JP2001321783A - Industrial water-cleaning method and corrosionproof method for industrial water circulating system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrial water-cleaning method capable of being advantageously utilized in industrial water cleaning work (especially, the corrosionproof work of a metal part forming a water flow channel), and provide a corrosionproof method for an industrial water circulating system. SOLUTION: In the industrial water-cleaning method and the corrosionproof method for the industrial water circulating system, a tourmaline molded object containing a large number of tourmaline fine particles and an inorganic insulating material is housed in a flexible non-conductive bag-like container with an opening ratio of 50% or more (especially 70% or more) and the bag-like container is suspended in the industrial water circulating system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying industrial water using a tourmaline mass formed by agglomerated tourmaline (an tourmaline) and a method for preventing corrosion of an industrial water circulation system.

[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, industrial water purification work has been realized by using chemicals. However, industrial water containing chemicals is difficult to maintain its purification effect.
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 research of the present inventors, the purification of industrial water is carried out by storing tourmaline particles or a tourmaline molded body as disclosed in the above-mentioned patent publications in a cartridge or a metal basket. (Especially, when used for anticorrosion work such as the action of preventing red rust, the effect was found to be weak. 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 easily broken in a short period of time, and the tourmaline particles tended to dissipate.

Accordingly, a main object of the present invention is to make use of the self-polarizing property of tourmaline in a tourmaline bulk molded body and to advantageously purify industrial water (in particular, anticorrosion work of a metal portion forming a water passage). An object of the present invention is to provide a method for purifying industrial water that can be used, and a method for preventing corrosion of an industrial water circulation system.

[0013]

According to the present invention, a tourmaline molded article containing a large number of tourmaline fine particles and an inorganic insulator is formed into a flexible non-conductive bag having an opening ratio of 50% or more (particularly 70% or more). A method for purifying industrial water, wherein the method is contained in a container, and the bag-shaped container is suspended in a circulation system for industrial water. The bag-like container used in the method for purifying industrial water of the present invention preferably comprises a bag made of a non-conductive synthetic fiber net and a metal ring having a function of retaining the shape thereof, and It is preferable that a string for suspension is attached to the container. And the side of the bag-like container,
Preferably, both the top surface and the bottom surface are in a mesh.

The tourmaline molded article used in the method for purifying industrial water of the present invention is characterized in that 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 have an inorganic adhesive component. It is desirable to form a spherical tourmaline mass (tourmaline ball) which is agglomerated by being fixed to each other in a point-adhesion state in the presence of a to form a porous spherical body.

According to the present invention, a porous tourmaline molded body containing a large number of tourmaline fine particles and an inorganic insulator is housed in a flexible non-conductive bag-like container having an opening ratio of 50% or more.
A method for preventing corrosion of an industrial water circulation system (for example, a circulation system in which at least one of a pipe and a tank is made of iron or an iron alloy material) characterized by suspending the bag-like container in an industrial water circulation system. There is also.

The bag-like container used in the method for preventing corrosion of an industrial water circulation system according to the present invention comprises a bag made of a non-conductive synthetic fiber net and a metal ring having a function of maintaining its shape. Preferably, the bag-shaped container is provided with a hanging string. And it is preferable that all of the side surface, the top surface, and the bottom surface of the bag-like container are in a net shape.

The tourmaline molded article used in the industrial water circulation anticorrosion method of the present invention also comprises a large number of tourmaline fine particles.
Inorganic insulator fine particles are interposed between tourmaline fine particles,
And a spherical tourmaline molded body (tourmaline ball) that forms a porous spherical body by being agglomerated by fixing the tourmaline fine particles and the inorganic insulating fine particles to each other in a point bonding state with an inorganic adhesive. Is preferred.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS There are no particular restrictions on the form of tourmaline used for carrying out the method for purifying industrial water and the method for preventing corrosion of a circulating system of industrial water according to the present invention. Mixing the insulating fine particles and an inorganic adhesive that melts within a temperature range of 600 to 950 ° C. in an amount of 1 to 10% of the total weight of the tourmaline fine particles and the inorganic insulating fine particles; Forming a lump while applying the organic adhesive aqueous solution to the resulting mixture;
By heating 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 produced using a method including a step of cooling. The porous spherical tourmaline molded body (tourmaline ball) described above is desirable.

