JP4185482B2 - Bathing materials and artificial hot springs - Google Patents

Description

The present invention mainly relates to a bath material used for general household, industrial use, commercial use, etc., and an artificial hot spring using the same.
In the present invention, “parts” and “%” are based on mass unless otherwise specified.

  The effective use of industrial byproducts is increasingly required. Blast furnace slag is known as a representative by-product. Among these, vitrified granulated blast furnace slag has an excellent latent hydraulic property that long-term strength does not decrease even when mixed in a large amount with cement, and is widely used in the cement and concrete field. On the other hand, blast furnace slow cooling slag is also called ballast and does not show hydraulic properties. For this reason, it has been mainly used as a roadbed material, but recently, recycled aggregate has been preferentially used as a roadbed material and is losing its conventional use. In other words, the effective utilization method is still in the sought state.

  As a result of various studies on effective utilization of the blast furnace slow cooling slag, the present inventor has found that the blast furnace slow cooling slag fine powder has a function of suppressing cement / concrete bleeding and neutralization. Furthermore, when applied to high-fluidity concrete, it can be made into high-fluidity concrete with excellent material separation resistance and fluidity retention performance, low self-shrinkage and low heat of hydration. I also learned that it becomes concrete. However, there is an urgent need to find many more applications for effective utilization of blast furnace slow cooling slag.

By the way, tap water contains chlorine for the purpose of disinfection. This is because hypochlorous acid is added. The added hypochlorite (HClO) is partially hypochlorite ions (ClO ^-) and chlorine ions (Cl ^-) present as, other, monochloramine (NH ₂ Cl), dichloramine (NHCl ₂₎ Also present as chlorine combined with nitrogen, such as trichloramine (NCl ₃ ). These are collectively called Kalki.

In particular, hypochlorous acid (HClO) and hypochlorite ion (ClO ⁻ ) have a strong bactericidal power. Utilizing these bactericidal powers, it is used for disillusioning bacteria such as Escherichia coli, but on the other hand, it has been pointed out to have an effect on human skin. That is, hypochlorous acid (HClO) and hypochlorite ions (ClO ⁻ ) are oxidizing agents and are deeply related to the aging phenomenon of human skin (see Patent Document 1). Especially in big cities with poor water quality, a lot of hypochlorous acid is added to disillusion the bacteria, so the amount of chlorite in tap water is very high, exceeding 1.0 mg / l. Relatively high calcium is dissolved. In recent years, the awareness of beauty and health has been increasing, especially among women.

  As a method for modifying water, it is known to modify water with weak oxidizing power by the negative ion effect of tourmaline (see Patent Document 2). However, tourmaline was a kind of gem and was very expensive. Not only that, but there are many things that do not have the desired reforming effects depending on the production area and characteristics. In addition, there are many various descaling agents and bathing agents containing the same (see, for example, Patent Documents 3 to 6).

  However, these descaling agents and bathing agents containing them do not have a sustained descaling effect. Moreover, it is a comparatively expensive thing as daily necessities. And in the inside, many components other than the descaling agent mainly composed of organic components are contained, and some of the components affect the environment.

JP-A-12-119161 Japanese Patent Laid-Open No. 07-132284 Japanese Patent Laid-Open No. 02-115117 Japanese Patent Laid-Open No. 05-317865 Japanese Patent Laid-Open No. 06-211643 JP 08-225442 A

In view of the above-mentioned problems, the present inventors have conducted research on inexpensive and environmentally friendly bath materials. As a result, it has been found that the blast furnace chilled slag has a very excellent peeling effect, the effect has a certain sustainability, and the sustaining effect can be controlled by the particle size. It was also found that blast furnace chilled slag can be used as a kind of artificial hot spring by putting it in hot water as a bath material.
As described above, the present inventors have found that it is possible to effectively use the blast furnace slow cooling slag and to develop a bath material and an artificial hot spring that are inexpensive and highly effective, and have completed the present invention.

That is, the present invention includes blast furnace gradual cooling of at least one of gravel, sand, and powder, containing 0.3% or more of sulfur present as non-sulfate sulfur and having a vitrification rate of 30% or less. and slag, a bath material comprising the one or carbonate component is two or more selected from among carbonates and bicarbonates, is La, artificial, which comprises using a bath timber It is a hot spring.

