JPH08157314A - Biocide - Google Patents

Abstract

PURPOSE: To obtain a biocide effective for inhibiting microorganisms and malodor caused by excreta of pets in sand pools in a park, etc. CONSTITUTION: This biocide is produced by mixing coal ash and/or used lime- based exhaust gas-treating agent with one of compound selected from the group consisting of hydrated lime, quick lime, gypsum and volcanic ash, hydrating and curing the mixture to obtain CaO, CaSO4 , Al2 O3 , SiO2 -based cured compound, and treating the cured compound with a sulfur dioxide-containing gas and further with an aqueous solution of at least one water-soluble antimicrobial metallic compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biocide, and more particularly to a biocide useful for controlling various germs caused by pet excrement and the like.

[0002]

2. Description of the Related Art In a sandbox in a park or the like, harmful microorganisms are generated due to excretions of pets, etc., and an offensive odor caused by the generation of these microorganisms is a problem in terms of environmental hygiene. However, for example, as a countermeasure against microorganisms generated in a sandbox, the present situation is that all or a part of the sand is replaced or expensive and transient disinfectant is sprayed, and there is still no good method. Therefore, a safe and inexpensive biocide that is easy to handle, has a high killing effect, and has a long-lasting effect is desired.

[0003]

The present invention has been made in order to meet the above-mentioned demand, and is an economical, sustainable, and safe biocide targeting harmful microorganisms generated by feces and the like of pets. It is intended to provide an agent, a method for producing the same, and a method for using the same.

[0004]

Means for Solving the Problems As a result of various studies to achieve the above object, the inventors have surprisingly found that a lime-based composition which the inventors have already developed as a flue gas treatment agent is used for flue gas treatment. It has been found that the activity after being subjected to is bactericidal, and by adsorbing the water solubility of a metal compound known to be conventionally bactericidal to this, its activity can be effectively utilized for a long period of time. Completed the invention.

That is, the present invention is: CaO, CaSO ₄ , Al ₂ O ₃ obtained by mixing at least one selected from the group consisting of slaked lime, quick lime, gypsum, and volcanic ash with a coal ash and / or a used lime-based exhaust gas treatment agent and hydration hardening A biocide obtained by treating a SiO ₂ -based cured product with a gas containing sulfurous acid gas. CaO, CaSO ₄ , Al ₂ O ₃ obtained by mixing at least one selected from the group consisting of slaked lime, quick lime, gypsum, and volcanic ash with a coal ash and / or a used lime-based exhaust gas treatment agent and hydration hardening _{2. A} biocide obtained by treating a SiO ₂ -based cured product with a gas containing sulfurous acid gas and further treating it with an aqueous solution containing at least one water-soluble antibacterial metal compound. 3. The biocide according to 2 above, wherein the antibacterial metal compound is a salt of at least one metal selected from silver, copper, zinc, and nickel. CaO, CaSO ₄ , Al ₂ O ₃ obtained by mixing at least one selected from the group consisting of slaked lime, quick lime, gypsum, and volcanic ash with a coal ash and / or a used lime-based exhaust gas treatment agent and hydration hardening , SiO ₂ hardened material is treated with a gas containing sulfurous acid gas, and a predetermined amount of an aqueous solution containing at least one water-soluble antibacterial metal compound is sprayed and absorbed and left in the air, and then the surface is dried. 4. A method for producing a biocide, characterized in that water is added until 5. The method for producing a biocide according to 4 above, wherein the antibacterial metal compound is a salt of at least one metal selected from silver, copper, zinc, and nickel; A method for cleaning and maintaining a sandbox, wherein 5 kg to 50 kg of the biocide according to claim 1 or 2 is sprayed and stirred per 1 m ² of surface area of the sandbox.

The coal ash used in the present invention is produced by the combustion of coal, and the kind of coal and the combustion method are not particularly limited. Here, the used lime-based exhaust gas treating agent is a used calcium-based desulfurizing agent produced from CaO, Ca (OH) ₂ , CaCO _3, etc., and JP-A-61-209038 and JP-A-63-1038. 283745
Etc., such as CaO, Al ₂ O ₃ , SiO ₂ , CaSO ₄
A desulfurization agent that has been used, such as a system composition, is used. C
Table 1 shows an example of the names and analysis values of materials that can be used as a raw material for a desulfurizing agent composed of aO, Al ₂ O ₃ , SiO ₂ , and CaSO ₄ compositions.

