JP2001322876A - Tourmaline ball and method for cleaning water - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize the high-efficiency cleaning of water, such as industrial water in particular, having a high degree of contamination (particularly high- efficiency corrosion prevention of piping and tanks to supply and store industrial water) by effectively utilizing the cleaning of water characteristic of the tourmaline. SOLUTION: Many tourmaline particulates are lumped by interposing inorganic insulator particulates (e.g. clay particulates) among the tourmaline particulates and fastening the tourmaline particulates and the inorganic insulator particulates to each other in a point-to-point contact state in the presence of inorganic adhesive materials (e.g. glassy components), the which the tourmaline balls forming the porous spherical bodies are obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spherical tourmaline mass in which tourmaline (an tourmaline) is agglomerated, and in particular, has an enhanced function useful for industrial water purification.

[0002]

2. Description of the Related Art It has long been known that tourmaline (tourmaline) has a self-polarizing effect and generates hydroxyl ions when placed in contact with water, which is useful for purifying water such as tap water. Have been. However, in the state of the rough tourmaline, the purification action is not sufficient, and thus, the rough tourmaline is usually used in the form of fine particles by grinding. In addition, by separating each of the finely divided tourmaline particles with an insulating material, self-polarization is generated independently in each tourmaline particle, and water purification of the tourmaline particles per weight or volume is performed. Some measures have been taken to enhance the effect. As the improvement of such tourmaline fine particles for water treatment, the following inventions have been proposed so far.

[0003] Patent Publication No. 2710768 (Japanese Patent Laid-Open No.
Japanese Patent Application Publication No. 110468) discloses a molded product in which tourmaline fine particles are dispersed in a glass matrix and is suitable for water purification treatment. Tokuhei 7-3898
No. 7 discloses a tourmaline granule obtained by electrically insulating and solidifying between tourmaline fine powders and a water surface activation device using the same.

Japanese Patent Application Laid-Open No. H11-165167 discloses a porous tourmaline-containing molded article formed from an alumina powder and a tourmaline powder. JP-A-9-157
No. 000 discloses a tourmaline ceramic obtained by sintering and pelletizing a mixture of tourmaline fine powder, ceramic powder, and silver, which is effective for improving water quality.

[0005] Japanese Patent Application Laid-Open No. 11-89906 discloses a ceramic for a bathroom, in which a hot spring component powder, a fine tourmaline powder, a glass powder and other binder powders are mixed and sintered to form a porous body. JP-A-10-17378 discloses a porous tourmaline molded product obtained by sintering a mixture of tourmaline fine powder and polyethylene or polypropylene fine powder.

JP-A-11-322469 discloses that tourmaline particles are used as a main material, porous fine particles (zeolite) are used as an auxiliary material, and an adhesive and a plastic material are kneaded and fired at a low temperature of about 800 ° C. Also disclosed are porous tourmaline ceramic materials.

[0007] Japanese Patent Application Laid-Open No. 11-192479 discloses an invention for improving the efficiency of water recycling by packing a raw tourmaline, a tourmaline molded product, or the like into a column provided in a water supply system. Japanese Patent Application Laid-Open No. Hei 10-314752 discloses that a material such as raw stone of tourmaline or molded body of tourmaline powder, which generates hydroxyl ions upon contact with water, is contained in a porous container such as a wire net and has a bottom in a water tank. A system for standing still in water to prevent the decay of water and the generation of odor is disclosed.

[0008] The water purifying action of tourmaline described in the above-mentioned patent-related publications is not particularly limited, but is used for purifying water of essentially high cleanliness such as tap water. No specific study has been made on the purification action (prevention of rust generation, prevention of algae generation, etc.) in industrial water, which is far less clean.

Conventionally, the purifying action of industrial water has been realized by using chemicals. However, industrial water containing chemicals is difficult to maintain the purifying effect of chemicals.
There are problems such as being unable to be discharged to an external water system as it is, and continuing to supply a necessary amount of chemicals for providing a sustainable purification effect, which is a great economic burden.

