JP2007209912A - Manufacturing method of ceramics particles for improving quality of chlorine treated water and quality improving method of chlorine treated water - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of ceramics particles capable of improving the quality of chlorine treated water while holding the beneficialness of chlorine and suppressing chlorine injury. <P>SOLUTION: A rock powder based on silicon (Si), aluminum (Al), an oxide, hydroxide or fluoride of iron (Fe) and containing an oxide, hydroxide or fluoride of a metal more easily reducible than iron as a very small amount component is used as a raw material. This rock raw material is baked at a high temperature of 1,000°C or above and raised to temperature of 500-1,000°C in a reducing atmosphere and rebaked to yield rebaked ceramics particles. The hardness of the rebaked ceramics particles can be more enhanced and the very small amount component in the rebaked ceramics particles can be reduced. Chlorine injury is suppressed while holding residual chlorine in water and the occurrence and propagation of Legionella bacteria can be suppressed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing ceramic particles for improving the quality of chlorinated water more effectively by using ceramic particles obtained by firing rock powder, and a method for improving the quality of chlorinated water.

  Conventionally, as this kind of ceramic particles, natural activated stone is refined and made into a sphere of about 3 mm to 5 mm with a binder, and then fired at a temperature of 1000 ° C. or higher for the purpose of improving the magnetic effect and hardness. It is said. Then, a circulating water bath using a furnace material of mineral ceramics is known that passes hot water between the ceramics to elute mineral components, sterilizes germs in the hot water, and deodorizes them (for example, Patent Documents). 1).

Further, as this kind of ceramic particles, ore of black vitreous quartz andesite is pulverized into fine particles of about 1 μm to 5 μm, and then the pulverized ore is mixed with clay, kneaded, put into a mold and molded. Thereafter, the shaped ore is pre-baked by unglazed baking, and then the unglazed baking is immersed in a solution in which fine particles are dissolved, so that the fine particles adhere to the surface of the unglazed baking. A ceramic far-infrared radiator configured by drying the unglazed product with the fine particles attached thereto and then firing in a ceramic kiln at a temperature of 1200 ° C. to 1300 ° C. is known (for example, Patent Document 2). reference.).
Japanese Utility Model Publication No. 4-17893 Japanese Patent Laid-Open No. 7-289174

  However, in the mineral ceramics and ceramic far infrared radiators described above, the mineral contained in the mineral ceramics is eluted in hot water, and the effect of the far infrared rays radiated from the surface of the ceramic far infrared radiator is the time. It is not economically superior because these mineral ceramics and ceramic far-infrared radiators need to be replaced periodically. In addition, these mineral ceramics and ceramic far-infrared radiators are excellent in activating water such as hot water, but it is easy to reduce the chlorine damage caused by chlorine contained in water such as hot water. It has a problem of not.

  This invention is made in view of such a point, and provides the manufacturing method of the ceramic particle | grain for the water quality improvement of chlorinated water which can reduce the chlorine damage by chlorinated water, and the water quality improvement method of chlorinated water With the goal.

  The method for producing ceramic particles for improving the quality of chlorinated water according to claim 1 mainly comprises at least one of oxides, hydroxides and fluorides of silicon (Si), aluminum (Al) and iron (Fe). A rock powder containing at least one of a reducible oxide, hydroxide and fluoride as an element is fired at a temperature of 1000 ° C. or higher to form primary fired ceramic particles, and the primary fired ceramic particles are low in oxygen. The temperature is raised to 500 ° C. or higher and 1000 ° C. or lower in an atmosphere to form refired ceramic particles.

  The method for producing ceramic particles for improving the water quality of chlorinated water according to claim 2 is the method for producing ceramic particles for improving the water quality of chlorinated water according to claim 1, wherein the primary fired ceramic particles are cooled and then reused. The sintered ceramic particles are used.

  The method for producing ceramic particles for improving the water quality of chlorinated water according to claim 3 is the method for producing ceramic particles for improving the water quality of chlorinated water according to claim 1 or 2, wherein the rock powder is fired to obtain a diameter of 0. A spherical primary fired ceramic particle having a diameter of 5 mm to 7 mm is used as a refired ceramic particle.

  The method for producing ceramic particles for improving the quality of chlorinated water according to claim 4 is the method for producing ceramic particles for improving the quality of chlorinated water according to any one of claims 1 to 3, wherein the atmosphere is low in oxygen. A reducing atmosphere in which an active gas is injected is used.

  The method for improving the quality of chlorinated water according to claim 5 includes a plurality of refired ceramic particles produced by the method for producing ceramic particles for improving the quality of chlorinated water according to any one of claims 1 to 4. The chlorinated water is passed through the container.

  The method for improving the quality of chlorinated water according to claim 6 is the method for improving the quality of chlorinated water according to claim 5, wherein chlorinated water in which Legionella bacteria remain in a container in which a plurality of refired ceramic particles are placed. Pass through.

  According to the method for producing ceramic particles for improving the quality of chlorinated water according to claim 1, at least one of oxides, hydroxides and fluorides of silicon (Si), aluminum (Al) and iron (Fe) After the rock powder containing at least one of a reducible oxide, hydroxide and fluoride is fired at a temperature of 1000 ° C. or higher to form primary fired ceramic particles, the primary fired ceramic particles are The element contained in the primary fired ceramic particles is reduced by raising the temperature to 500 ° C. or higher and 1000 ° C. or lower in an oxygen-poor atmosphere to reduce the elements contained in the primary fired ceramic particles. The structure changes. Therefore, by passing chlorinated water between these refired ceramic particles, chlorine damage from this chlorinated water can be prevented without removing chlorine contained in this chlorinated water, and the generation of Legionella bacteria is suppressed. In addition, since the redox potential and surface tension of this chlorinated water can be reduced, the water quality of the water can be improved efficiently with these refired ceramic particles.

