bacteria in treated water. SOLUTION: The surface of a ceramic base material molded into a spherical shape or the like is coated with a siliceous (SiO2 ) quartz glass material containing respective crystals of tricon tetroxide (Fe3 O4 ) and anatase titanium oxide (TiO2 ) and pref. containing crystals of zirconium oxide (ZrO2 ) and aluminum oxide (Al2 O3 ) and the coated base material is baked to form a contact type water quality modifying agent having a glassy coating layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a contact for improving the quality of drinking water such as drinking water, domestic wastewater, rainwater, industrial wastewater, or other various kinds of water such as seawater or the like. It relates to a type water quality improver.

[0002]

2. Description of the Related Art Generally, it is harmful to the environment for pretreatment when using water such as water supply or industrial water from rivers, well water (groundwater), lakes and marshes, or when returning used wastewater to the natural environment. Purification processing is performed in order not to give the wastewater. Evaluation criteria for the degree of such purification treatment include biochemical oxygen demand (BOD), chemical oxygen demand (COD), suspended solids (SS), chromaticity, turbidity, odor, taste, pH , Chlorine, nitrogen, general bacteria, presence or absence of coliforms, etc.

[0003] As a conventional water treatment method for improving the evaluation criterion as described above and improving the water quality, water to be treated is sequentially passed through a tank, and precipitation and filtration of suspended solids are repeated. Depending on the conditions, an adsorbent or a coagulant may be placed in the tank to adsorb or coagulate inorganic or organic substances,
A method of chemically decomposing is employed.

[0004] In order to improve the above-mentioned water quality evaluation items, the contaminants mixed in the water are physically and chemically separated and removed, and microorganisms such as bacteria are killed. It is thought that it can be improved to be harmless.

[0005]

However, the above-mentioned conventional apparatus for improving water quality requires a large area for a septic tank and other facilities, and is small enough to be attached to a pipe if necessary. Not a device.

Further, when water purification equipment is used, a deposit called scale composed of algae, water scale, rust, and precipitated inorganic substances may be formed in the water distribution pipe. There was no water treatment device.

[0007] As a simple water purification device, there is a device for drinking water in which a filtration material such as activated carbon or a hollow fiber membrane is attached and the water to be treated is passed through the filtration material. In addition, the filter material (filter) had to be periodically replaced, and the filter material could not be regenerated and used, and had no bactericidal action.

Accordingly, an object of the present invention is to solve the above problems and provide an effective contact-type water quality improver by filling a small-sized water purification device which can be attached to a required portion of a pipe.・ A contact-type water quality improver that can prevent the generation of scale in the pipe through which sewage passes. In addition, the water-purifying function is renewable and can be used for a long period of time. To provide an agent.

[0009]

According to the present invention, in order to solve the above-mentioned problems, a ferrous oxide (Fe ₃ O ₄ ) and an anatase type titanium oxide (TiO ₂ ) This was a contact type water quality improver obtained by forming a vitreous coating layer containing each crystal.

Alternatively, a vitreous material containing, on the surface of a ceramic substrate, 10 to 20% by weight of iron tetroxide (Fe ₃ O ₄ ) and 40 to 80% by weight of anatase type titanium oxide (TiO ₂ ) This is a contact type water quality improver formed with a coating layer.

Further, in order to solve the above-mentioned problems, each crystal of triiron tetroxide (Fe ₃ O ₄ ), anatase type titanium oxide (TiO ₂ ) and zirconium oxide (ZrO ₂ ) is formed on the surface of a ceramic substrate. Thus, a contact type water quality improver obtained by forming a vitreous coating layer containing a body was obtained.

Further, in order to solve the above-mentioned problem, on a surface of a ceramic base material, ferric oxide (Fe ₃ O ₄ ), anatase type titanium oxide (TiO ₂ ), zirconium oxide (Zr
It is also possible to employ a contact type water quality improver obtained by forming a vitreous coating layer containing each crystal of O ₂ ) and aluminum oxide (Al ₂ O ₃ ).

As described above, the contact type water quality improver of the present invention containing a predetermined crystal as an essential component of the vitreous coating layer which comes into contact with the water to be treated is iron trioxide (Fe ₃ O ₄ ) and anatase. Each type of titanium oxide (TiO ₂ ) is an unstable crystal, and ferric oxide is ferromagnetic and conducts electricity fairly well, and iron ions outside the complex group can easily exchange charge. In addition, titanium oxide forms a solid solution with iron oxide, which is considered to exert some physicochemical action when it comes into contact with the water to be treated.

Further, in addition to triiron tetroxide (Fe ₃ O ₄ ) and anatase type titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), and aluminum oxide (Al ₂ O ₃ )
It is considered that the above-mentioned action is further ensured by including each crystal of the above.