Preferred embodiments of the above tourmaline ball are described below. (1) The average particle size ratio between the tourmaline fine particles and the inorganic insulating fine particles is in the range of 0.2 to 5 for the former and 1 for the latter. (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 the tourmaline ball (globular tourmaline mass) 10 described above. 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. And
The tourmaline fine particles 11 and the inorganic insulating fine particles 12
They are joined to each other by a vitreous or other inorganic adhesive component 13 fixed around the contact point or the proximity 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.

There are no particular restrictions on the fine particles of tourmaline that can be used for the production of the above-mentioned tourmaline balls, provided that they are porous tourmaline molded bodies containing fine particles of tourmaline and an inorganic insulator. That is, by crushing a natural mineral known as tourmaline or tourmaline for a long time, and performing a classification operation to adjust the particle diameter to an appropriate particle size as desired, to obtain tourmaline fine particles that can be used in the production of the above tourmaline ball. be able to.
However, the tourmaline fine particles used in the production of the above tourmaline ball preferably have a particle size (mean an average particle size in the present specification) of 1 to 50 μm,
It is more preferably in the range of 3 to 30 μm, and particularly preferably in the range of 5 to 20 μm.

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 achieve effective insulation between 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 insulating 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 above tourmaline ball,
In order to realize strong bonding by point contact between the tourmaline fine particles and the inorganic insulating fine particles, 600-95
It is preferable to use an inorganic adhesive such as a vitreous powder that melts in a temperature range of 0 ° C. (eg, powdered silicate binder). 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.Therefore, the inorganic adhesive is made up of the total weight of the tourmaline fine particles and the inorganic insulator fine particles. 1 to 1
Preferably, it is used in an amount in the range of 0% (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,
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, respectively, and then a tumbling granulator (eg, a bread granulator) or the like is used. Using a 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).

In the method of purifying industrial water or the method of preventing corrosion of the industrial water circulation system according to the present invention, a flexible non-conductive synthetic fiber net 21 as shown in FIG. It is housed in a bag-shaped porous container 23 formed from the metal ring 22 (the side, the bottom, and the top are both open, and the opening ratio is preferably 50% or more, particularly preferably 70% or more). As shown in Fig. 3, a reservoir (or water storage tank) storing industrial water
31 and the like, by the string 24 attached to the container,
It is preferable to hang and suspend the bridge-like passage 32 bridged on the upper part of the reservoir 31 to carry out.

As shown in FIG. 3, the bag-shaped porous container 23 filled with the tourmaline molded body is provided with a tank for storing industrial water or a flash tower (cooling) for circulating industrial water. Similarly, in the inside of the (tower) 33, it is also possible to arrange them in a suspended state inside them or in a state where they are fixed to the bottom so as not to flow out. In particular, 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, so that the contact between newly flowing water and the tourmaline ball increases, and Solid contaminants such as sludge and algae which are likely to be generated in industrial water can be effectively prevented from adhering and accumulating on the tourmaline ball surface.

When solid contaminants such as sludge and 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 the container string and rocking the container is performed. By
Solid contaminants can be easily removed.

[0033]

[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 is 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 plant, in which a normal anticorrosive is added to the industrial water and circulated for use, For the circulation system in which a large amount of red rust was generated in the iron part inside the exchanger, the tourmaline balls manufactured in Example 1 were filled into a synthetic fiber net bag-shaped container having the structure shown in FIG. Then, as shown in FIG.
1 and was moored at the bottom of the flash tower 33. 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. There was very little destruction of the tourmaline balls in the tourmaline ball container, and there was little adhesion of solid contaminants such as sludge and algae.

[Comparative Example 1] A spherical tourmaline molded body produced by agglomerating a large number of tourmaline fine particles covered with a glassy insulator was placed in a stainless steel basket-like container, and allowed to stand on the floor of a reservoir. When a water purification action similar to that of the tourmaline ball of Example 2 was evaluated, almost no red rust removal function was observed. Also,
It was confirmed that a large amount of sludge was attached around the spherical tourmaline molded product filled in the basket-like container.