  According to the method for producing ceramic particles for improving water quality of chlorinated water according to claim 2, in addition to the effect of the method for producing ceramic particles for improving water quality of chlorinated water according to claim 1, primary sintered ceramic particles are used. By cooling to refired ceramic particles, the temperature of the primary fired ceramic particles can be reliably increased.

  According to the method for producing ceramic particles for improving water quality of chlorinated water according to claim 3, in addition to the effect of the method for producing ceramic particles for improving water quality of chlorinated water according to claim 1 or 2, primary fired ceramics Since the hardness of the refired ceramic particles can be further improved, the water quality can be improved by the refired ceramic particles over a longer period of time.

  According to the method for producing ceramic particles for improving water quality of chlorinated water according to claim 4, in addition to the effect of the method for producing ceramic particles for improving water quality of chlorinated water according to any one of claims 1 to 3, oxygen By injecting an inert gas as a low atmosphere, the atmosphere becomes a reducing atmosphere, so that at least one of oxide, hydroxide and fluoride contained in the refired ceramic particles can be reduced more reliably. Therefore, the quality of chlorinated water by these refired ceramic particles can be improved more efficiently.

  According to the water quality improvement device of chlorinated water according to claim 5, a plurality of refired ceramic particles produced by the method for producing ceramic particles for improving the quality of chlorinated water according to any one of claims 1 to 4 are provided. By allowing the chlorinated water to pass through the filled container, chlorine damage can be suppressed while maintaining the sterilizing effect of chlorine contained in the chlorinated water.

  According to the method for improving the quality of chlorinated water according to claim 6, in addition to the effect of the method for improving the quality of chlorinated water according to claim 5, Legionella bacteria are contained in a container containing a plurality of refired ceramic particles. By allowing the remaining chlorinated water to pass, the growth of Legionella contained in the chlorinated water can be suppressed.

  Hereinafter, the configuration of an embodiment of a water quality improvement apparatus using ceramic particles of the present invention will be described with reference to FIG. 2 and FIG.

  2 and 3, reference numeral 1 denotes a water quality improvement device. This water quality improvement device 1 is not theoretically clear, but, for example, tap water, well water, bathtub water, As a result, the quality of water W, which is chlorinated water that is treated water, such as ground water, is improved. That is, the water quality improvement device 1 changes the properties of the water W by reducing the redox potential (ORP) and surface tension of the water W. Further, the water quality improvement device 1 is contained in the water W while retaining the residual chlorine contained in the chlorinated water W containing chlorine introduced for ensuring water quality safety. While suppressing the generation | occurrence | production of Legionella bacteria which are easy to reproduce at the temperature below degrees C, the proliferation of this Legionella bacteria is suppressed.

  Specifically, this water quality improvement apparatus 1 includes a processing tank 2 as a bottomed substantially cylindrical processing container having an axial direction along the vertical direction. At the bottom of the processing tank 2 is provided a lower arcuate surface portion 3 having an arcuate surface curved upward from the center region toward the side region. Further, at the upper end of the processing tank 2, there is provided an upper arcuate surface portion 4 having an arcuate surface shape curved in a direction facing from the side region toward the center region.

  At the center of the upper end of the upper circular arc surface portion 4 of the processing tank 2, a cylindrical outlet 5 is provided to project the water W that has flowed into the processing tank 2 and then flow out to the outside. ing. The outlet 5 has an axial direction along the vertical direction, and is provided concentrically with respect to the processing tank 2. A cylindrical inflow port 6 through which water W flows into the processing tank 2 is projected from the center of the lower end of the lower arc surface 3 of the processing tank 2. This inflow port 6 also has an axial direction along the vertical direction and is provided concentrically with respect to the processing tank 2.

  Further, the processing tank 2 includes a tank lower part 11 having an inflow pipe 6, a tank upper part 12 having an outflow port 5, and a tank intermediate part 13 that connects these tank lower part 11 and tank upper part 12 in a concentric manner. And is formed by. Further, between the tank lower part 11 and the tank intermediate part 13, and between the tank intermediate part 13 and the tank upper part 12, a disc-like mesh body 14 in plan view is attached. These mesh bodies 14 are formed with holes of such a size that the refired ceramic particles 15 filled in the processing tank 2 do not pass through.

  That is, the mesh body 14 attached between the tank intermediate portion 13 and the tank upper portion 12 is filled in the processing tank 2 when water W is introduced from the inlet 6 of the processing tank 2. The outflow of the refired ceramic particles 15 from the outlet 5 is prevented. The mesh body 14 attached between the tank lower part 11 and the tank intermediate part 13 is filled in the processing tank 2 when the inflow of water W from the inlet 6 of the processing tank 2 is stopped. Thus, the outflow from the inlet 6 due to the dead weight of the refired ceramic particles 15 accommodated is prevented. Further, the mesh body 14 serves as a tray when the refired ceramic particles 15 are accommodated from above the tank intermediate portion 13, and the refired ceramic particles 15 accommodated in the tank intermediate portion 13 are connected to the inlet. Prevents backflow from 6 to the outside.