[0007]

[Table 1] A preferred combination of these raw materials is at least one combination selected from the group consisting of coal ash and / or a used lime-based exhaust gas treating agent and slaked lime, quick lime, gypsum and volcanic ash. Hydration hardening (described later) by mixing these raw materials
As a result, a CaO, CaSO ₄ , Al ₂ O ₃ , and SiO ₂ type cured product is obtained.

In the present invention, the hydration hardening means that water is added to the raw material mixture to carry out a hydration treatment for hardening, and specifically, it is the following treatment. Hydration treatment is described in, for example, JP-A-6
As disclosed in 4-38130, it refers to a treatment necessary to promote the hydration reaction between the above-mentioned substances (raw materials), and includes, for example, wet air curing, hot water curing, steam curing and the like. In the treatment, the mixing ratio (solid-liquid ratio) of the raw materials and water is set to be small, for example, 1: 0.2 to 1: 0.99 to promote bonding between the material particles and obtain a cured product. If necessary, it can be performed in two steps. Wet air curing in the curable hydration treatment is performed at a temperature of 10 ° C to 40 ° C.
Relative humidity of 50% to 100%, preferably for several minutes or several tens of days, and steam curing is performed at a temperature of 40 ° C to 180 ° C.
It is preferable that the relative humidity is 100% for several minutes to several days.

The cured product thus obtained can be dried, conditioned, crushed or further shaped.
Crushing of hardened material which is wet or dried, compression molding of crushed material and dried material of slurry-like substance are generally used for mulmelizer, disk pelleter, briquette machine, tablet molding machine, extrusion molding machine and others. It can be performed by a pressure formable device.

The biocide of the present invention can be obtained by treating the above cured product with a gas containing sulfurous acid gas (abbreviated as SO ₂ treatment). SO ₂ treatment is performed with SO ₂ of 10
A gas containing 0 ppm to 90% at a temperature of 80 ° C to 500 ° C,
The treatment may be performed at SV of 5 to 50,000 h ⁻¹ for a time sufficient to bring at least 1 mol of SO ₂ into contact with 1 Kg of the cured product.

CaO, CaSO ₄ , Al ₂ O ₃ , SiO ₂
The respective component ratios in the system cured product and the cured product after SO ₂ treatment are CaO 2 to 8% CaSO ₄ 0.1 to 70% Al ₂ O ₃ 5 to 70% SiO ₂ 5 to 80%. In addition, the safety was confirmed by performing an acute oral toxicity test, an acute dermal toxicity test, a skin irritation test, an eye mucous membrane irritation test, etc. of the cured product after SO ₂ treatment.

Since the cured product of the present invention before the SO ₂ treatment has the composition of a known lime-based exhaust gas treating agent, it has a desulfurization ability. Not only can it be used as a biological agent, it can also be used as a deodorant as disclosed in JP-A-4-176466. Therefore, in this case, an extremely economical biocide having deodorizing ability can be provided.

The biocide of the present invention can be used as a powdery material, a granular material or a molded material by a known method depending on the object of application.

The SO ₂ -treated cured product is treated with an aqueous solution containing an antibacterial metal ion that dissociates from salts of at least one metal selected from silver, copper, zinc, and nickel, to obtain nematicidal activity. It is possible to give the effect and to maintain the effect. It was also found that the cured product treated with this aqueous solution also has a deodorizing effect like the cured product before the treatment.

The treatment with the above aqueous solution is as follows: 1. A method in which the cured product is immersed in an aqueous solution of a certain concentration and then dried by heating or left to dry in the air. After spraying a fixed amount of a fixed amount of liquid evenly on the cured product and leaving it in the air to dry, water until the surface becomes dry (water fills the internal space of the cured product but does not adhere to the surface). There is a method of adding and adding the antibacterial metal in the air, and the latter method is preferable in order to add a calculated amount of the antibacterial metal. When the biocide of the present invention is used in a sandbox in a park or the like, it can be handled in the same manner as ordinary sand, and it is mixed with sand before use. The amount used depends on the degree of sand contamination, but the amount that can be used without giving a feeling of strangeness is about 5 kg to about 50 kg per 1 m ² of area (sand depth of about 3
0 cm is 1 to 10% by weight).

