JP2002167215A - Pearlite ore-based artificial zeolite and industrial materials obtained by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pearlite ore-based artificial zeolite, which is inexpensive, is high in performance, is white in powder and is used in various applications, and provide various industrial materials based on it. SOLUTION: In manufacturing a pearlite ore-based artificial zeolite, a Na ion of a Na type artificial zeolite obtained by treating a pearlite ore with a caustic soda, is replaced with each ion of Fe, Ca, Mg, Cu, Ti, Zn, Al and H or its chelate compound. By mixing a Cu type zeolite, plasters for outside building walls, paints, and antibacterial concrete structures are obtained. By mixing a Ca type artificial zeolite, plasters for inside building walls are obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an artificial zeolite raw material made of pearlite ore, which has a relatively large cation exchange capacity and is inexpensive, safe and versatile, and is obtained by substituting Na with various ions or chelate compounds thereof. White artificial zeolite. Also, the present invention relates to industrial materials (plaster for building outer walls, plaster for building inner walls, paints, antibacterial resins, concrete structures for hydrosphere, and antibacterial concrete structures) using these artificial zeolites.

[0002]

2. Description of the Related Art It has been known that natural, artificial and synthetic zeolites can gradually release exchange ions.
Artificial ones have a larger cation exchange capacity than natural ones and synthetic ones are even larger, but synthetic zeolites are quite expensive and difficult to use frequently as industrial materials. It is also known that activated carbon, silica and the like other than zeolite exhibit the same effect as zeolite. Further, many antibacterial agents are known to be heavy metal and organic.

[0003] As an example of a conventional artificial zeolite,
Fly ash is treated with caustic soda to form a raw material zeolite of Na type, and this raw material is immersed in an aqueous solution of various ions, for example, Fe ions, so that an inexpensive artificial zeolite of iron type can be obtained.

This Fe type artificial zeolite is disclosed in
As shown in 77709, Fe ions can be gradually released by being mixed into a concrete structure. However, fly ash is black and cannot be mixed into stucco or the like, which must be white.

[0005] On the other hand, various antibacterial agents have been developed and are widely used in various household and industrial products. Particularly, heavy metals have been pointed out as having a drawback of polluting the sea and rivers due to their toxicity, and their improvement has been awaited. Is where In addition, in order to use antibacterial agents frequently in various industrial products, there are problems of price, properties, and color.For example, development of antibacterial agents that can be used safely and effectively in industrial products such as cement is needed. This is where you can wait.

[0006] Specifically, according to the damage reports of 67 municipalities nationwide, hydrogen sulfide adheres to concrete walls of sewage systems and is converted to sulfuric acid by aerobic bacteria in the air. Some concrete walls have collapsed or holes have been drilled in the underground sewer pipes. It is clear that an antibacterial agent should be mixed into the cement, but there is no antibacterial agent that can be adapted due to toxicity and other problems. Also,
The use of organic salts and heavy metal-based paints has been banned as ship bottom paint, but no alternative antibacterial paint has been developed yet. In addition, shellfish and seaweed adhere to the fishing nets and seawalls, causing damage to their functions. However, the actual situation is that no measures have been taken.

[0007] In addition, the plaster white walls frequently used in various buildings are damaged by mold by rainwater or other moisture, and the color is darkened and unsanitary. In addition, aquatic plants are not sufficiently prosperous in fish reefs, and the habitat of fish and shellfish has not been sufficiently raised.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a powdery, white artificial zeolite which can be manufactured at low cost, has a large cation exchange capacity, and can be widely used for industrial purposes.

The artificial zeolite thus obtained is used for various industrial materials (plasters, paints, daily necessities, concrete structures) by defining ions as an antibacterial material, a moisture adjusting material, and a nutritional supplement, and its functions are expanded. , To preserve.