  By using the bath material of the present invention, water can be modified into water that is preferable from the viewpoint of beauty and health, and an artificial hot spring can be obtained.

  Hereinafter, the present invention will be described in detail.

The blast furnace slag used in the present invention is a blast furnace slag which has been cooled and crystallized.
The components of blast furnace slow-cooled slag have the same composition as granulated blast furnace slag. Specifically, SiO ₂ , CaO, Al ₂ O ₃ , MgO, etc. are the main chemical components, and TiO. ₂ , MnO, Na ₂ O, S, P ₂ O ₅ , Fe ₂ O _{3 and the} like. The compound, as a main component a so-called melilite is a mixed crystal of gehlenite _{2CaO · Al 2 O 3 · SiO} 2 and Akerumanaito 2CaO · MgO · 2SiO _2, other, dicalcium silicate 2CaO · SiO _2, rankinite night 3CaO · 2SiO _2, calcium silicates, such as wollastonite CaO · SiO _2, Merubinaito 3CaO · MgO · 2SiO _2, calcium magnesium silicate, such as Monte celite CaO · MgO · SiO _2, anorthite _{CaO · Al 2 O 3 · 2SiO} 2, Liu Site (K ₂ O, Na ₂ O) / Al ₂ O ₃ / SiO ₂ , spinel MgO / Al ₂ O ₃ , magnetite Fe ₃ O ₄ , and sulfides such as calcium sulfide CaS and iron sulfide FeS There is.

  In the present invention, it is preferable to use a blast furnace slow-cooled slag containing 0.3% or more of sulfur present as non-sulfate sulfur (hereinafter simply referred to as non-sulfate sulfur). Those containing 0.5% or more are more preferable, and those containing 0.7% or more are most preferable. If the non-sulfuric sulfur is less than 0.3%, the effects of the present invention, that is, the effect of removing chalk and the pharmacological effect as a bath material may not be sufficiently obtained.

  The amount of non-sulfuric sulfur is determined by quantifying the amount of total sulfur, the amount of elemental sulfur, the amount of sulfide sulfur, the amount of thiosulfuric sulfur, and the amount of sulfuric sulfur (sulfur trioxide). The method for quantifying sulfur in different states can be obtained by the method of Yamaguchi and Ono. This is described in detail in a paper entitled “Analysis of Sulfur State in Blast Furnace Slag” (Naoji Yamaguchi, Shogo Ono: Steel Research No. 301, pp. 37-40, 1980). Further, the amount of sulfate sulfur (sulfur trioxide) and the amount of sulfide sulfur can also be determined by the method defined in JIS R 5202.

  The vitrification rate of the blast furnace annealed slag used in the present invention is preferably 30% or less, and more preferably 10% or less. If the vitrification rate exceeds 30%, the effects of the present invention, that is, the effect of removing the chalk and the pharmacological effect as a bath material may not be sufficiently obtained.

The vitrification rate (X) referred to in the present invention is determined as X (%) = (1−S / S ₀ ) × 100. Here, S is the main crystalline compound in slow-cooled slag obtained by powder X-ray diffractometry (mixed crystal of gelenite 2CaO · Al ₂ O ₃ · SiO ₂ and akermanite 2CaO · MgO · 2SiO ₂ ). The area of the main peak, S ₀ represents the area of the main peak of melilite after slowly cooling the slag at 1000 ° C. for 3 hours and then cooling at a cooling rate of 5 ° C./min.

  The particle size of the blast furnace slow cooling slag is not particularly limited. Various sizes are available, such as gravel with a size exceeding 5 mm, a sandy shape below 5 mm, and a powdery one. Depending on the particle size of the blast furnace slow-cooled slag, it is possible to adjust the sustainability of the pharmacological effect as a bathing material and the effect of removing chalk. When expecting immediate effect, it is preferable to use a powdery material, and when expecting sustainability, it is preferable to use a gravel or sandy material.