For this reason, a technique has been proposed in which industrial water is brought into contact with an ion exchanger such as an anion exchange resin or zeolite in order to prevent rust of pipes and vessels for distributing or containing industrial water or the like (JP-A-Hei. No. 6-158364).

[0011]

According to the study of the present inventors, tourmaline particles or a tourmaline molded body as disclosed in the above-mentioned patent publications have a purifying effect on industrial water (particularly a red rust preventing effect, etc.). Anti-corrosion effect)
It has been found that the effect is weak, and the purifying action of essentially pure water such as tap water is not always at a satisfactory level. It was also found that when placed in a flow path of industrial water, which may come into contact with a violent water flow, the molded body was broken in a short period of time, and the tourmaline particles tended to dissipate. Further, it has been found that the above-mentioned water purification method using an ion exchanger such as an anion exchange resin or zeolite does not show a sufficient effect on the purification effect of industrial water.

Accordingly, an object of the present invention is to make use of the self-polarizing property of tourmaline, and particularly to purify water such as industrial water (especially an anticorrosion effect of a metal portion forming a water passage). It is to provide a molded article. Another object of the present invention is to provide a purifying molded body that is useful not only for industrial water but also for purifying water such as ordinary tap water or purifying an environmental atmosphere such as air.

[0013]

SUMMARY OF THE INVENTION The present inventors have further improved the purifying action of water by tourmaline (especially the anticorrosive action of metallic materials that come into contact with water), and particularly from the use of iron or iron alloy materials such as industrial water. Research has been conducted with the aim of developing a tourmaline-based purifying material that can be advantageously used in a system that easily generates rust (particularly red rust) in piping sections and water storage containers. As a result, tourmaline is used as fine particles, and an insulating material (insulator) is arranged between adjacent tourmaline fine particles to isolate the tourmaline fine particles from each other. By making the surface of the fine particles of tourmaline contact with the inorganic adhesive as small as possible (point contact) using an inorganic adhesive, the water purification action (in particular, industrial water made of iron or iron alloy material) Excellent anticorrosion effect on pipes and water storage containers), and its water purification action is maintained at a high level for a long period of time. The present inventors have found that a tourmaline-containing molded article that can be maintained without causing the present invention is obtained, and reached the present invention. The tourmaline-containing molded article of the present invention can be advantageously used for decomposing and removing harmful components in gas.

According to the present invention, a large number of tourmaline fine particles have inorganic insulating fine particles interposed between the tourmaline fine particles, and the tourmaline fine particles and the inorganic insulating fine particles are fixed to each other in a point contact state in the presence of the inorganic adhesive component. A tourmaline ball characterized by being aggregated to form a porous spherical body. Note that the tourmaline ball of the present invention does not need to be a true sphere, but includes a normal tourmaline ball, such as a normal pellet, tablet, or spheroid, or a molded ball tourmaline.

[0015] The tourmaline ball of the present invention described above can be made, for example, by using a large number of tourmaline fine particles, a large number of inorganic insulating fine particles, and a total amount of tourmaline fine particles and inorganic insulating fine particles in the range of 1 to 10%. Mixing an inorganic adhesive that melts within a temperature range of 950 ° C. to 950 ° C .; forming an agglomerate while applying an organic adhesive aqueous solution to the mixture produced in the mixing step;
By heating to 00 to 950 ° C., the inorganic adhesive is melted or reacted while substantially maintaining the shapes of the tourmaline fine particles and the inorganic insulating fine particles, and then advantageously produced using a method including a step of cooling. be able to.

The present invention also relates to the use of the above-mentioned tourmaline ball for purifying water such as industrial water or tap water.

The present invention also provides a method for purifying industrial water, which comprises contacting the above-mentioned tourmaline ball with industrial water in a moving or stored state. The present invention also relates to a method for preventing corrosion of an iron or iron alloy container or pipe, which comprises contacting the tourmaline ball with industrial water in a moving or stored state in a container formed of iron or an iron alloy. There is also.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the tourmaline ball of the present invention are described below.