  And between the mesh bodies 14 in the processing tank 2 formed by connecting each of the tank lower portion 11, the tank upper portion 12 and the tank intermediate portion 13, water W flowing in from the inlet 6 of the processing tank 2. A large number of refired ceramic particles 15 that improve the water quality of the water are filled and contained. The re-fired ceramic particles 15 are filled in the middle part of the processing tank by 5% or more and 50% or less, preferably 15% with respect to the volume in the processing tank. Further, the refired ceramic particles 15 are water quality improving materials that lower the oxidation-reduction potential of the water W and reduce the surface tension of the water W when improving the water quality of the water W.

  Here, the refired ceramic particles 15 are mainly composed of at least one of silicon (Si), aluminum (Al), iron (Fe) oxide, hydroxide and fluoride, and these silicon (Si), Contains at least one of metal oxide, hydroxide and fluoride, which can be reduced more easily than at least one of aluminum (Al), iron (Fe) oxide, hydroxide and fluoride, as a minor component Since the rock powder is granulated from the raw material, a method for producing the refired ceramic particles 15 will be described.

  First, the rock powder as a raw material was subjected to scan quality X-ray (SQX) analysis and found to contain the elements shown in Table 1.

  Specifically, as shown in Table 1, the rock powder is about 56.20% by mass of silicon (Si), about 12.13% by mass of iron (Fe), and about 9.73% by mass of aluminum (Al). %, Calcium (Ca) about 8.60% by mass, potassium (K) about 8.54% by mass. The rock powder is about 1.24% by mass of sodium (Na), about 1.14% by mass of titanium (Ti), about 0.95% by mass of magnesium (Mg), and about 0 of barium (Ba). 36% by mass and about 0.36% by mass of manganese (Mn). Further, the rock powder is about 0.28% by mass of strontium (Sr), about 0.12% by mass of phosphorus (P), about 0.08% by mass of zirconium (Zr), and about 0 of chlorine (Cl). 0.07% by mass and about 0.06% by mass of rubidium (Rb). The rock powder is about 0.04 mass% chromium (Cr), about 0.04 mass% zinc (Zn), about 0.04 mass% sulfur (S), and about 0 nickel (Ni). About 0.22% by mass is contained.

  Table 2 shows the result of converting this result into an oxide.

Specifically, as shown in Table 2, the rock powder is about 68.3 mass% silicon dioxide (SiO ₂ ), about 11.9 mass% alumina (Al ₂ O ₃ ), third iron oxide ( Fe ₂ O ₃₎ of about 6.42 wt%, about 5.00 wt% of calcium oxide (CaO), containing the potassium oxide _{(K 2} O) by about 4.55 wt%. Further, this rock powder has about 1.24% by mass of sodium monoxide (Na ₂ O), about 1.08% by mass of magnesium oxide (MgO), about 0.75% by mass of titanium dioxide (TiO ₂ ), About 0.17% by mass of manganese oxide (MnO) and about 0.16% by mass of barium oxide (BaO) are contained. Further, this rock powder has about 0.13 mass% diphosphorus pentoxide (P ₂ O ₅ ), about 0.11 mass% strontium oxide (SrO), and about 0.04 sulfur trioxide (SO ₃ ). It contains about 0.03% by mass of zirconium oxide (ZrO ₂ ) and about 0.03% by mass of chlorine (Cl). Further, this rock powder has about 0.02 mass% of _third chromium oxide (Cr ₂ O ₃ ), about 0.02 mass% of rubidium oxide (Rb ₂ O), and about 0.02 mass of zinc oxide (ZnO). About 0.01% by mass of nickel oxide (NiO) is contained.

  Then, this rock powder is pulverized into a fine powder having an average particle size of 0.5 μm or more and 10 μm or less as a pulverization step (step 1).

  Thereafter, as a granulation step, water or an organic solvent such as ethanol is added to the crushed rock and kneaded to granulate spherical fine particles having an average particle diameter of, for example, 0.5 mm to 7 mm (Step 2). ).

  In this state, as the first firing step which is the primary firing step, the granulated rock powder is fired at a high temperature of 1000 ° C. or more to be converted into ceramics, thereby obtaining primary fired ceramic particles (step 3).

  Here, when the primary sintered ceramic particles were analyzed by scan quality X-ray (SQX) analysis, they contained the elements shown in Table 3.

  Specifically, as shown in Table 3, the primary fired ceramic particles are about 53.89% by mass of silicon (Si), about 21.50% by mass of aluminum (Al), and about 9.50% of iron (Fe). 14% by mass, about 7.12% by mass of potassium (K) and about 4.99% by mass of calcium (Ca) are contained. Further, the primary fired ceramic particles are composed of about 1.51% by mass of titanium (Ti), about 0.65% by mass of sodium (Na), about 0.41% by mass of magnesium (Mg), and strontium (Sr). About 0.23 mass% and about 0.16 mass% of zirconium (Zr) are contained. Further, the primary fired ceramic particles comprise about 0.13 mass% phosphorus (P), about 0.11 mass% zinc (Zn), about 0.08 mass% rubidium (Rb), and sulfur (S). About 0.07% by mass is contained.

  Table 4 shows the result of converting this result into an oxide.