[0010] Specifically, in the plaster for the building outer wall,
It is an object of the present invention to provide a plaster for an outer wall that can keep mold white by maintaining the coordination of whiteness, suppressing the growth of mold, stopping the growth of mold even by absorbing rainwater or the like, and maintaining the whiteness and strength permanently.

[0011] In a plaster for a building inner wall, a respiratory inner wall that deodorizes formalin, formaldehyde and other organic odors generated from new building materials and the like, absorbs excess moisture in the room, and supplies it during periods of insufficient moisture. The purpose is to provide stucco for use.

It is an object of the present invention to provide a paint that can be used as a ship bottom paint and other antibacterial coating agents by imparting antibacterial properties to paints with minimum toxicity.

[0013] An object of the present invention is to provide an antibacterial resin such that a fishing net is formed by mixing the resin into polyester, for example, and a shell or algae does not adhere to the fishing net.

It is an object of the present invention to provide an aquatic concrete structure capable of appropriately supplying a required nutrient source to aquatic plants such as algae, such as a fish reef.

Another object of the present invention is to provide an antibacterial concrete structure which minimizes toxicity, does not naturally elute to the outside, and does not adhere to aerobic bacteria or the like. I do.

[0016]

SUMMARY OF THE INVENTION In order to solve the above problems, the present invention provides a powdery, white Fe, Ca, Mg, Cu, Ti, Zn, Al, H type powder as described in the claims. An artificial zeolite and an industrial material (plaster, paint, antibacterial resin, concrete structure) using the same were configured.

The artificial zeolite (hereinafter referred to as "parazeo") using the pearlite of the present invention as a raw material is prepared by treating a pearlite ore with caustic soda to form a Na-type parazeo (cation exchange capacity CEC 450 to 480). Na
The ions are obtained by substituting ions with ions such as Fe, Ca, Mg, Cu, and Ti (hereinafter referred to as service ions). The obtained parazeo is white with a particle size of 0.3 to 0.03 μm and does not change its color even when added to various materials. However, Cu-type parazeo is slightly brown. That is, in the parazeo of the present invention, the raw material itself is inert,
Including cement, paint, resin and other industrial materials,
It can be used for various colors as well as white.

The Fe, Ca, and Mg types can be used when such components are provided to the object as nutrients.
The Cu type has a strong antibacterial action and can be applied to an object for which it is desired to suppress the occurrence of mold and plants. Ti can be used as a catalyst to decompose PCBs and dioxins. Zn and Al types can prevent the whitening phenomenon of concrete. Type H can be used for soil improvement.

The plaster for building exterior walls of the present invention is prepared by mixing Cu-type parazeo at a ratio of 1 to 15, preferably 3 to 10, more preferably 5 to 8 parts by weight with respect to 100 parts by weight of slaked lime. It is kneaded with water together with straw and other connecting materials, and is used as a white wall for castles, houses, and doors. The finished wall is white, and by the antibacterial action of Cu-type parazeo, the growth of mold and aerobic bacteria can be suppressed, and the whiteness and strength can be made permanent for many years.

The plaster for the inner wall of the building according to the present invention is obtained by adding Ca-type parazeo to 5 to 30 preferably 1 to 100 parts by weight of slaked lime.
It is mixed with water at a ratio of 0 to 25, more preferably 12 to 20 parts by weight, and is kneaded with water together with a binding material such as seaweed and straw, and is finished with a white wall. The Ca-type parazeo has a function of absorbing gas such as formalin and formaldehyde and a function of adjusting moisture, and can absorb odors and harmful gases generated from new building materials and the like to suppress the occurrence of atopy and allergy. In addition, it absorbs the moisture of the humid air from the rainy season, prevents condensation on the wall surface, and can supply water during the dry season to improve the indoor environment.