(1) The average particle size ratio between the tourmaline fine particles and the inorganic insulating fine particles is 0.2
To 5 in the range. (2) The average particle size ratio of the tourmaline fine particles to the inorganic insulating fine particles is in the range of 0.5 to 2 for the former and 1 for the former. (3) The diameter of the tourmaline fine particles is in the range of 1 to 50 μm. (4) The diameter of the tourmaline fine particles is in the range of 3 to 30 μm.

(5) The weight ratio of tourmaline fine particles to inorganic insulating fine particles is in the range of 0.2 to 5 for the former and 1 for the latter. (6) The inorganic insulating fine particles are clayey fine particles. (7) The particle diameter of the inorganic insulating fine particles is in the range of 1 to 50 μm. (8) The particle diameter of the inorganic insulating fine particles is in the range of 3 to 30 μm. (9) An inorganic adhesive component is a vitreous material that melts in the range of 600 to 950 ° C., or a reaction product or decomposition product thereof. (10) The compressive strength of the tourmaline ball is 15 kg or more (particularly 20 kg or more, the average value of the compressive strength of each tourmaline ball). (11) The average diameter of the tourmaline ball is in the range of 2 to 15 mm, preferably 4 to 15 mm, particularly 4 to 10 mm.

FIG. 1 shows a conceptual diagram of the internal structure of a tourmaline ball (globular tourmaline mass) 10 of the present invention.
FIG. 1 shows a partially enlarged internal structure of the tourmaline ball. In FIG. 1, a hatched circular portion 11 represents a cross section of tourmaline fine particles. A plurality of adjacent tourmaline fine particles 11 are spatially separated from each other by inorganic insulating fine particles 12. The tourmaline fine particles 11 and the inorganic insulating fine particles 12 are joined to each other by an inorganic adhesive component 13 such as a vitreous material fixed around the contact point or a close point. Therefore, the surface of the tourmaline fine particles 11 on which the inorganic adhesive component 13 is not disposed is exposed toward the pores. Accordingly, each of the tourmaline fine particles 11 self-polarizes inside thereof and reacts with water, water vapor, or the like in contact with the exposed surface to generate active ions such as hydroxyl ions.

The tourmaline ball of the present invention may be, for example, 600 to 950 of a large number of tourmaline fine particles, a large number of inorganic insulating fine particles, and a weight of 1 to 10% of the total weight of the tourmaline fine particles and the inorganic insulating fine particles. Mixing the inorganic adhesive that melts within a temperature range of 0 ° C., then forming an agglomerate while applying the aqueous organic adhesive solution to the resulting mixture, and heating the agglomerate to 600-950 ° C. It can be advantageously produced by melting the inorganic adhesive or its components while substantially maintaining the shapes of the tourmaline fine particles and the inorganic insulating fine particles, and then cooling.

There are no particular limitations on the fine tourmaline particles that can be used in the production of the tourmaline ball of the present invention. That is, by crushing natural minerals conventionally known as tourmaline or tourmaline, and performing a classification operation to adjust the particle diameter to an appropriate particle size as desired, tourmaline fine particles that can be used in the production of the tourmaline ball of the present invention are obtained. Obtainable. However, the tourmaline fine particles used for producing the tourmaline ball of the present invention are:
The particle size (meaning the average particle size in the present specification) is preferably in the range of 1 to 50 μm, and more preferably 3 to 3 μm.
It is preferably in the range of 0 μm, particularly 5 to 20 μm.
m is preferably in the range.

As the inorganic insulating fine particles, for example,
Inorganic insulator particles such as various clay particles, kaolin, alumina particles, titanium dioxide particles, and talc can be used. The inorganic insulator fine particles to be used do not melt in the firing step at the time of agglomeration after mixing with the tourmaline fine particles, and it is necessary to substantially maintain their own shape. However, its melting point (melting temperature) is generally 700 ° C. or higher, preferably 900 ° C. or higher, and particularly preferably 1000 ° C. or higher.