Specifically, as shown in Table 4, this primary fired ceramic particle is about 60.56% by mass of silicon dioxide (SiO ₂ ), about 26.05% by mass of alumina (Al ₂ O ₃ ), and third oxidized. It contains about 4.56% by mass of iron (Fe ₂ O ₃ ), about 3.50% by mass of potassium oxide (K ₂ O), and about 2.69% by mass of calcium oxide (CaO). Further, the primary fired ceramic particles have about 0.93% by mass of titanium dioxide (TiO ₂ ), about 0.77% by mass of sodium monoxide (Na ₂ O), and about 0.48 mass of magnesium oxide (MgO). %, Diphosphorus pentoxide (P ₂ O ₅ ) about 0.13 mass% and zirconium oxide (ZrO ₂ ) about 0.09 mass%. Further, the primary fired ceramic particles comprise about 0.09 mass% of strontium oxide (SrO), about 0.08 mass% of sulfur trioxide (SO ₃ ), about 0.04 mass% of zinc oxide (ZnO), About 0.03% by mass of rubidium oxide (Rb ₂ O) is contained.

Next, after cooling the primary fired ceramic particles as a cooling process (step 4), the primary fired ceramic particles are placed in a kiln (not shown) as, for example, nitrogen gas (N ₂ ) In a reducing atmosphere where an inert gas such as ₂ ) is injected and the atmosphere is low in oxygen, for example, held at a temperature of 500 ° C. or higher and 1000 ° C. or lower for 15 minutes or more and refired, and included in these primary fired ceramic particles The metal oxide that has been reduced is reduced to produce refired ceramic particles 15 as refired ceramics (step 5).

  Here, a scan quality X-ray (SQX) analysis of the refired ceramic particles 15 revealed that the elements shown in Table 5 were contained.

  Specifically, as shown in Table 5, the refired ceramic particles 15 are about 51.50 mass% silicon (Si), about 21.38 mass% aluminum (Al), and about 11 iron (Fe). 0.06% by mass, about 6.53% by mass of potassium (K), and about 5.34% by mass of calcium (Ca). The refired ceramic particles 15 are composed of about 1.46% by mass of titanium (Ti), about 0.65% by mass of sodium (Na), about 0.58% by mass of magnesium (Mg), and silver (Ag). About 0.40% by mass and about 0.35% by mass of zirconium (Zr). Further, the refired ceramic particles 15 are composed of about 0.24% by mass of strontium (Sr), about 0.20% by mass of manganese (Mn), about 0.14% by mass of phosphorus (P), zinc (Zn). About 0.10% by mass and about 0.09% by mass of rubidium (Rb).

  Table 6 shows the result of converting this result into an oxide.

Specifically, as shown in Table 6, this refired ceramic particle 15 is about 59.01% by mass of silicon dioxide (SiO ₂ ), about 25.96% by mass of alumina (Al ₂ O ₃ ), third It contains about 5.65% by mass of iron oxide (Fe ₂ O ₃ ), about 3.33% by mass of potassium oxide (K ₂ O), and about 3.00% by mass of calcium oxide (CaO). The re-fired ceramic particles 15 are about 0.93% by mass of titanium dioxide (TiO ₂ ), about 0.76% by mass of sodium monoxide (Na ₂ O), and about 0.67 of magnesium oxide (MgO). It contains about 0.15% by mass, about 0.15% by mass of zirconium oxide (ZrO ₂ ), and about 0.14% by mass of diphosphorus pentoxide (P ₂ O ₅ ). Further, the refired ceramic particles 15 are composed of about 0.14% by mass of first silver oxide (Ag ₂ O), about 0.09% by mass of manganese oxide (MnO), and about 0.09 of strontium oxide (SrO). It contains about 0.04% by mass of zinc oxide (ZnO) and about 0.03% by mass of rubidium oxide (Rb ₂ O).

  Next, the Vickers hardness of the primary fired ceramic particles and the refired ceramic particles 15 was measured and compared.

  First, when Vickers hardness of a total of five different primary fired ceramic particles was measured as the primary fired ceramic particles, as shown in Table 7, the Vickers hardness of these five primary fired ceramic particles averaged 918. It became.

  Next, the Vickers hardness of a total of five different refired ceramic particles 15 as refired ceramic particles 15 was measured. As shown in Table 8, the Vickers hardness of these five refired ceramic particles 15 was averaged. 965, which was larger than the average Vickers hardness of the primary fired ceramic particles.

  Next, a water quality improvement method using the water quality improvement apparatus 1 according to the embodiment will be described.

  First, water W is introduced from the inlet 6 of the processing tank 2. Then, this water W flows into the tank lower part 11 of the processing tank 2 from the inlet 6.

  Thereafter, the water W that has flowed into the tank lower part 11 from the inlet 6 collides with the inner surface of the tank lower part 11 and is rebounded upward at any position in the tank lower part 11. .

  As a result, after the water W is stored in the processing tank 2, the direction of the flow due to the flow of the water W is almost eliminated in the processing tank 2, and in almost the entire area of the processing tank 2. It flows so as to spring up almost uniformly in a certain direction from below to above.

  When the water W passes between the refired ceramic particles 15, the contact of the water W with the refired ceramic particles 15 reduces the oxidation-reduction potential and the surface tension of the water W. The water quality changes and the water quality is improved.

  At the same time, the water W passes between a plurality of refired ceramic particles 15 so that residual chlorine added in advance to the water W is retained, and the ability to suppress the generation of Legionella against the water W is improved. In addition, the growth inhibitory power of Legionella is improved.

  At this time, the water W changes to the alkali side while the pH is minute. Moreover, the water quality improvement effect of this water W can be improved, so that the water contact area and time by the rebaked ceramic particle 15 to the water W at this time are increased.

  Thereafter, the water W whose water quality has been improved passes through the mesh body 14 of the treatment tank 2 as improved water and then flows out from the outlet 5 to the outside.

  Next, an installation example of the water quality improvement apparatus 1 will be described.

