JP2002020150A - Production process for antibacterial concrete and cement composition therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a concrete structure having antibacterial activity by preparing an antibacterial agent for inhibiting the growth of sulfur-oxidizing bacteria and/or sulfuric acid-producing bacteria, both of which bacteria are liable to cause deterioration of the concrete structure, while utilizing waste containing a silicic acid component and an aluminum component, as an effective resource, and mixing the prepared antibacterial agent with cement. SOLUTION: This antibacterial concrete production process comprises: mixing waste containing both a silicic acid component and an aluminum component or waste containing any one of such a silicic acid component and an aluminum component with waste containing at least one of such a silicic acid component and an aluminum component, to obtain a waste mixture having a desired Si/Al atomic ratio (or SiO2/Al2O3 molar ratio); further mixing the waste mixture with an alkali aqueous medium; reacting them with each other in a pressure reaction vessel while heating the mixture and/or applying a pressure to the mixture, to obtain a reaction product; depositing an antibacterial cation and/or an antibacterial organic compound on the reaction product; and mixing the resulting material with cement.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an incineration ash for general garbage and a coal incineration ash rich in a silicate component and an aluminum component.
Utilize industrial waste such as activated sludge incineration ash, industrial waste liquid containing aluminum component, volcanic eruption product containing silicic acid component, and natural waste such as rice husks and plants of grasses under alkaline conditions. The present invention relates to a method for producing concrete having excellent antibacterial properties by allowing an antibacterial substance to be supported on a reaction product obtained by pressurization and further blending it with cement, and a cement composition thereof.

[0002]

2. Description of the Related Art Conventionally, as a method of imparting antibacterial properties to a concrete structure, a method has been used in which an antibacterial substance is added to a concrete coating agent and applied to the concrete surface to form an antibacterial property on the concrete outer wall. Japanese Unexamined Patent Publication No. Hei 10-139609 discloses that a currently used silica, oxide ceramic, non-oxide ceramic, zeolite, silicon, ferrite and an antibacterial metal adhered to the surface by a reheating treatment are used for antibacterial treatment. Cement,
There is disclosed a method of mixing antibacterial cement and antibacterial concrete into concrete.

[0003]

However, in the conventional method of making the surface of a concrete structure antibacterial with a coating film containing an antibacterial substance, sulfur oxidizing bacteria or sulfuric acid which grows inside the concrete structure and destroys the concrete composition are produced. The growth of bacteria that destroy the concrete composition such as bacteria cannot be suppressed, and the above ceramics are reheated with an antibacterial metal at about 800 ° C and the antibacterial metal is attached to the surface as an antibacterial agent. When antibacterial cement and antibacterial concrete were mixed into cement and concrete, the dissolution power of antibacterial metal ions was not stabilized.

[0004]

According to the first aspect of the present invention, a waste containing a silicate component and an aluminum component and a waste containing at least one of a silicate component and an aluminum component are provided. The mixture obtained by mixing with the alumina ratio was mixed with an alkaline aqueous medium, and reacted by heating or pressurizing while adding ultrasonic oscillation in a pressure-resistant reaction vessel.The resulting reaction product was treated with an antibacterial cation or A material carrying one or both of the antibacterial organic substances is mixed with cement to make the concrete antibacterial.

[0005] A second aspect of the present invention is to provide a method in which a waste containing either one of a silicate component and an aluminum component and a waste containing one or both of a silicate component and an aluminum component are mixed at a desired silicate ratio. The mixture is mixed with an alkaline aqueous medium, and reacted by heating or pressurizing while adding ultrasonic oscillation in a pressure-resistant reaction vessel, and one of an antibacterial cation and an antibacterial organic substance is added to the obtained reaction product. Alternatively, a material carrying both of them is mixed with cement to make the concrete antibacterial.

The invention according to claim 3 provides a waste containing either a silicate component or an aluminum component, a waste containing a silicate component and an aluminum component, and a waste containing a silicate component or an aluminum component. Alternatively, a mixture of wastes containing both at a desired silicate ratio, mixed with an alkaline aqueous medium, and reacted by heating or pressurizing while adding ultrasonic oscillation in a pressure-resistant reaction vessel, was obtained. An antibacterial cement composition in which a reaction product carrying one or both of an antibacterial cation and an antibacterial organic substance is added to a cement.

[0007]

Embodiments of the present invention will be described below.

The waste containing a silicic acid component and an aluminum component as described in the present invention includes natural and industrial waste incinerated ash containing silicate and aluminum as amorphous aluminum silicate salt, and combustible waste. It means incineration ash. The above-mentioned natural waste refers to a volcanic eruption product, which is a substance that has descended after being erupted by volcanic activity, and refers to pumice, volcanic ash, etc. Since the lava is rapidly cooled in the air, it is preferable to use a non-crystalline volcanic glass having small particles formed before the crystallization proceeds. Examples of the incineration ash of the industrial waste include coal incineration ash, paper sludge incineration ash, activated sludge waste incineration ash, and grass incineration ash.