The paint of the present invention contains Cu-type parazeo in a proportion of 0.5 to 10, preferably 3 to 8, more preferably 4 to 7 parts by weight per 100 parts by weight of solids in various paints. Things. As the paint, it can be applied to each color except aquatic, oily, rubber, coating agent, and transparent, and is particularly effective for ship bottom paint. In ship bottom paints, Cu ions do not naturally elute into the sea, but if seaweed attaches and absorbs Cu ions, it releases Cu ions accordingly. Don't worry.

The antibacterial resin of the present invention comprises a Ca-type parazeo,
0.5 to 10 for 100 parts by weight of various resins including rubber,
It is preferably mixed at a ratio of 3 to 8, more preferably 4 to 7 parts by weight. According to this antibacterial resin, it has an antibacterial action, does not naturally release toxic Cu ions,
If bacteria such as molds are generated and the Cu ions are released by the absorbed amount, they can be used for various types without deteriorating the environment. For example, when used for a rubber seal of a refrigerator door, a black mold does not occur and a clean seal can be realized. In addition, when used for a polyester fishing net, for example, seaweed and shellfish do not adhere, and the algae removal operation that is performed once a year becomes unnecessary.

The concrete structure for hydrosphere of the present invention is
e, Ca, Mg-type parazeo mixed at a rate of 5 to 30 parts by weight with respect to 100 parts by weight of cement as a whole, determined in proportion to the hydrosphere conditions (separation of sea, river, eutrophication) It is. Concrete structures, such as fish reefs, whose nutrient sources are determined in this way, gradually release various ions, promote the adhesion of seaweed and diatoms, grow and prosper, and create an environment suitable for the growth of fish and shellfish. Can be. Since the CEC is slightly more than 2.5 times higher than that of the conventional fly ash artificial zeolite, the mixing ratio can be reduced to half or less.

[0024] The antibacterial concrete structure of the present invention comprises C
u-type parazeo is added in an amount of 0.5 to 100 parts by weight of cement.
15, preferably 3 to 15, more preferably 4 to 10 parts by weight, and kneaded with water together with the aggregate to form a concrete structure. Since this concrete structure has antibacterial properties and can prevent plant adhesion, it can be frequently used for concrete structures in roads, sewage corrugates, concrete walls of sewage treatment plants, tunnel walls, and the like. In addition to simply maintaining the appearance, corrosion and collapse due to sulfuric acid gas or sulfuric acid can be prevented, and strength can be maintained.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Parazeo is produced as follows. First, pearlite ore produced in the Kyushu region and Yamagata prefecture is sintered at 600 to 800 ° C. and crushed to obtain a powder material having a particle size of 0.03 to 0.3 μm. This powder material is sieved to make the powder diameter uniform, then immersed in caustic soda of 1 to 5 N, and subjected to a stirring treatment in an autoclave at a temperature of 50 to 150 ° C. and a pressure of 1 to 5 atm for 30 to 120 minutes. By this stirring process, Na ions are bonded to the ore surface, and Na-type parazeo is generated. The particle size can be further reduced by changing the pulverization method or using a ball mill.

After completion of the autoclave treatment, the mixture is rapidly quenched so that the CEC does not decrease by the subsequent reaction, washed with water, and dried to produce a white Na-type artificial zeolite having a predetermined particle size (raw material parazeo). . The ion exchange capacity of the parazeo thus obtained is 450-700 CEC.

[0027] The obtained raw material parazeo contains various ions F
It can be ion-converted with e, Ca, Mg, Zn, Al, H, Cu, Ti or a chelate compound thereof. In this ion conversion, an aqueous solution containing each ion, for example, Fe ₂ CL ₃ , C
aCl, MgCl, CuSO ₄ titanium chloride or an aqueous solution of a citric acid compound which is a chelate compound thereof is 20 to
By immersing, washing with water, and drying at 60 ° C. under normal pressure for several hours, for example, 3 hours, parazeo of each ion type can be produced.