[0016]

The present invention will be described below with reference to examples.
The present invention is not limited to this. The parts and% in the text are based on weight. Example 1 To 25 parts by weight of coal ash B shown in Table 1, 35 parts by weight of slaked lime and 40 parts by weight of a used lime-based exhaust gas treating agent were powder-mixed, and 40 parts by weight of water was added to 100 parts by weight of solid content. After kneading and molding, steam curing was carried out for about 15 hours as hydration treatment, and dried to prepare a cured product having a diameter of 6 mm and a length of 10 mm. This was contacted with the exhaust gas at a superficial velocity of 400 h ^{-1 for} about 300 hours and then sized to a particle size of 0.1 to 1.0 mm to obtain a biocide of the present invention.

The composition of the exhaust gas used was SO ₂ 400 p
pm, NO _x 150 ppm, O ₂ 5%, CO ₂ 14%,
The remaining 8% water was N ₂ . Note that about 80% of Ca in the raw material slaked lime was converted to CaSO ₄ by this exhaust gas treatment. To confirm the biocidal activity, tests against bacteria and tests against nematodes were performed. In the test against bacteria, first, 100 mg and 1 g of the above biocide was weighed, mixed with 10 ml of agar medium heated and dissolved, and poured into a 9 cm Petri dish to prepare an agar plate. Next, on this agar plate, E. coli (Sankyo strain) and Bacillus subtilis (B. subtilis ATCC 6633 strain) were added.
Streaks were inoculated respectively, and after culturing at 27 ° C. for 24 hours, the presence or absence of growth was visually observed, and the results are shown in Table 2. In the test for nematodes, 100 mg of the above biocide was put in a sample bottle.
Then, 1 g was weighed and charged, and a suspension (500 heads / 10 ml) of the nematode nematode as an index organism of nematodes such as roundworm and hookworm, which may be contaminated by feces of pets, was poured and left to stand. After 24 hours, the life and death of nematodes in the test solution were observed with a stereoscopic microscope to calculate the mortality of nematodes. The results are shown in Table 3. As shown, only biocidal activity was observed with the biocide of this example.

Example 2 The sized and cured product after SO ₂ treatment obtained in Example 1 was treated with silver nitrate 5
% Aqueous solution for 1 hour and then left in the air for 7 days to obtain the biocide of the present invention. The activity of this biocide against bacteria and nematodes was examined in the same manner as in Example 1 and shown in Table 2 and Table 3, respectively.

Example 3 Example 2 except that the concentration of the aqueous silver nitrate solution was changed to 10%.
The biocide of the present invention was obtained in the same manner as above, and the same test as in Example 1 was carried out. The results are shown in Tables 2 and 3.

Example 4 The sized and cured product after SO ₂ treatment obtained in Example 1 was mixed with silver nitrate 5
% Aqueous solution so as to be contained in 10% in the agent, and allowed to stand in the air for 1 day, and then water was added until the surface became dry, and allowed to stand for 7 days to obtain a biocide of the present invention. The activity of this biocide against bacteria and nematodes was examined in the same manner as in Example 1 and shown in Table 2 and Table 3, respectively.

Example 5 Example 4 except that the concentration of the aqueous silver nitrate solution was changed to 10%.
The biocide of the present invention was obtained in the same manner as described above, the same test as in Example 1 was conducted, and the results are shown in Tables 2 and 3.

[0022]

[Table 2]

[0023]

[Table 3] Example 6 The elution rate of silver ions by water passage of the biocide obtained in Examples 2 to 5 was examined with time. In the water flow test, an acrylic column with an inner diameter of 15 mm was filled with 10 ml of the biocide, the thickness of the agent was 55 mm, and the water flow rate was 200 ml per time, and water was passed 10 times at intervals of one day. The elution amount of ions was measured. Table 4 shows the analytical values of the biocides of Examples 2 to 5, and Table 5 shows the results of the water flow test.