  First, when the water quality improvement device 1 is installed in a system for circulating bath water H such as a public bath, the outlet 5 of the water quality improvement device 1 is placed upstream of the heat exchanger 21 as shown in FIG. Connect. The heat exchanger 21 is a device that heats the bathtub water H by heating the bathtub water H passing through the heat exchanger 21. Furthermore, the downstream side of the heat exchanger 21 is connected to an inlet 23 provided on the upstream side of the bathtub 22 in which the bathtub water H is stored.

  Further, a hair collector 25 for separating hair contained in the bathtub water H flowing out from the bathtub 22 from the bathtub water H is attached to the outlet 24 provided on the downstream side of the bathtub 22. ing. A chlorine injector 26 for injecting chlorine into the bathtub water H that has passed through the hair collector 25 is attached to the downstream side of the hair collector 25. Connected to the downstream side of the chlorine injector 26 is an upstream side of a filter 27 that filters the bathtub water H injected with chlorine by the chlorine injector 26 with a filter (not shown).

  The downstream side of the filter 27 is connected to the inlet 6 of the water quality improvement apparatus 1. Further, the water quality improvement apparatus 1 is attached to a bypass line 29 connected to a main flow line 28 where the downstream side of the filter 27 and the upstream side of the heat exchanger 21 are connected. The main flow line 28 is provided with a flow rate adjusting valve 31 for adjusting the flow rate of the bathtub water H passing through the main flow line 28, and flows to the bypass line 29 by adjusting the flow rate adjusting valve 31. The flow rate of the bathtub water H, that is, the flow rate of the bathtub water H passing through the water quality improvement device 1 is adjusted. In addition, on the upstream side and the downstream side of the water quality improvement device 1 of the bypass line 29, water stop valves 32 and 33 that can open and close the bypass line 29 are respectively attached. Furthermore, between the upstream side of the water quality improvement apparatus 1 and the water stop valve 32, a constant flow valve 34 for automatically adjusting the flow rate of the bathtub water H flowing into the water quality improvement apparatus 1 to a constant amount is attached. Yes.

  As a result, the bath water H flowing out of the bathtub 22 is filtered by the filter 27 after the hair or the like is separated by the hair collector 25 and then injected by the chlorine injector 26. Further, at least part of the bathtub water H filtered by the filter 27 passes through the water quality improvement apparatus 1 and a plurality of refired ceramics filled in the treatment tank 2 of the water quality improvement apparatus 1. By improving the water quality when passing between the particles 15, the residual chlorine previously added to the bath water H is retained, and the generation of Legionella in the bath water H is suppressed. Growth is suppressed. And the bathtub water H which passed this water quality improvement apparatus 1 is heated to predetermined temperature, when passing the heat exchanger 21, is sent to the inflow port 23 of the bathtub 22, and is supplied in this bathtub 22 Is done.

  As described above, according to the one embodiment, the main component is at least one of silicon (Si), aluminum (Al), iron (Fe) oxide, hydroxide, and fluoride. Si), aluminum (Al), iron (Fe) oxide, hydroxide and fluoride can be reduced more easily than at least one of metal oxide, hydroxide and fluoride Refired ceramics produced by firing rock powder as a component at a high temperature of 1000 ° C. or higher and then completely cooling it, then raising the temperature to 500 ° C. or higher and 1000 ° C. or lower in a reducing atmosphere. A configuration using particles 15 was adopted.

  At this time, when primary fired ceramic particles fired at a high temperature of 1000 ° C. or higher are refired at a temperature of 1000 ° C. or higher in a reducing atmosphere, the reduction of the elements in the primary fired ceramic particles proceeds excessively, The hardness and toughness of the refired ceramic particles 15 produced by refired fired ceramic particles are impaired.

  In addition, when the primary fired ceramic particles are refired at a temperature of 500 ° C. or less in a reducing atmosphere, the trace components contained in the primary fired ceramic particles cannot be efficiently reduced. The water quality improvement effect of the refired ceramic particles 15 produced by firing cannot be expected. Therefore, the re-baking of the primary sintered ceramic particles in a reducing atmosphere is preferably a temperature of 500 ° C. or higher and 1000 ° C. or lower. However, this temperature can vary depending on the degree of reduction of an inert gas flowing into a furnace (not shown) that refires the primary fired ceramic particles.

  As a result, by refiring the plurality of refired ceramic particles 15 in a reducing atmosphere, the hardness of the refired ceramic particles 15 is further improved, and the surface of the refired ceramic particles 15 is tightened and smoothed. The Therefore, since the stress concentration on the surface of the refired ceramic particles 15 can be avoided by smoothing the surface of the refired ceramic particles 15, it is possible to prevent the refired ceramic particles 15 from being damaged or broken. For this reason, these refired ceramic particles 15 can be used for a longer period of time.

  Further, since the refired ceramic particles 15 are not configured to collide with each other, it is not necessary to replace the refired ceramic particles 15 every predetermined period. Further, since these refired ceramic particles 15 do not improve the water quality by the precipitation action or the charging action, it is not necessary to wash or replace these refired ceramic particles 15. Further, since the water quality of the water W is improved by the wet action of the refired ceramic particles 15, the water quality improvement effect can be obtained even when the water W passes between the refired ceramic particles 15 at a low speed. Can do.

  Here, the longer the water contact time with these refired ceramic particles 15, the better the water quality of the water W. However, since the reactivity of these refired ceramic particles 15 themselves is improved, these refired ceramic particles 15 The effect can be obtained even if the water contact time with the particles 15 is shortened to some extent.