In order for the inorganic insulating fine particles to realize effective insulation between the adjacent tourmaline fine particles and to maintain the ratio of the exposed surface of the tourmaline fine particles at a suitable level, the particle size of the tourmaline fine particles is required. The ratio of the particle diameter of the inorganic insulating fine particles to the former is preferably in the range of 0.2 to 5 for the former 1, and more preferably in the range of 0.5 to 2 for the former 1. In particular, the former is preferably 0.8 to 1.2 with respect to the former 1.
Is preferably within the range. Therefore, the particle diameter of the inorganic insulator fine particles is preferably in the range of 1 to 50 μm, more preferably in the range of 3 to 30 μm, and particularly preferably in the range of 5 to 20 μm.
The inorganic insulator fine particles are preferably used in an amount of 0.2 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, based on 1 part by weight of the tourmaline fine particles. Preferably, it is used in an amount in the range of 0.7 to 1.5 parts by weight.

In the production of the tourmaline ball of the present invention, in order to realize a strong bonding by point contact between the fine particles of tourmaline and the fine particles of the inorganic insulator, 600 to 600 parts are used.
It is preferable to use an inorganic adhesive such as a vitreous powder (eg, powdered silicate binder) that melts in a temperature range of 950 ° C. In addition, when a large amount of the inorganic adhesive is used, the amount attached to the surface of the tourmaline fine particles increases, and the exposed surface area of the tourmaline fine particles decreases.
1 of the total weight of tourmaline fine particles and inorganic insulator fine particles
Preferably, it is used in an amount in the range of 10% to 10% (particularly 2 to 8%). And, with respect to the tourmaline fine particles, the inorganic adhesive is preferably used in an amount of 0.5 to 5% by weight (particularly, 1 to 4% by weight).

In producing the tourmaline ball of the present invention, first, a large number of tourmaline fine particles, a large number of inorganic insulating fine particles, and a particulate inorganic adhesive are mixed in a dry state, and then tumbled. Using a granulation device such as a granulation device (eg, a bread-type granulator), a spherical mass is formed while applying the aqueous organic adhesive solution to the resulting mixture, for example, in the form of a mist. In this granulation step, the inorganic adhesive particles are mainly localized around the junction or close point between the tourmaline fine particles and the inorganic insulating fine particles. If necessary, tourmaline fine particles, inorganic insulating fine particles, or inorganic adhesive particles may be replenished in the step of forming the massive compact.

The aqueous organic adhesive solution used in the above-mentioned mass production step is self-supporting and can maintain the mass form until the inorganic adhesive is fixed by melting after the start of the subsequent firing step. Aqueous solution of an adhesive for molding, for example, CMC (carboxymethylcellulose)
And a 5 to 10% by weight aqueous solution. It is preferable that the massive compact has a spherical shape with an average diameter of 2 to 15 mm.

The bulk compact obtained in the above step is then placed in a heating furnace, and usually at about 600 to 950 ° C. (preferably about 700 to 950) for about 3 to 15 hours.
° C), and then fired for about 30 minutes to 2 hours, while substantially maintaining the shape of the molded body of tourmaline fine particles and inorganic insulating fine particles, and mainly of tourmaline fine particles and inorganic insulating fine particles. The inorganic adhesive localized around the proximity point is melted or reacted. The fired massive compact is then cooled in the heating, taken out of the heating furnace, and cooled to room temperature to obtain the target tourmaline ball (average diameter is preferably 2 to 15 mm).

The tourmaline ball of the present invention obtained as described above can be packed in a column or a cassette and arranged so as to be interposed in a water distribution system such as tap water. However, the tourmaline ball 10 of the present invention,
In particular, when used for the purification treatment of industrial water, as shown in FIG. 2, a bag formed of a flexible non-conductive synthetic fiber net 21 and a metal ring 22 for maintaining the shape thereof. 3 (opened at both sides, bottom, and top, and the opening ratio is preferably 50% or more, particularly preferably 70% or more), as shown in FIG.
Inside a reservoir (or a water storage tank) 31 storing industrial water, a string 24 attached to a container suspends the suspension from a bridge-like passage 32 bridged above the reservoir 31 in a suspended state. It is desirable to arrange in. Also,
Similarly, as shown in FIG. 3, in a tank for storing industrial water or in a flash tower (cooling tower) 33 for circulating industrial water, etc. Or at the bottom,
It is desirable to arrange it in such a state that it does not flow out. In particular, since the tourmaline ball container 23 placed in a suspended state in a reservoir or a water storage tank sways due to movement of water and changes its position, contact between newly flowing water and the tourmaline ball increases, Solid contaminants such as algae, which are likely to be generated in industrial water, can be effectively prevented from adhering and accumulating on the tourmaline ball surface. Since the tourmaline ball of the present invention has a high compressive strength, the tourmaline ball container is not easily broken even if the swinging of the tourmaline ball container in water is repeated.