The above-mentioned incinerated ash of combustible waste refers to combustible ash among wastes generated by various human activities, such as solid fuel incineration ash, incineration ash of city garbage, solidification of garbage. Examples include incinerated ash and coal ash when the fuel is burned as a heat source. Examples of the industrial waste include flammable waste such as wood and paper generated during civil engineering and construction work.

The waste containing a silicate component according to the present invention is a waste containing a high content of a silicate component such as cullet of silicate glass or soda glass, diatomaceous earth, or an alkaline extract of a botanical plant. .

Examples of the cullet of the silicate glass include cullets such as silicate glass, soda-lime glass, potassium lime glass, lead glass, barium glass, and borosilicate glass. Examples of soda-lime glass include plate glass, bottle glass, and crown glass. Therefore, in the present invention, sheet glass,
It is possible to use cullet, which is waste after using bottle glass, tableware glass, household glass, electric glass, lighting glass, physics and chemistry glass, medical glass, optical glass, and the like. In order to carry out the present invention, powdery glass having small particles is preferable.

[0012] The diatomaceous earth is a diatom remains, most of which are unicellular algae, that is, siliceous sediments made of diatom shells, which are usually mixed with clay, volcanic ash, and organic matter. Its essence is hydrous amorphous silicon dioxide. Diatomaceous earth is used for a wide range of applications, such as adsorbents, filter aids, heat insulators, cold insulators, fillers, abrasives, etc.Depending on the application, diatomaceous earth is crushed and refined to suit the intended use It is common to do. However, in the present invention, diatomaceous earth used for various purposes and waste diatomaceous earth after use can be used.

[0013] The alkaline extract of the above-mentioned hominaceous plants is a crushed seed shell or plant of a honeygrass plant such as rice, wheat, corn, millet, hirsut, pampas grass, and scotch.
~ 4N mixed with strong alkaline aqueous solution, 50 ~
By heating to 100 ° C., amorphous silica is eluted as a water-soluble silicate from the seed shell or plant.

The waste containing an aluminum component according to the present invention refers to a waste liquid obtained by dissolving and washing an aluminum component adhered to an aluminum product forming frame with an aqueous alkali solution in an aluminum product manufacturing industry or a process for producing alumite. Refers to the acidic waste liquid produced in In addition, aluminum-containing waste such as empty cans and waste aluminum discharged from ordinary households, and aluminum dross that has come out as waste in the process of melting aluminum can be used as an aluminum raw material.

The reaction product according to the present invention is a mixture of various kinds of compounds consisting of silica aluminosilicates, reaction intermediates and impurities, which are not mixed due to the difference in unburned carbon content of selected starting materials. There are cases where the mixture is a gray cation exchange material mixture containing activated carbon analogs derived from combustion carbon, and cases where it is a pure white cation exchange material mixture containing no carbon content.

The reaction product has a composition of a cation exchange substance which varies depending on an alum ratio (a molar ratio of silicon dioxide to alumina or an atomic ratio of silicon to aluminum). Although there are some differences depending on the cation exchange material mixture containing a large amount of hydroxysodalite when the silicate ratio is about 1.0, and when the silicate ratio is 1.5 to 2.0, the philipsite is removed. It becomes a cation exchange material mixture containing much.

Further, when the sulphate ratio exceeds 2.0, a cation exchange substance mixture containing a large amount of faujasite is obtained. A cation exchange substance mixture containing a large amount of zeolite X is produced when the uranium ratio is about 3, and a cation exchange substance mixture containing a large amount of zeolite Y is produced when the uranium ratio is about 4.0.

The alkaline aqueous medium according to the present invention is a hydroxide of an alkali metal which is soluble in water, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, lithium hydroxide and the like. It refers to an aqueous solution, and in the present invention, it is particularly preferable to use an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide.

In producing the cation exchange material mixture, it is possible to carry out the reaction at an alkali concentration in the range of 0.5 to 4.5 N.

As long as the heating conditions during the reaction are 80 ° C. or more, there is no problem in carrying out the present invention. However, in order to shorten the reaction time, a pressure-resistant reaction vessel is used at 80 to 230 ° C.
Or pressurized using a saturated vapor pressure to generate heat. At this time, the pressure in the pressure-resistant reaction vessel is 2 to 30 kg /
cm ² , that is, 120 to 230 ° C. is preferable for smooth reaction, and the reaction for obtaining the cation exchange material mixture is rapidly performed.