  At the same time, by refiring these refired ceramic particles 15 in a reducing atmosphere, trace components that are elements contained in these refired ceramic particles 15 are reduced. In other words, by reducing and re-firing the refired ceramic particles 15, it is possible to reduce the trace components in the primary fired ceramic particles before the refired ceramic particles, and to make the refired ceramic particles 15 having high reducibility. For this reason, while maintaining the residual chlorine in the chlorinated water with these refired ceramic particles 15, it is possible to improve the water quality by the reducing power and the antibacterial power.

  Therefore, by filling the processing tank 2 of the water quality improvement apparatus 1 with the plurality of refired ceramic particles 15 and passing the water W between the plurality of refired ceramic particles 15 in the processing tank 2, the water W The oxidation-reduction potential and surface tension of can be reduced. Therefore, since the reducing action of the water W can be further improved, chlorine damage such as metal oxidation and deterioration can be prevented while retaining the residual chlorine previously contained in the water W, and the inside of the water W can be prevented. Generation of Legionella bacterium can be suppressed, and the growth of Legionella bacterium present in the water W can be suppressed.

  For this reason, by reducing the oxidation-reduction potential of the water W, the water W can be given a reducing power. As a result, it is possible to easily generate water W having a reducing action, an antioxidant action, and an anti-corrosion action.

  Further, when the water W is improved in quality, the surface tension of the water W can be increased by reducing the surface tension of the water W, so that the surface activity of the water W can be increased. it can. Then, by circulating this water W through a tube (not shown), stone such as calcium and silica adhering to the inner wall of the tube, that is, scale, red rust, urine stone, etc. can be gradually dissolved and removed.

  Moreover, by using this water W, chlorine damage such as deterioration of various devices in a pool facility, a hot spring facility, or the like can be reduced.

  As a result, by passing the chlorinated water W between the refired ceramic particles 15, it is possible to suppress oxidation while maintaining residual chlorine without increasing the amount of chlorine, and is excellent in reducing power and antibacterial power. Since water quality can be improved, deterioration of water quality can be suppressed for a long period of time in many fields of drinking water and domestic water, and the current purification method by chlorine sterilization can be made more effective. In addition, the chlorine damage to the human body and living body due to the increase in the amount of chlorine input and the chlorine damage to various devices can be suppressed, the cost can be reduced due to the life extension effect of these devices, etc. Can promote environmental improvement. Therefore, the water quality improvement apparatus 1 excellent in handling property, maintenance property, and cost can be provided.

  Here, it is considered that removing chlorine in tap water currently leads to improvement of water quality, and most households use water purifiers to remove chlorine from tap water. On the other hand, if ice is made with tap water from which chlorine has been removed with a general refrigerator ice maker, general bacteria may grow in the tap water, and tap water from which chlorine has been removed can be drunk immediately. However, general bacteria will grow in tap water left for a long time.

  In addition, water tanks installed on the rooftops of buildings and condominiums have problems such as the growth of general bacteria and the deterioration of water quality such as oxidation of tap water because tap water is retained. For this reason, although there is a tendency not to use a water receiving tank, it is not preferable from the viewpoint of securing water for disaster prevention.

  On the other hand, by using the water quality improvement device 1 described above, the tap water stored in the water receiving tank is circulated through the flow path including the water quality improvement device 1, thereby reducing the redox potential of this tap water. At the same time, it was confirmed that the surface tension can be reduced and the water quality such as the reduction of harmful substances can be improved. In addition to tap water and other public water, improvement of water quality is a problem not only in public bath water H.

  In particular, in bath water H, it is not easy to cope with Legionella in general bacteria. The Ministry of Health, Labor and Welfare has announced the management guidelines such as hygiene for public baths and inns. In this management guideline, the temperature of the bath water H stored in the hot water tank is kept at 60 ° C or higher, and a circulation filtration device is used. It is described that an aerosol generation device is not installed for the bathtubs. However, in this circulation filtration device, dirt adheres to and accumulates on the filter medium used in this circulation filtration device, and microorganisms such as Legionella spp. Once attached and propagated, chemical cleaning is required.

  On the other hand, by circulating the bathtub water H in a state where the above-described water quality improvement apparatus 1 is installed in the subsequent stage of the circulation filtration apparatus, Legionella bacteria are compared with the bathtub water H in which the water quality improvement apparatus 1 is not installed. Can be suppressed. At this time, most of the filter media in the filtration apparatus in which bacteria are likely to propagate conventionally do not change.

  Here, as a method for sterilizing Legionella, there are methods such as chlorine sterilization containing hypochlorous acid, ozone sterilization, ultraviolet sterilization, and heat sterilization. Among these, ozone sterilization is effective from the viewpoint of disinfection and sterilization of pathogenic organisms, biodegradability improvement of difficult-to-decompose organic matter, etc., and since ozone is decomposed into oxygen after use, it is an environmentally friendly sterilization method However, if a person inhales ozone even in a very small amount, there is a possibility that it may cause damage to the bronchi and lungs.

  In addition, UV sterilization can inactivate Legionella bacteria and bacteria by irradiating the bath water with UV light, but if the circulation system including this UV sterilization is stopped, the bacteria can easily grow in the bath water. Therefore, continuous operation of this circulation system is required. Further, in order to maintain the effect of this ultraviolet sterilization, periodic cleaning is important and maintenance is not easy.