If solid contaminants such as algae accumulate on the surface of the tourmaline ball in the tourmaline ball container due to long-term use, a cleaning operation such as grasping and swinging the string of the container is performed. , Solid contaminants can be easily removed.

[0032]

[Example 1-Production of tourmaline ball] 50 parts by weight of fine tourmaline powder (produced in China, purity: about 100%, 325 mesh pass, average particle size: about 7 µm), clay powder (drying of Frogme clay) Powder, 325 mesh pass, average particle size: about 7 μm) 45 parts by weight and sodium silicate powder (low temperature sintered vitreous forming binder) 5 parts by weight,
This mixture was placed in a bread granulator and subjected to rotary granulation. At the time of this rotary granulation, carboxymethylcellulose (CM
C) Aqueous solution (Cellogen WSC (commercial product), concentration: about 7
%) Was appropriately sprayed on the granules to obtain granules.

Next, the obtained granulated product was placed in a heating furnace, heated to 700 ° C. over 8 hours, and then heated and calcined at the same temperature for 1.5 hours. The mixture was allowed to cool for 8 hours. And take it out of the heating furnace,
A spherical tourmaline molded body was obtained. The resulting tourmaline molded body is agglomerated by a large number of tourmaline fine particles, the clay powder being interposed between the tourmaline fine particles, and the tourmaline fine particles and the clay powder being fixed to each other in a point contact state by vitreous material. And a porous spherical body (average particle size: 6 mm). In addition, the compressive strength of the obtained porous spherical body (compressive strength of one spherical body (measurement method: a porous spherical body is sandwiched between two steel plates) is pressed at a speed of 1 mm / min. (Measured weight when the body was broken) was about 35 kg.

Example 2 Purification of Industrial Water Using Tourmaline Balls A circulating system for industrial water of a chemical factory, in which a normal anticorrosive is added to the industrial water and circulated for use, The water purification action of the tourmaline ball manufactured in Example 1 was tested for a circulatory system in which a large amount of red rust was generated in the iron portion inside the exchanger.

The tourmaline ball obtained in Example 1 was filled into a synthetic fiber net bag having the structure shown in FIG. 2 and suspended in a reservoir 31 as shown in FIG.
Also, it was arranged at the bottom of the flash tower 33 in a moored state. Then, factory water was continuously passed through the pipe as before. After one month, when the condition inside the heat exchanger was examined, the red rust disappeared, and the heat exchanger surface was covered with strong black rust (passive film). In addition, if this black rust is formed on the surface of the iron material, further corrosion of the iron material does not easily progress, which is advantageous for long-term use of the piping. Also, the destruction of the tourmaline balls in the tourmaline ball container was extremely small.

Comparative Example 1 A water purification action similar to the water purification action of the tourmaline ball of Example 2 was evaluated by using a spherical body produced by agglomerating a large number of tourmaline fine particles with a glassy insulator. When a tourmaline molded body was used in the same manner, its red rust removing function was hardly observed.

[Comparative Example 2] Evaluation of the water purification action similar to the water purification action of the tourmaline ball of Example 2 was carried out by using a mixture of a large number of tourmaline fine particles and insulating fine particles using a vitreous adhesive. When carried out in the same manner using a spherical tourmaline lumps produced by baking without, after one month, the spherical tourmaline lumps are destroyed,
Most of it spilled out of the container. Also, the red rust removing function was hardly observed.

[0038]

The tourmaline ball of the present invention has high breaking strength, but also has a large exposed area of tourmaline particles, so that the excellent water purification action of tourmaline can be effectively exhibited. Therefore, the tourmaline ball of the present invention is advantageously used particularly for purification of industrial water (particularly, rust prevention of iron pipes and tanks that come into contact with industrial water). However, it also works effectively for purification of generally clean water such as tap water.