[0037]

According to the present invention, a porous tourmaline molded article containing a large number of tourmaline fine particles and an inorganic insulator is provided.
By storing the bag in a flexible non-conductive bag having a high opening ratio and suspending the bag in an industrial water circulation system, purification of industrial water and corrosion prevention of the industrial water circulation system can be effectively performed. This realizes less adhesion of solid contaminants such as sludge and algae to the porous tourmaline molded article, and also reduces the destruction of the porous tourmaline molded article. Furthermore, even when solid contaminants adhere to the porous tourmaline molded article due to long-term use, the solid contaminants can be easily removed by shaking the bag-like container in water.

When the above-mentioned tourmaline ball is used for the treatment of industrial water of the present invention, since the exposed area of the tourmaline particles is large while having high breaking strength, the excellent water purification action of tourmaline can be effectively used. Be demonstrated.

[Brief description of the drawings]

FIG. 1 is a diagram schematically showing an internal structure of a tourmaline ball advantageously used in the present invention.

FIG. 2 is a perspective view of a tourmaline ball container (a bag-shaped porous container composed of a flexible non-conductive synthetic fiber net and a metal ring) (a tourmaline ball is housed therein) which is advantageously used in the present invention. Is).

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) C23F 15/00 C23F 15/00

Claims (13)

[Claims] 1. A tourmaline molded body containing a large number of tourmaline fine particles and an inorganic insulator is accommodated in a flexible non-conductive bag-like container having an opening ratio of 50% or more, and the bag-like container is circulated for industrial water. A method for purifying industrial water, wherein the method is suspended in a system. 2. The bag-shaped container according to claim 1, wherein the bag-shaped container comprises a bag made of a non-conductive synthetic fiber net and a metal ring having a function of retaining the shape thereof. Industrial water purification method. 3. The method for purifying industrial water according to claim 1, wherein a hanging string is attached to the bag-like container. 4. The method for purifying industrial water according to claim 1, wherein an opening ratio of the bag-shaped container is 70% or more. 5. The method for purifying industrial water according to claim 1, wherein all of the side surface, the top surface, and the bottom surface of the bag-like container are formed in a net shape. 6. The tourmaline molded article is obtained by forming a large number of tourmaline fine particles with inorganic insulating fine particles interposed between the tourmaline fine particles, and forming the tourmaline fine particles and the inorganic insulating fine particles in a point-adhered state in the presence of the inorganic adhesive component. The industrial water purification method according to any one of claims 1 to 5, wherein the spherical tourmaline mass is formed into a porous spherical body by being agglomerated by being fixed to each other. 7. A porous non-conductive bag-like container having an opening ratio of 50% or more is accommodated in a porous tourmaline molded body containing a large number of tourmaline fine particles and an inorganic insulator. A method of preventing corrosion of a circulating system of industrial water, wherein the method is suspended in a circulating system. 8. The method for preventing corrosion of an industrial water circulation system according to claim 7, wherein the bag-like container comprises a bag made of a non-conductive synthetic fiber net and a metal ring. . 9. The method for preventing corrosion of an industrial water circulation system according to claim 7, wherein a hanging string is attached to the bag-like container. 10. The method for preventing corrosion of an industrial water circulation system according to claim 7, wherein an opening ratio of the bag-shaped container is 70% or more. 11. The bag-like container according to claim 7, wherein all of the side, top and bottom surfaces are net-shaped.
The method for circulating corrosion protection of industrial water according to any one of the above items. 12. The apparatus according to claim 7, wherein at least one of the pipe and the tank is made of iron or an iron alloy material.
12. The method for preventing corrosion of a circulating system of industrial water according to any one of items 11 to 11. 13. A tourmaline molded body, wherein 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 bonding state with an inorganic adhesive. The method for preventing corrosion of a circulating system of industrial water according to any one of claims 7 to 12, wherein the method is a spherical tourmaline molded body which is formed into a mass by forming a porous spherical body.