  Furthermore, chlorine sterilization is easy because it only adds chlorine to the bath water, and the effect can be improved by increasing the amount of chlorine input. Not only the skin but also the equipment is caused by chlorine damage, and the environment deteriorates due to drainage deterioration. On the other hand, by incorporating the above-described water quality improvement apparatus 1 into various piping systems, the beneficial effect of chlorine can be improved while solving the problems caused by chlorine sterilization.

  In the above embodiment, by passing the chlorinated water W through the water quality improvement device 1, the oxidation-reduction potential and the surface tension of the water W are reduced, and generation and growth of Legionella are suppressed. However, it only needs to have an effect on at least one of these redox potential, surface tension, and generation inhibition of general bacteria such as Legionella.

  The primary fired ceramic particles were cooled and then refired in a reducing atmosphere to obtain refired ceramic particles 15. However, even if the primary fired ceramic particles were refired without cooling, Can be manufactured.

<Example 1>
Next, Example 1 using the water quality improvement apparatus 1 will be described.

  In the first embodiment, tap water in Kyoto city is used as raw water, and the original ceramics which are primary fired ceramic particles subjected only to primary firing in the tap water, and the refired ceramic filled in the water quality improvement device 1 are used. The re-fired ceramic as the particles 15 was immersed, and the redox potential (ORP) and the water temperature were measured immediately after the immersion and 1 hour after the start of the immersion.

  As a result, as shown in Table 9, in the tap water in which the refired ceramic particles 15 are submerged, the oxidation-reduction potential immediately after the immersion is 364 mV, the water temperature is 27.0 ° C., and the oxidation-reduction potential one hour after the start of the immersion is The water temperature became 27.6 ° C. at 329 mV. On the other hand, in tap water in which primary fired ceramic particles are immersed, the oxidation-reduction potential immediately after immersion is 452 mV, the water temperature is 27.7 ° C., the oxidation-reduction potential 1 hour after the start of immersion is 428 mV, and the water temperature is 28. It reached 0 ° C. Furthermore, in tap water in which nothing is submerged, the redox potential immediately after submerging the ceramic particles 15 and the primary fired ceramic particles in other tap water is 586 mV, the water temperature is 28.1 ° C., and one hour after the start of submergence The oxidation-reduction potential was 428 mV and the water temperature was 28.2 ° C.

  Therefore, it was found that the redox potential of tap water can be lowered by immersing the refired ceramic particles 15 in tap water as compared with the case where no re-immersion is performed and the case where the primary fired ceramic particles are immersed.

  Furthermore, this tap water is passed through each of the processing tank 2 filled with the primary fired ceramic particles, the processing tank 2 containing the refired ceramic particles 15 and the processing tank 2 not housed at all. The redox potential (ORP) and the water temperature when this tap water was circulated once were measured.

  As a result, as shown in Table 10, in the tap water that circulated once through the treatment tank 2 filled with the refired ceramic particles 15, the oxidation-reduction potential was 498 mV and the water temperature was 25.8 ° C. On the other hand, in tap water that circulated once through the treatment tank 2 filled with the primary fired ceramic particles, the oxidation-reduction potential was 528 mV and the water temperature was 25.5 ° C. Furthermore, in the tap water which circulated through the treatment tank which is not filled with anything, the redox potential was 603 mV and the water temperature was 26.1 ° C.

  From this result, by circulating tap water in the processing tank 2 filled with the re-fired ceramic particles 15, the inside of the processing tank 2 not filled at all or the processing tank 2 filled with the primary fired ceramic particles is obtained. It was found that the redox potential of tap water can be lowered from each of the cases where the water is circulated.

<Example 2>
Next, Example 2 using the refired ceramic particles 15 will be described.

  In this Example 2, tap water in Kyoto city is used as raw water, and the primary fired ceramic particles subjected to primary firing only in the raw water and the refired ceramic particles 15 filled in the water quality improvement device 1 are used. The surface tension (dyn / cm) immediately before the immersion, 15 minutes after the start of the immersion, 30 minutes after the start of the immersion, 1 hour after the start of the immersion, and 2 hours after the start of the immersion is obtained. ), Water temperature, and pH.

  As a result, as shown in Table 11, in the raw water in which the refired ceramic particles 15 are immersed, the surface tension immediately before the immersion is 73.5 dyn / cm, the water temperature is 24 ° C., the pH is 7.0, and the surface 15 minutes after the start of the immersion. When the tension is 70.2 dyn / cm, the water temperature is 25 ° C. and the pH is 7.0. After 30 minutes from the start of water immersion, the surface tension is 67.4 dyn / cm and the water temperature is 26.5 ° C. and the pH is 7.0. When the tension was 63.3 dyn / cm, the water temperature became 27 ° C. and pH 7.1, and after 2 hours from the start of water immersion, the surface tension became 61.2 dyn / cm and the water temperature became 26.7 ° C. and pH 7.2.

  In contrast, in the raw water in which the primary fired ceramic particles are immersed, the surface tension immediately before the immersion is 73.5 dyn / cm, the water temperature is 24 ° C., the pH is 7.0, and the surface tension 15 minutes after the start of the immersion is 70.4 dyn / cm. The water temperature was 25 ° C. and pH 7.0 at 30 cm, the surface tension 30 minutes after the start of water immersion was 68.3 dyn / cm, the water temperature was 26.5 ° C. and pH 7.0, and the surface tension 1 hour after the start of water immersion was 64.6 dyn / The water temperature was 27 ° C. and the pH was 7.1 at cm, and the surface tension after 2 hours from the start of water immersion was 62.8 dyn / cm and the water temperature was 26.7 ° C. and the pH was 7.2.