[Brief description of the drawings]

FIG. 1 is a view schematically showing an internal structure of a tourmaline ball of the present invention.

FIG. 2 is a tourmaline ball container (a bag-like porous body composed of a flexible non-conductive synthetic fiber mesh and a metal ring) which is advantageously used when the tourmaline ball of the present invention is used for purification treatment of industrial water. FIG. 2 is a perspective view of a (container) (contains tourmaline balls).

FIG. 3 is a schematic diagram showing a state in which a container accommodating the tourmaline balls of FIG. 2 is arranged in an industrial water circulation system so as to come into contact with water.

[Explanation of symbols]

 Reference Signs List 10 tourmaline ball 11 tourmaline fine particles 12 inorganic insulating fine particles 13 inorganic adhesive material 21 non-conductive synthetic fiber net 22 metal ring 23 flexible bag-shaped porous container 24 container string 31 industrial water reservoir 32 bridge-like passage 33 Flash (cooling) tower

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C02F 1/68 520 C02F 1/68 520N 520S 530 530G C23F 15/00 C23F 15/00 F term (Reference) 4G019 FA01 GA01 4K062 AA05 BA14 BA17 DA01 FA02 FA04 FA16 GA10

Claims (14)

[Claims] 1. A large number of tourmaline fine particles, wherein inorganic insulating fine particles are interposed between tourmaline fine particles, and the tourmaline fine particles and the inorganic insulating fine particles are fixed to each other in a point contact state in the presence of an inorganic adhesive component. A tourmaline ball characterized by being agglomerated by the compound to form a porous spherical body. 2. The tourmaline ball according to claim 1, wherein the average particle size ratio of the tourmaline fine particles to the inorganic insulator fine particles is in the range of 0.2 to 5 for the former and 1 for the latter. . 3. The tourmaline ball according to claim 1, wherein the average particle size ratio of the tourmaline fine particles to the inorganic insulating fine particles is in the range of 0.5 to 2 for the former. . 4. A tourmaline fine particle having a particle size of 1 to 50 μm.
The tourmaline ball according to any one of claims 1 to 3, wherein m is in a range of m. 5. The tourmaline fine particles having a particle size of 3 to 30 μm.
The tourmaline ball according to claim 4, wherein m is in a range of m. 6. The tourmaline ball according to claim 1, wherein the weight ratio of the tourmaline fine particles to the inorganic insulating fine particles is in the range of 0.2 to 5 for the former. 7. The tourmaline ball according to claim 1, wherein the inorganic insulator fine particles are clay fine particles. 8. The tourmaline ball according to claim 1, wherein the inorganic adhesive is a vitreous material that melts in the range of 600 to 950 ° C. 9. The tourmaline ball according to claim 1, having a compressive strength of 15 kg or more. 10. The tourmaline ball according to claim 1, which is for water treatment. 11. The tourmaline ball according to claim 10, which is used for water treatment for industrial water. 12. A method for purifying industrial water, comprising bringing the tourmaline ball according to any one of claims 1 to 9 into contact with industrial water in a moving or stored state. 13. Industrial water which is moving or stored in a container made of iron or iron alloy.
10. A method for preventing corrosion of an iron or iron alloy container or piping, which comprises contacting the tourmaline ball according to any one of items 9 to 9. 14. A number of tourmaline microparticles, a number of inorganic insulator microparticles, and an amount ranging from 1 to 10% of the total weight of the tourmaline microparticles and inorganic insulator microparticles of 600.
Mixing an inorganic adhesive that melts within a temperature range of from 950 ° C. to 950 ° C .; forming an agglomerate while applying an organic adhesive aqueous solution to the mixture produced in the mixing step; 2. The tourmaline ball according to claim 1, further comprising a step of melting or reacting the inorganic adhesive while substantially maintaining the shapes of the tourmaline fine particles and the inorganic insulator fine particles by heating the mixture, and then cooling. Manufacturing method.