Comparative Examples 1 and 2 The same operation as in Example 2 was repeated except that the natural zeolite and sand similarly sized in place of the sized and hardened product were used, and the natural zeolite and sand impregnated with the aqueous silver nitrate solution were used. Then, the same water flow test as in Example 6 was performed, and Comparative Example 1 and Comparative Example 2 were obtained.
And Table 4 shows the analytical values of the water flow test samples of Comparative Examples 1 and 2, and Table 5 shows the results of the water flow test.

[0025]

[Table 4]

[0026]

[Table 5] Example 7 Taking sand (thickness 30 cm) from a sandbox actually used,
1% by weight of the biocide of the present invention obtained in Examples 1 to 5 was sprayed and mixed, and after 24 hours, sand was collected and washed with sterile water. Table 6 shows the results of observing the presence or absence of growth of bacteria and larvae in the wash water with a stereoscopic microscope.

[0027]

[Table 6] +: Survival −: Death As is clear from the above examples, CaO and Ca of the present invention.
Not only is the agent itself obtained by treating SO ₄ , Al ₂ O ₃ , and SiO ₂ cured products with SO ₂ bactericidal properties, but treatment with an aqueous solution of an antibacterial metal compound also imparts nematicidal properties. In addition, the active ingredient (metal ion) from the metal compound is retained and used effectively for a long time without being easily washed away by rainwater or urine when the biocide is applied to a sandbox. I understand.

[0028]

As described above, according to the present invention, a used biocidal treatment agent of lime type is used, and it has a deodorizing effect as well as a biocidal effect, and has a stable effect for a long period of time. Agents can be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number in the agency FI technical display location (A01N 59/06 59:16) Z (72) Inventor Kunihiro Mori 4 Migaoka, Toyohira-ku, Sapporo, Hokkaido 9-21-1 Hokkaido Electric Power Co., Inc. Research Center (72) Inventor Tsutomu Ueno 4-92-1 Migamioka, Toyohira-ku, Sapporo-shi, Hokkaido Hokkaido Electric Power Co. Research Center (72) Inventor Takeshi Murayama Hokkaido Sapporo Mihogaoka, Toyohira-ku, Japan 4-92-1, Hokkaido Electric Power Co., Inc. Research Institute (72) Inventor Yukio Seki, Kita 2-jo East 7, Chuo-ku, Sapporo, Hokkaido Japan System Equipment Co., Ltd. (72) Inventor Kazu Saito Satoshi Enoniksu Co., Ltd. 1-24-1 Shimonoboro Techno Park, Atsubetsu-ku, Sapporo, Hokkaido

Claims (6)

[Claims] 1. CaO, CaSO ₄ obtained by mixing coal ash and / or a used lime-based exhaust gas treatment agent with at least one selected from the group consisting of slaked lime, quick lime, gypsum, and volcanic ash and hydration hardening , Al ₂ O ₃ , SiO ₂ type cured product is treated with a gas containing sulfurous acid gas. 2. CaO, CaSO ₄ obtained by mixing at least one selected from the group consisting of slaked lime, quick lime, gypsum, and volcanic ash with a coal ash and / or a used lime-based exhaust gas treatment agent and hydration hardening , Al ₂ O ₃ , SiO ₂ -based cured product is treated with a gas containing sulfurous acid gas, and further treated with an aqueous solution containing at least one water-soluble antibacterial metal compound. 3. The biocide according to claim 2, wherein the antibacterial metal compound is a salt of at least one metal selected from silver, copper, zinc and nickel. _4. CaO, CaSO ₄ obtained by mixing coal ash and / or a used lime-based exhaust gas treating agent with at least one selected from the group consisting of slaked lime, quick lime, gypsum, and volcanic ash and hydration hardening , Al ₂ O ₃ , and SiO ₂ type cured products are treated with a gas containing sulfurous acid gas, and a predetermined amount of an aqueous solution containing at least one water-soluble antibacterial metal compound is sprayed and absorbed, and left in the air. Then, a method for producing a biocide, which comprises adding water until the surface becomes dry and then leaving it in the air again. 5. The method for producing a biocide according to claim 4, wherein the antibacterial metal compound is a salt of at least one metal selected from silver, copper, zinc and nickel. 6. A method for cleaning and maintaining a sandbox, wherein 5 kg to 50 kg of the biocide according to claim 1 is sprayed and stirred per 1 m ² of surface area of the sandbox.