  Therefore, it was found that the surface tension of the raw water can be lowered by immersing the re-fired re-fired ceramic particles 15 in the raw water as compared with the case where the primary fired ceramic particles are immersed.

<Example 3>
Next, Example 3 using the water quality improvement apparatus 1 will be described.

  In this Example 3, the water quality improvement apparatus 1 is attached to a water receiving tank installed in an arbitrary building, and the tap water serving as drinking water stored in the water receiving tank is circulated to the water quality improvement apparatus 1. Each of the general bacteria, Escherichia coli, lead, and lead compound was measured for the untreated water in the state and the treated water in a state after the tap water was circulated through the water quality improvement apparatus 1.

  As a result, as shown in Table 12, in untreated water, lead and a lead compound were detected in an amount of 0.019 mg / L higher than the reference value (0.01 mg / L or less). In contrast, as shown in Table 13, in the treated water, only 0.002 mg / L of lead and a lead compound that were lower than the reference value was detected.

  Therefore, the content of harmful lead and lead compounds contained in the tap water can be lowered by circulating the tap water to the water quality improvement device 1, and as shown in Table 12 and Table 13, it is based on the Water Supply Law. It was found that drinking water that complies with water quality standards (Ministry of Health, Labor and Welfare Ordinance No. 101) can be obtained.

<Example 4>
Next, Example 4 using the water quality improvement apparatus 1 will be described.

  In this Example 4, tap water in Kyoto city is used as raw water, and after this tap water is passed through the water quality improvement device 1, untreated water and after this tap water is passed through the water quality improvement device 1 It measured about each of the treated water of the state.

  As a result, as shown in Table 14, in untreated water, lead and lead compounds were detected in an amount of 0.005 mg / L, nitrate nitrogen and nitrite nitrogen were detected in an amount of 3.4 mg / L, and zinc and zinc About 0.039 mg / L of compound was detected, about 0.04 mg / L of copper and copper compounds were detected, and about 110 mg / L of evaporation residue was detected.

  On the other hand, as shown in Table 15, in treated water, lead and lead compounds were detected in less than 0.001 mg / L, nitrate nitrogen and nitrite nitrogen were detected in an amount of 0.03 mg / L, zinc and zinc The compound was detected as 0.010 mg / L, copper and copper compounds were detected as less than 0.01 mg / L, and the evaporation residue was detected as 85 mg / L.

  Therefore, by passing the tap water through the water quality improvement device 1, harmful lead, lead compound, nitrate nitrogen, nitrite nitrogen, zinc, zinc compound, copper, copper compound and evaporation contained in this tap water It was found that each of the residues was reduced.

<Example 5>
Next, Example 5 using the water quality improvement apparatus 1 will be described.

  In the fifth embodiment, the bath water before and after mounting the water quality improvement device 1 in a system such as a circulation filtration device that circulates the bath water H that is hot spring water (raw water) in the bathtub 22 installed in an arbitrary inn. Each of the H states was measured.

  As a result, as shown in Table 16, in the state before the bath water H is circulated to the water quality improvement apparatus 1, the Legionella spp. About 120 CFU / 100 mL was detected. On the other hand, as shown in Table 17, in the state after circulating this bathtub water H to the water quality improvement apparatus 1, no Legionella spp. (The number of bacteria) was detected from this bathtub water H (detection) (Limit: 10 CFU / 100 mL).

  Therefore, since the number of Legionella bacteria contained in the bathtub water H is reduced by circulating the bathtub water H to the water quality improvement device 1, the generation of Legionella bacteria in the bathtub water H is generated. It was found that the growth of Legionella in the bath water H can be suppressed.

It is a flowchart which shows one Embodiment of the manufacturing method of the ceramic particle | grains of this invention. It is explanatory drawing which shows the water quality improvement apparatus provided with ceramic particle same as the above. It is explanatory drawing which shows the installation state of a water quality improvement apparatus same as the above.

Explanation of symbols

2 Processing tank as a container
15 Refired ceramic particles W Water as chlorinated water

Claims (6)

Silicon (Si), aluminum (Al) and iron (Fe) oxides, hydroxides and fluorides as main elements, at least any of reducible oxides, hydroxides and fluorides The rock powder containing is fired at a temperature of 1000 ° C. or higher to form primary fired ceramic particles,
A method for producing ceramic particles for improving water quality of chlorinated water, characterized in that the primary fired ceramic particles are heated to a temperature of 500 ° C. or higher and 1000 ° C. or lower in an oxygen-poor atmosphere to obtain refired ceramic particles. The method for producing ceramic particles for improving the quality of chlorinated water according to claim 1, wherein the primary fired ceramic particles are cooled and then re-fired ceramic particles. 3. The quality of chlorinated water according to claim 1 or 2, wherein the rock powder is fired into spherical primary fired ceramic particles having a diameter of 0.5 mm or more and 7 mm or less to refire ceramic particles. Of producing ceramic particles. The method for producing ceramic particles for improving the quality of chlorinated water according to any one of claims 1 to 3, wherein a reducing atmosphere in which an inert gas is injected is used as an atmosphere containing little oxygen. The chlorinated water is allowed to pass through a container containing a plurality of refired ceramic particles produced by the method for producing ceramic particles for improving the quality of chlorinated water according to any one of claims 1 to 4. Water quality improvement method for chlorinated water. The method for improving the quality of chlorinated water according to claim 5, wherein chlorinated water in which Legionella bacteria remain is passed through a container in which a plurality of refired ceramic particles are placed.

Images