Powdery ones, generally preferably those in the range of about 2000~8000cm ² / g in Blaine specific surface area, more preferably of about 3000~7000cm ² / g, the Blaine specific surface area is less than 2000 cm ² / g is Since the immediate effect cannot be expected so much, there is no point in using the powder, and pulverization to exceed 8000 cm ² / g is uneconomical because the pulverization power becomes large and the blast furnace slow cooling slag is weathered. There is a tendency for quality to deteriorate over time.

The carbonic acid component of the present invention is a general term for substances that can supply CO ₃ ²⁻ or HCO ³⁻ ions when placed in water. Specific examples thereof include charcoal salts, such as bicarbonate salts. Examples of the carbonate include alkali metal carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate, and alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate. Examples of the bicarbonate include alkali metal bicarbonates such as sodium bicarbonate, potassium bicarbonate, and lithium bicarbonate.

  In the present invention, the use ratio of the blast furnace slow cooling slag and the carbonic acid component is not particularly limited, but usually the blast furnace slow cooling slag is 50 to 99.9 in a total of 100 parts of the blast furnace slow cooling slag and the carbonic acid component. Part is preferable, and 70 to 99 parts are more preferable. Moreover, 0.1-50 parts is preferable and, as for a carbonic acid component, 1-30 parts is more preferable. If the slow cooling slag is less than 50 parts or the carbonic acid component exceeds 50 parts, the reduction effect may be reduced, conversely, the blast furnace slow cooling slag exceeds 99.9 parts, or the carbonic acid component is 0.00. If it is less than 1 part, the pH may be high and the alkalinity may be too strong.

  Although the usage-amount of the bath material of this invention (henceforth this material) is not specifically limited, Usually, it can be used in the range of 0.1-100 parts with respect to 100 parts of water, 1-50 parts is more preferable. If the amount is less than 0.1 part, the effects of the present invention may not be sufficiently obtained, and even if the amount exceeds 100 parts, further enhancement of the effect cannot be expected.

The effect of removing chlorine can be evaluated by measuring the concentration of hypochlorous acid or hypochlorite ion in the water quality or by measuring the oxidation-reduction potential.
The concentration of hypochlorous acid or hypochlorite ion can be measured by the DPD method (diphenyl-p-phenylenediamine method), the current method, the spectrophotometric method, the syringaldazine method (Syringaldazine), or the like. Among these, the syringaldazine method is characterized by extremely little influence of iron, manganese and nitrite ions, and low reactivity with monochloramine and dichloroamine, and a measurement range of 0.1 to 10 mg / l. It is a wide and useful measurement method. Recently, a test paper based on this method has been developed, and it is convenient and convenient to use it.

  The concentration of hypochlorous acid and hypochlorite ion is strongly related to the oxidation-reduction potential. Therefore, it can be evaluated by a redox potential. The redox potential can be easily measured with a redox potential meter. The redox potential changes in conjunction with pH. Therefore, when comparing, it is necessary to compare at the oxidation-reduction potential at the same pH. It means that the oxidation-reduction potential is more oxidizing as it goes to the + (plus) side, and it is reducing as it goes to the-(minus) side. Usually, the pH of tap water is in a neutral region (around 7), and the oxidation-reduction potential at that time is +300 to 800 mV. In particular, in large cities such as Tokyo and Osaka, the oxidation-reduction potential has a high value. In Osaka, there are many places of about +700 mV and in Tokyo about +500 mV. This means that the tap water in Osaka and Tokyo is highly oxidative and rich in calcite.

  In the present invention, conventionally used bathing agents can be used in addition to the present material.

  Hereinafter, further description will be given based on experimental examples of the present invention.

Experimental example 1
Using tap water from Osaka, we confirmed the water reforming effect of the bath material. As shown in Table 1, blast furnace slag (0.2 to 5 mm) having different characteristics and various carbonic acid components were blended as shown in Table 1 to prepare bath materials. 3 parts of this bath material was used with respect to 100 parts of water and left for 3 hours with slight stirring. The total amount of hypochlorous acid and hypochlorite ions, the redox potential, and the pH before and after that were measured. The results are also shown in Table 1.