When a reaction for obtaining a cation exchange substance mixture is performed using a pressure-resistant container, the reaction is accelerated by applying an ultrasonic vibration of 18 to 500 kHz to the pressure-resistant container. This method is employed in the present invention because the exchange substance mixture has a fine particle size and is homogeneous, and a cation exchange substance is generated inside the particles. Equipment used: 1 L autoclave with stirring (manufactured by Toyo Koatsu Co., Ltd.): Ultrasonic oscillator (MODEL US- manufactured by Nippon Seiki Seisakusho Co.
600T)

Antibacterial cations according to the present invention include silver,
Refers to copper and zinc ions. Antibacterial metals include other metals having antibacterial properties such as tin, cadmium and nickel, but it is preferable not to use them from the viewpoint of safety. Examples of the antibacterial organic substances include plant extracts such as Hiba oil and licorice extract, aliphatic quaternary ammonium salts, and benzalkonium chloride. In the present invention, benzalkonium chloride is used, but other antibacterial organic substances can be used.

When the antibacterial metal ion or the antibacterial organic substance is supported on the cation exchange substance mixture, only the antibacterial metal ion may be supported. When loaded on a substance mixture, a material having an antibacterial property having a broad antibacterial spectrum can be obtained. It is also possible to carry a combination of different kinds of antibacterial metals, and further to carry an antibacterial organic substance.

The preparation method for supporting antibacterial metal ions on the cation exchange substance mixture is as follows: a 0.2 N aqueous solution of copper sulfate, silver nitrate or zinc chloride is added to the cation exchange substance mixture, and the mixture is shaken with a reciprocal shaker. After being shaken and sufficiently saturated with copper ions, silver ions and zinc ions, excess inorganic salts were washed away with water and dried at 105 ° C. to obtain a powder.
In addition, as an example in which an antibacterial organic substance is further supported on a support of an antibacterial metal, a support which further supports an antibacterial organic substance on a support of copper was separately prepared.

There is no particular limitation on the cement in which the cation exchange material mixture carrying the antibacterial substance is blended, but the cation exchange material mixture produced in the present invention contains unburned carbon. There are two types, a gray one and a pure white one which does not contain unburned carbon. In particular, the pure white cation exchange material mixture is preferable when blended in white Portland cement because the white color of the cement is maintained.

The proportion of the cation-exchange substance mixture carrying the antibacterial substance of the present invention when incorporated into the cement differs depending on the starting material and the cation-exchange substance mixture produced differs. However, there is no limitation as it depends on the concrete composition.

The present invention is configured as described above, and an embodiment will be described below.

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, an outline of the present invention will be described. The present invention relates to a waste containing a silicic acid component and an aluminum component, a waste containing either a silicic acid component or an aluminum component, and a waste containing silicic acid or a waste containing aluminum. The mixture of the two is mixed with an alkaline aqueous medium such as sodium hydroxide or potassium hydroxide, and heated or pressurized while applying ultrasonic transmission in a pressure-resistant reaction vessel to cause a reaction. Then, a material carrying one or both of an antibacterial cation and an antibacterial organic substance is mixed with cement to produce an antibacterial concrete.

When one or both of the above-mentioned antibacterial cations and / or antibacterial organic substances are supported on the reaction product, the ratio of the compound to the cement is 0 to the cement weight.
%, 5%, 10%, 20%, and 50%, and put sand as an aggregate in this (ratio of cement to aggregate, 1: 2). And the mixture was kneaded and solidified to prepare a cylindrical concrete block having a diameter of 1 cm and a height of 5 cm.

[0029] The antibacterial property of concrete is determined by cutting a piece (pellet having a radius of 0.5 cm and a thickness of 0.5 cm) from the concrete block cured for one month, embedding it in an agar medium, and adding sulfur-oxidizing bacteria or sulfuric acid. The resulting bacteria are inoculated and cultured in an incubator (culture temperature 36 ° C,
It is confirmed by measuring the size of the growth inhibition zone during the culture period of 5 days.

Example 1 A 1-liter autoclave with a stirrer (manufactured by Toyo Koatsu Co., Ltd.) was placed in an ultrasonic transmitter (Model US-600 manufactured by Nippon Seiki Seisaku-sho, Ltd.).
T), and fly ash having a non-crystalline aluminum silicate content of 95% in this reaction vessel and an aluminium ratio of about 2.5 (obtained from the Fly Ash Association, manufactured by Matsuura Power Station, Electric Power Development Co., Ltd.) ) 20 g and 5 g of glass cullet powder (manufactured by West Japan Environmental Development Cooperative Association) were mixed and placed in a pressure-resistant reaction vessel.
After putting 00ml and closing the lid, 25kHz at 600W
While oscillating the ultrasonic wave, pressure was applied with saturated steam, and heating was performed until the internal temperature reached 120 ° C.