The thus-obtained parazeo exhibits a sustained ion release characteristic as shown in FIG. 1 and FIG. FIG. 1 is a diagram showing, for example, the sustained release characteristics of Fe-type parazeo 1 in water mixed in a concrete structure for aquatic water in comparison with other contaminants (iron oxide 2, pure iron 3). FIG. 2 shows the sustained release characteristics when Fe type or Cu type parazeo is left in the air. The dashed line shown in FIG. 1 indicates the appropriate amount of ion release that is normally required by seaweeds.

As shown in FIG. 1, the Fe ions in water are sharp for pure iron 3, then fast for iron oxide 2, and slow for Fe-type parazeo. This sustained release property is that, when a nutrient absorption site of an aquatic plant such as a seaweed or a diatom contacts the Fe ion carried on the Fe adsorption carrier, the ion is converted into a hydrogen ion secreted from this site and released, and the aquatic plant Is absorbed by
Unless iron is absorbed by plants, almost no iron ions are released, so that an excess amount of Fe is not released into the sea. This is the principle of sustained release of parazeo. Therefore, as shown in FIG. 2, the amount of released ions of Fe and other ions, for example, Cu-type parazeo 4 in natural standing is almost zero unless an ion-converting substance in the air acts, deteriorating the environment. Nothing.

Next, Fe, C produced as described above
Examples of application to various industrial materials using a, Mg, Cu, Zn, Al, H, Ti type and other parazeo are stucco for building outer walls, stucco for building inner walls, paint, antibacterial resin, concrete structures for aquatic environments, Shown in the order of antibacterial concrete structures.

(Plaster for Building Exterior Wall) 7 parts by weight of Cu-type parazeo, seaweed and straw are filled with 100 parts by weight of slaked lime.
Knead with water to make a white wall. The finished wall is pure white.
Usually, the outer wall is hit by rain and collects on the lower surface, where bacteria inhabit and mold grows, darkens, and collapses after a few years. Since the plaster for the outer wall of this example contains Cu-type parazeo, it does not generate mold and has a sustained release of the degree shown in FIG. 2 so that its function can be maintained and the white wall can be preserved for a long time. .

(Plaster for building inner wall) 20 parts by weight of Ca-type parazeo, 100% by weight of slaked lime, seaweed and cotton binder are added, and the mixture is kneaded with water to form a white wall. Plastering may be done closely. Ca-type parazeo has a gas and moisture absorption function. Therefore, the inner wall absorbs harmful gases generated from new building materials such as formalin, cleans the indoor air, and can prevent the occurrence of atopy and other allergic diseases. Also Ca
The type Parazeo has a moisture adjustment function, and can absorb unnecessary moisture such as rainy season and prevent dew condensation. In addition, the absorbed moisture is released during the drying period, and has an effect of keeping the indoor moisture constant. Further, 0.5 to 3 parts by weight of Cu-type parazeo is added,
Mold generation can also be suppressed.

(Paints) As paints, various kinds of paints such as organic solvent-based, aqueous emulsion-based, rubber-based, and coating agent-based can be applied, including adhesives. Since it is intended to have an antibacterial action due to mixing of Cu-type parazeo, it is particularly useful for use in ship bottom paint, which is currently a problem.

In the ship bottom paint, for example, 5 parts by weight of Cu-type parazeo having a particle size of about 0.03 to 0.3 μm is added to 100 parts by weight of the solid content of the paint. Since the eluted ions are slower due to the use in the sea but larger than those in the air, the blending amount is slightly larger. When seaweed species adhere to the paint in the sea and start to absorb nutrients, Cu ions are supplied. This causes the species to refuse it, fall off the bottom of the ship, or die there. As the ship sails, the species are released into the sea. Therefore, nothing is always attached to the bottom of the ship, and the bottom is kept clean.

(Antimicrobial resin) The resin includes a rubber in addition to a temporary plastic material. In the case of a resin, for example, a polyester for producing fishing nets, 5 parts by weight of a Cu-type parazeo having a particle size of 0.03 to 0.3 μm is blended with 100 parts by weight of the polyester. Polyester is hydrolyzed by moisture, but the material to be mixed, especially parazeo, is sufficiently extracted and vacuum-dried. This fishing net made of polyester has an antibacterial effect and, like the bottom paint,
It does not accept seaweeds and shellfish and can be used without adhering dirt for many years.