<Materials used>
Blast furnace slag A: Blast furnace slow-cooled slag, vitrification rate 5%, specific gravity 3.00, non-sulfuric sulfur 0.7%
Blast furnace slag B: Blast furnace slow-cooled slag and blast furnace slag A were dipped in water and aged to make non-sulfuric sulfur 0.5%. Vitrification rate 5%, specific gravity 3.00.
Blast furnace slag C: Blast furnace slow-cooled slag and blast furnace slag A were dipped in water and aged to make non-sulfuric sulfur 0.3%. Vitrification rate 5%, specific gravity 3.00.
Blast furnace slag D: Blast furnace slow-cooled slag and blast furnace slag A are dipped in water and aged to make non-sulfuric sulfur 0.1%. Vitrification rate 5%, specific gravity 3.00.
Blast furnace slag E: Blast furnace slow-cooled slag, vitrification rate 10%, specific gravity 2.97, non-sulfuric sulfur 0.7%
Blast Furnace Slag F: Blast Furnace Slow Cooling Slag, Vitrification Ratio 30%, Specific Gravity 2.94, Non-sulfate Sulfur 0.7%
Blast furnace slag G: Granulated blast furnace slag, 95% vitrification, 2.90 specific gravity, 0.7% non-sulfuric sulfur
Carbonic acid component A: Sodium bicarbonate Carbonic acid component B: Sodium carbonate Carbonic acid component C: Carbon dioxide component B and carbonic acid component B
Water: Osaka tap water, total amount of hypochlorous acid and hypochlorite ion is 2.1 mg / l, redox potential is +700 mV.

<Measurement method>
Total amount of hypochlorous acid and hypochlorite ion: Measured by the syringaldazine method.
Redox potential: Measured with a redox potential meter. However, the redox potential of tap water was adjusted by adjusting the pH with sodium hydroxide and compared with the redox potential when the pH was the same as when using a blast furnace slow cooling slag.

  From Table 1, it can be seen that by using the bath material of the present invention, the hypochlorous acid concentration and oxidation-reduction potential of tap water are lowered. Therefore, a bathing material that exhibits an excellent effect in removing water from water can be obtained, and an artificial hot spring can be obtained.

Experimental example 2
The same procedure as in Example 1 was performed except that a bath material comprising 95 parts of blast furnace slow cooling slag A and 5 parts of carbonic acid component A was used and the amount of the bath material was changed as shown in Table 2. The results are also shown in Table 2.

  From Table 2, it can be seen that the hypochlorous acid concentration and redox potential of tap water decrease as the amount of the bath material of the present invention increases.

Experimental example 3
Blast furnace slow cooling slag A was used, and as shown in Table 2, those having different particle sizes were prepared. And the same experiment as Example 1 was repeated and the sustainability of the descaling effect was confirmed. The results are also shown in Table 3.

  From Table 3, it can be seen that the effect of lowering the hypochlorous acid concentration of tap water persists as the particle size of the bath material of the present invention becomes coarse.

Experimental Example 4
A bath material consisting of 95 parts of gravel-like blast furnace slag A and 5 parts of carbonic acid component a was used, and 10 kg of the bath material was put into 200 liters of tap water in Aomi Town, Niigata Prefecture, and the bath was boiled. In addition to examining the pH and components of this bath, 10 men and 5 men took a bath to evaluate the quality of the water. The results are shown in Table 4.

<Measurement method>
pH: Measured with a pH meter.
Chemical component: Sulfur content and carbonic acid component were analyzed. The concentration of sulfide ion, thiosulfate ion, and sulfate ion was measured by ion chromatography.

  From Table 4, it can be seen that the artificial hot spring using the bath material of the present invention can prepare a pseudo-high quality sulfur-carbonate spring.

  By using the bath material of the present invention, water can be modified into water that is preferable from the viewpoint of beauty and health, and an artificial hot spring can be obtained. It can be applied to reforming.

Claims (2)

One or more types of blast furnace chilled slag of gravel, sand or powder, containing 0.3% or more of sulfur present as non-sulfate sulfur and having a vitrification rate of 30% or less , carbonate and A bath material comprising a carbonate component that is one or more selected from bicarbonates. An artificial hot spring comprising the bath material according to claim 1 .