The contact-type water quality improver of the present invention is obtained by coating the surface of a ceramic base material with the glassy coating layer containing the above-mentioned predetermined components and melt-coating the same. Even if the ceramic base material is formed into a shape having a surface area as large as possible, such as a cylindrical shape, the resistance to flowing water is relatively small, and water is easy to contact and pass. The contact type water quality improver formed into various shapes can constitute a water quality improvement device simply by filling it into a small water-permeable container.

As will be apparent from the test results of the examples described later, the contact type water quality improver having a vitreous coating layer containing a predetermined crystal according to the present invention removes water that has passed through the contact type water quality improver by piping. It is water that does not easily generate scale inside, and after long-term use, it can be reused and reused by simply removing adhering substances on the surface by washing with water. It is also effective.

It is further estimated from the test results that the contact-type water quality improver of the present invention decomposes the molecular structure of the contacted water so that the clusters become smaller, and converts the molecular structure into so-called monomolecular water or the vitreous coating layer. It is also presumed that there is an ion exchange action or an antibacterial action associated therewith.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The ceramic substrate used in the present invention can be employed without any particular limitation on its components, but if possible, a material which generates a large amount of far-infrared rays at room temperature or a magnetic material is preferable. Aluminum ceramics (Al ₂ O ₃ ), zinc oxide (ZnO), titanium oxide (TiO ₂ ), tin oxide (S
nO ₂ ), barium titanate (BaTiO ₃ ), cadmium sulfide (CdS), silicon nitride (Si ₃ N ₄ ), silicon carbide (SiC), carbon (C), silicon oxide (SiO ₂ ), ferrite, zirconia (ZrO) ₂ ) and well-known ceramic materials such as boron nitride (BN).

In particular, magnetite (Fe ₃ O ₄ ), alumina (Al ₂ O ₃ ) and silicon oxide (SiO ₂ ) are blended at a predetermined ratio (for example, 38% by weight, 34% by weight, and 28% by weight in this order). The radiation efficiency of far-infrared rays, which are a kind of electromagnetic waves, is relatively high even at about room temperature.As is clear from the experimental results described below, the water treatment efficiency evaluated by reducing the turbidity of the water to be treated is high. It is also preferable in terms of good points.

Such a ceramic substrate is formed by shaping the sized raw material powder mixture into a spherical shape, an elliptical spherical shape, a cylindrical or other pellet shape, a polyhedral shape, or the like, or by applying it to a water contact surface of a water treatment apparatus. After this, the molded body is calcined to be solidified. For example, a mixture of 38% by weight of magnetite, 34% by weight of alumina and 28% by weight of silicon oxide can be calcined at 800 ° C. to a required hardness.

The ferric oxide (Fe ₃ O ₄ ) used as a crystal component of the vitreous coating layer of the present invention is naturally produced as magnetic steel (magnetite). This crystal has an inverse spinel structure belonging to the equiaxed system and has a melting point of 1
Ferromagnetic and conductive at 538 ° C. This conductivity is
It is said that the crystal structure represented by Fe ^II Fe ^III [Fe ^III O ₄ ] is because iron ions outside the complex group can easily exchange charges.

Iron trioxide is added to the glassy coating layer by 10 to 2 times.
It is preferable to mix at a ratio of 0% by weight. Because
If the amount is less than 10% by weight, the amount of iron ions acting on the anatase type titanium oxide is insufficient. If the amount exceeds 20% by weight, the amount of anatase type titanium oxide and SiO
_This is because the amount of glassy material such as ₂ · nH ₂ O becomes insufficient, which is not preferable.

The anatase-type titanium oxide (TiO ₂ ) used in the present invention is one of anatase (also called anatase), brookite, and rutile, which are known as crystal forms of titanium, and is heated to 700 to 1000 ° C. Then, it is a tetragonal crystal form that changes to rutile. Anatase-type titanium oxide is commercially available as an industrial material, and can be used for paper sheeting / coating agents, matting of chemical fibers, and coloring agents for rubber. Titanium oxide is chemically stable, hot concentrated sulfuric acid, inorganic acids other than hydrofluoric acid,
It is not attacked by organic acids, alkalis and solvents, has good heat resistance and weather resistance, and has no toxicity.

Such anatase-type titanium oxide is preferably blended in the glassy coating layer at a ratio of 40 to 80% by weight. The reason for this is that if the amount is less than 40% by weight, the catalytic action on main iron ions is weaker than expected, and if the amount is more than 80% by weight, the catalytic action of anatase-type titanium oxide is mainly reduced. SiO ₂ · n to increase the amount of iron ions and the surface area
This is because the amount of glass such as H ₂ O is insufficient, which is not preferable.