The same applies to the case of a rubber seal used for a refrigerator door. For 100 parts by weight of rubber, for example, chloroprene, a vulcanizing agent, a filler, etc.
% To make a rubber seal. By using white carbon as the filler, white carbon can be obtained. The rubber seal does not come into contact with food when the door is normally opened and closed, and there is no Cu ion toxicity problem since Cu ions are not naturally left in the air. The generation of mold can be prevented by the effect of Cu ions. The same applies to a resin such as vinyl chloride instead of rubber.

(Concrete structure for hydrosphere) Cement 1
100 parts by weight, 20 parts by weight of Fe, Ca, and Mg type parazeo in a mixing ratio determined according to the hydrosphere conditions, and 100 parts by weight of sand and 150 parts by weight of aggregate, and kneaded with water, To make a reef. The hydrosphere conditions are, for example, Fe: Ca: Mg = 50: 40: 10 in the sea, and Fe: Ca: Mg = 4 in freshwater in consideration of the provision of the insufficient nutrient.
0:30:30. The obtained fish reef gradually releases each ion, so that seaweed or diatoms can proliferate well, and an environment suitable for fish and shellfish can be created. Since Parazeo has a cation exchange capacity 2.5 times more than the artificial zeolite by fly ash, it has more than twice the effect for the same composition, and less than half of the same effect is obtained. Just mix. Although the cost is slightly higher than fly ash at present, it can be mass-produced from pearlite ore, as shown in the Parazeo manufacturing method, and eventually becomes cheaper. For synthetic zeolites it is inexpensive to compare. In addition, the color is not deteriorated even by blending in a large amount.

(Antibacterial concrete structure) Cement 1
3 to 8 parts by weight of Cu-type parazeo are added to 00 parts by weight, and 100 parts by weight of sand and 150 parts by weight of gravel are added to the mixture, and the mixture is kneaded with water. Make a concrete structure.

When the concrete structure is a tunnel or a road structure, the amount of the Cu-type parazeo is 5 parts by weight. The toxicity is not a problem at all, the release is not a problem as in underwater use, and the reference amount is sufficient. As shown in the conventional example, in places with a lot of water, aerobic bacteria transform hydrogen sulfide into sulfuric acid and destroy concrete, but since Cu ions prevent bacteria from adhering, they prevent mold and corrosion. The effect of can be exhibited.

When the concrete structure is a concrete wall or a sewage pipe of a sewage treatment plant, the blending amount of Cu-type parazeo is 7 parts by weight. Since there is a portion used in water, the release of Cu ions is relatively large in that portion, and the blending amount was increased in order to obtain a permanent effect. If this composition is too large, there is a concern that Cu ions may elute into water and contaminate it even though it is sewage. However, as shown in FIG. 1, Cu-type parazeo is a sustained release in which Cu ions are released only after some absorber acts, so it is considered that there is no concern about contamination even with a larger formulation. Can be

(Others) When the concrete structure is a flue, by mixing Ti-type parazeo into the concrete constituting the flue, its catalytic action causes
Decomposes CB and dioxin and can drastically reduce it. In addition, when mixed with synthetic fibers, in the case of clothes, harmful substances can be decomposed to maintain skin health.

In the case of Zn and Al type parazeo, by mixing with concrete, it is possible to suppress the whitening phenomenon in which a white substance is produced by the reaction with the reaction.
H-type parazeo can react with alkali to neutralize alkaline soil and alkaline solutions. The feature of this example is that the neutralization can be carried out moderately and slowly.

The present invention is not limited to the above-described embodiment, but can be implemented in various forms with various modifications by making appropriate design changes using ordinary techniques.

[0044]

As described above, the present invention is newly created, and various service ions Fe, Ca, Mg, Cu, Ti, Z
Since it is an artificial zeolite made of pearlite in the form of a white powder and loaded with n, Al, and H, it can be widely used for various purposes while expanding and maintaining its functions in various industrial materials.

In the plaster for the building outer wall, the mixing of Cu-type parazeo does not impair the whiteness, can prevent the growth of mold, and can maintain its whiteness and strength for many years.

The plaster for the inner wall of the building can absorb harmful gas, adjust moisture, and keep the indoor environment healthy by mixing Ca-type parazeo.

The paint can exhibit a slow-release antibacterial action by the incorporation of Cu-type parazeo. In particular, in the case of ship bottom paint, the adhesion of algae and shellfish can be prevented.

The resin can exhibit a slow-release antibacterial action by mixing with Cu-type parazeo. For example, in a fishing net made of polyester, adhesion of algae and shellfish can be prevented. Mold can be prevented while maintaining hygiene and safety.

For hydrosphere concrete, Fe, C
a, By mixing Mg-type parazeo, it is possible to appropriately supply nutrients to aquatic plants, promote their attachment and prosperity, and create an environment suitable for the growth of fish and shellfish.

In the concrete structure, by mixing Cu-type parazeo, the sustained release of Cu ions can prevent hygroscopic and invasive bacteria while maintaining hygiene and safety. And a durable concrete structure.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing the sustained release characteristics of ions of parazeo of the present invention and the release characteristics of each component.

FIG. 2 Fe or Cu in the air of the parazeo of the present invention
It is explanatory drawing which shows the emission characteristic of an ion.

[Explanation of symbols]

1 Slow release characteristics of Fe-type parazeo in water in the present invention 2 Iron release characteristics of iron oxide as a comparative example 3 Iron release characteristics of pure iron as a comparative example 4 Slow air release of Fe or Cu-type parazeo of the present invention Characteristic

────────────────────────────────────────────────── ─── of the front page continued (51) Int.Cl. ⁷ identification mark FI theme Court Bu (reference) C09D 5/14 C09D 5/14 201/00 201/00 E04F 13/02 E04F 13/02 a F -term (reference 4G012 PA03 PA04 PA22 4G073 BA02 BA10 BA11 BA20 BA36 BA48 BA52 BA57 FB30 FD08 UB07 4H011 AA02 BA01 BB18 BC18 DA23 4J038 HA466 NA05 PB07

Claims (7)

[Claims] 1. A Na-type artificial zeolite produced by treating a pearlite ore with caustic soda as a raw material, and Na in the raw material is converted to Fe, Ca, Mg, Cu, T
Powdery, white artificial zeolite obtained by substituting with ions of i, Zn, Al, H or a chelate compound thereof. 2. A plaster for building exterior walls, characterized in that the Cu-type artificial zeolite obtained in claim 1 is mixed at a ratio of 2 to 15 parts by weight with respect to 100 parts by weight of slaked lime. 3. A plaster for building interior walls, wherein the Ca-type artificial zeolite obtained in claim 1 is mixed in a ratio of 5 to 30 parts by weight with respect to 100 parts by weight of slaked lime. 4. The paint of claim 1, wherein the Cu-type artificial zeolite obtained in claim 1 is used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of a solid part.
A paint characterized by being mixed in parts by weight. 5. An antibacterial resin, wherein the Cu-type artificial zeolite obtained in claim 1 is mixed at a ratio of 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin. 6. A concrete structure for hydrosphere wherein at least one of the Fe, Ca, and Mg type artificial zeolites obtained in claim 1 is mixed in a ratio of 5 to 30 in total with respect to 100 parts by weight of cement. object. 7. An antibacterial concrete structure wherein the Cu-type artificial zeolite obtained in claim 1 is mixed at a ratio of 0.5 to 20 with respect to 100 parts by weight of cement.