The zirconium oxide (Zr) used in the present invention
O ₂ ) is obtained by heating zirconium hydroxide, and usually contains 2% or less of hafnium.
There are two types of crystal types, Badelli type and Zirconia type.
The latter cannot be used in the present invention because it is soluble in cold and hot water, and the former crystal form can be used. This zirconium oxide has extremely high corrosion resistance and is a monoclinic crystal having a melting point of 270.
0 ° C.

The aluminum oxide (Al) used in the present invention
₂ O ₃ ) is industrially called alumina, but α-Al ₂ O ₃ can be used as a water-insoluble crystal form. Note that γ-Al ₂ O ₃ has high chemical reactivity, dissolves in water and exhibits amphoteric properties, and is difficult to use in the present invention. The addition of such alumina increases the strength of the vitreous coating layer and improves the pressure resistance.

Incidentally, the vitreous coating layer in the present invention is an amorphous solid which keeps the above-mentioned crystals in a dispersed state. As the three-dimensional network polymer forming a vitreous material, a polymer in which an alkali metal or an alkaline earth metal is partially contained in a network structure of silicon oxide is preferable because it is stable. The vitreous material is capable of incorporating most of its elements into its structure. Specific examples thereof include quartz glass having only a network structure of silica (SiO ₂ ) and Na ₂ O · CaO · 5SiO ₂ . And borosilicate glass having a network in which boric acid and silicic acid are copolymerized.

In order to maintain the above-mentioned crystals in a dispersed state with such a vitreous coating layer, a glass component (preferably 10 to 30 wt. %), Each crystal of iron tetroxide, anatase type titanium oxide, zirconium oxide, and aluminum oxide is mixed, and a glaze-like suspension to which water is added is applied, and this is fired at a predetermined temperature.

The temperature condition during firing may be a temperature at which the above-mentioned crystals maintain a predetermined crystal form and the vitreous material is melted. For example, Fe ₃ O ₄ , TiO ₂ , SiO ₂ .nH
_When applying and firing a suspension containing ₂ O, Al ₂ O ₃ and ZrSiO ₂ , firing conditions of holding at 1300 ° C. for about 2 hours are preferable, and TiO ₂ and SiO _2.
When applying and baking a suspension containing nH ₂ O,
Firing conditions of holding at 950 ° C. for about 2 hours are preferable.

It is to be noted that the components of such a vitreous coating layer are prepared as necessary by adjusting the expansion coefficient to the above-mentioned ceramic substrate.

[0031]

EXAMPLES [Examples 1 to 3, Comparative Example 1] Magnetite (Fe ₃ O ₄₎ 38 wt%, alumina (Al ₂ O ₃₎ 34 wt% of silicon oxide and (SiO ₂₎ 28 wt% blended mixture Pre-compression molding into a sphere (1.5-3cm in diameter)
By firing at 00 ° C. for 2 hours to form a spherical ceramic substrate, the surface of the substrate was made of Fe at the mixing ratio shown in Table 1 below.
An aqueous suspension containing ₃ O ₄ , TiO ₂ , SiO ₂ .nH ₂ O, Al ₂ O ₃ and ZrSiO ₂ is applied by a dipping method, and heated at 950 ° C. for 2 hours to form an anatase type titanium oxide. The resulting mixture was fired to be a vitreous material containing the crystal of (1), thereby obtaining 30 kg of a spherical contact-type water quality improver.

[0032]

[Table 1]

The following test was conducted on Example 1 to compare the water quality of the blank (water before treatment) with the water quality after treatment. That is, 25 kg of the obtained spherical contact-type water quality improver was accommodated between the mesh plates 2 of the cylindrical water-permeable device 1 made of stainless steel pipe shown in FIG. 1, the valves 3 and 4 were opened, and the valve 5 was closed. To flow the treated water at a flow rate of 1.8 liter / sec.
After passing through the water permeation apparatus 1 for 5 seconds, the water quality improving agent 6 in contact with the spherical water quality improving agent 6 was passed. The number 7 in the figure is a flow meter.

Next, the water quality of the blank (pre-treatment water) and the water quality after the treatment were tested according to the ministerial ordinance concerning the water quality standards of the Water Supply Law, and the test items and the results are also shown in Table 2. In addition, tests were conducted on well bacteria (blanks and treated water) collected in different areas for general bacteria and Escherichia coli in exactly the same manner, and the results are also shown in Table 2.

[0035]

[Table 2]

As is clear from the results in Table 2, the well water that has passed through the contact-type water quality improver of Example 1 has a remarkably reduced turbidity from 0.8 to 0.1, and a reduced chlorine ion. It was reduced from 340 mg / l to 220 mg / l. Also,
The number of general bacteria was also reduced from 140 / ml or more of the blank to 8 / ml, and E. coli detected in the blank was not detected in the well water after the treatment.

For Example 2, the water quality of the blank (water before treatment) and the water quality after treatment were compared by the following test, using the same water-permeable apparatus as in Example 1. Table 3 shows the test items, test methods and test results.

[0038]

[Table 3]

As is evident from the results in Table 3, the septic tank wastewater that passed through the contact type water quality improver of Example 2 was compared with the blank septic tank wastewater in terms of its BOD, COD, and S.
S, chromaticity and turbidity were significantly reduced.

Also in Example 3, the water quality of the blank (water before treatment) and the water quality after treatment were compared by the following test, using the same permeation apparatus as in Example 1. The test items and test results are shown in Table 4.

[0041]

[Table 4]

As is clear from the results in Table 4, tap water which passed through the contact-type water quality improver of Example 3 in comparison with blank tap water had a higher bacterial count, iron (mg / l),
The chromaticity was significantly reduced.

For Comparative Example 1, the water quality of the blank (water before treatment) and the water quality after treatment were tested in exactly the same manner as in Example 1 using the same permeation apparatus as in Example 1 and compared. . The test items and test results are shown in Table 5.

[0044]

[Table 5]

As is evident from the results in Table 5, turbidity of tap water passed through a water quality improver in which the components of the vitreous coating layer do not satisfy the predetermined composition can be reduced as compared with blank tap water. Did not.

COMPARATIVE EXAMPLE 2 Magnetite (Fe ₃ O ₄ ) 38% by weight and alumina (Al ₂
A mixture containing 34% by weight of O ₃ ) and 28% by weight of silicon oxide (SiO ₂ ) was pre-compressed into a sphere (diameter: 1.5 to 3 cm) and fired at 1300 ° C. for 2 hours to form a spherical ceramic base material. TiO ₂ on the surface as shown in Table 1
An aqueous suspension containing 0% by weight and 20% by weight of SiO ₂ .nH ₂ O was applied to the surface of a spherical ceramic substrate by a dipping method, and heated at 1300 ° C. for 2 hours to form a surface of rutile titanium oxide. The mixture was calcined so as to be glassy containing a crystal to obtain 30 kg of a spherical contact-type water quality improver.

For Comparative Example 2, the water quality of the blank (water before treatment) and the water quality after treatment were compared in exactly the same manner as in the test method of Example 1 using the same water permeation apparatus as in Example 1. Table 6 shows test items and test results.

[0048]

[Table 6]

As is clear from the results in Table 6, Comparative Example 2 containing rutile-type titanium oxide crystals as a component of the vitreous coating layer has the ability to kill general bacteria contained in blank groundwater. However, E. coli was not completely sterilized.

[0050]

According to the present invention, as described above, at least ferric tetroxide (Fe
_Since it is a contact type water quality improver formed with a vitreous coating layer containing each crystal of ₃ O ₄ ) and anatase type titanium oxide (TiO ₂ ), it is formed into various shapes such as spheres and filled in a small device. It is a contact-type water quality improver that can be used as it is. The physicochemical action of predetermined crystals in the vitreous coating layer prevents scale from forming in the pipes, and the water purification function can be regenerated by washing the surface, and the water purification function can be regenerated. There is an advantage that it works effectively for a period of time and becomes a contact-type water quality improver that is also effective for removing bacteria.

The vitreous coating layer is coated with triiron tetroxide (F
e ₃ O ₄ ) and anatase-type titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), and aluminum oxide (Al ₂ O ₃ ).
There is also an advantage that the above-mentioned effect becomes more reliable.

[Brief description of the drawings]

FIG. 1 is an explanatory view of a use state of a contact type water quality improving agent.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Permeation apparatus 2 Steel plate 3, 4, 5 Valve 6 Water quality improving agent 7 Flow meter

Claims (4)

[Claims] 1. The method according to claim 1, wherein the surface of the ceramic base material is coated with iron tetroxide (Fe ₃ O ₄ ) and anatase type titanium oxide (TiO 2).
₂ ) A contact type water quality improver obtained by forming a vitreous coating layer containing each crystal. 2. A vitreous material comprising, on the surface of a ceramic base material, 10 to 20% by weight of iron tetroxide (Fe ₃ O ₄ ) and 40 to 80% by weight of anatase type titanium oxide (TiO ₂ ). A contact type water quality improver comprising a coating layer. 3. A vitreous coating layer containing crystals of triiron tetroxide (Fe ₃ O ₄ ), anatase type titanium oxide (TiO ₂ ) and zirconium oxide (ZrO ₂ ) on the surface of a ceramic base material. A contact type water quality improver formed. 4. The method according to claim 1, wherein the surface of the ceramic base material is provided with iron trioxide (Fe ₃ O ₄ ), anatase type titanium oxide (TiO ₂ ),
A contact type water quality improver comprising a vitreous coating layer containing crystals of zirconium oxide (ZrO ₂ ) and aluminum oxide (Al ₂ O ₃ ).