After maintaining this state for 1 hour, the steam was released and the pressure was returned to atmospheric pressure, and the internal reaction product was taken out. This reaction product was washed with water and air-dried, and then supported with copper ion, silver ion, zinc ion, and a combination of copper ion and benzalkonium chloride to prepare an antibacterial agent.

The ratio of the antibacterial agent to the cement is 0%, 5%, 10%, 20% based on the weight of the cement.
%, 50%, sand as an aggregate (ratio of cement to aggregate, 1: 2), clean fresh water containing no salt or foreign matter at 50% water cement ratio, knead and knead. ,
A concrete block having a diameter of 1 cm and a height of 5 cm was prepared and cured for one month.

(Example 2) 50 g of glass powder (manufactured by West Japan Environmental Development Cooperative Association) was mixed with 50 g of incineration ash (obtained from the Municipal Cleaning Bureau, Machida City, Tokyo) of solidified fuel, and the pressure resistance of Example 1 was mixed. The reaction mixture was placed in a reaction vessel, and 240 ml of a 3.5N aqueous sodium hydroxide solution was added thereto.
While oscillating a 25 kHz ultrasonic wave at W, heating was performed with saturated steam until the internal temperature reached 90 to 95 ° C.
This state was maintained for 5 hours, and the excess sodium hydroxide of the reaction product was washed with water and air-dried to obtain a powdery reaction product. The reaction product was supported by a combination of copper ion, silver ion, zinc ion, copper ion and benzalkonium chloride to prepare an antibacterial agent. The proportion when the antibacterial agent was added to the cement and the conditions when preparing the concrete block were the same as in Example 1.

(Example 3) The content of amorphous silica was 9
20 g of rice husk incineration ash and 30 g of aluminum dross (obtained from the Japan Light Metal Association) obtained from the Kyun Yangon Thermal Power Station (using rice hulls as fuel) in Myanmar with 3% and 0.1% alumina content After mixing, the mixture was placed in the reaction vessel of Example 1, the balun ratio was set to about 2, 300 ml of a 0.5N sodium hydroxide aqueous solution was added from above, the lid was closed, and then 25 kHz ultrasonic waves were transmitted at 600 W. Pressurized with saturated vapor pressure while the internal temperature is 120
Heat until it reaches ° C.

After maintaining this state for one hour, the steam was released and the pressure was returned to the atmospheric pressure, and the internal reaction products were taken out.
This reaction product is washed with water and air-dried, and the resulting powdery reaction product is supported on a combination of copper ion, silver ion, zinc ion, copper ion and benzalkonium chloride, respectively.
An antimicrobial agent was prepared. The proportion when the antibacterial agent was added to the cement and the conditions when preparing the concrete block were the same as in Example 1.

(Example 4) The ratio of silicate from Kagoshima was about 3.2.
Crushed volcanic glass in an automatic mortar, 20 g of it, and 5 g of aluminum dross (obtained from Japan Light Metal Association)
Was placed in the reaction vessel used in Example 1, 200 ml of a 2N aqueous solution of sodium hydroxide was placed thereon, and after closing the lid, while oscillating 25 kHz ultrasonic waves at 600 W,
It was heated with saturated steam until the internal temperature reached 200 ° C.

After maintaining this state for 5 hours, the internal product was taken out, the reaction product was washed with water, and air-dried. The reaction product obtained was mixed with copper ion, silver ion, zinc ion, copper ion and chloride. An antibacterial agent was prepared by carrying each in combination with benzalkonium. The proportion when the antibacterial agent was added to the cement and the conditions when preparing the concrete block were the same as in Example 1.

(Example 5) 20 g of incinerated ash (manufactured by the Machida City Cleaning Bureau Incineration Plant, Tokyo) having an amorphous aluminum silicate content of 80% and an alum ratio of about 2.0 was manufactured. Example 1 5 g of powder (made by West Japan Environmental Development Cooperative Association)
Into the reaction vessel used above, 200 ml of a 4N aqueous sodium hydroxide solution was placed from above, and the lid was closed.
While oscillating an ultrasonic wave of 25 kHz at, heating was performed by saturated vapor pressure until the internal temperature reached 120 ° C.

After maintaining this state for 5 hours, the steam was released and the pressure was returned to the atmospheric pressure, and the internal reaction product was taken out. The reaction product was washed with water and air-dried, and the resulting reaction product was loaded with copper ion, silver ion, zinc ion, and a combination of copper ion and benzalkonium chloride to prepare an antibacterial agent. The proportion when the antibacterial agent was added to the cement and the conditions when preparing the concrete block were the same as in Example 1.

Example 6 A 1-liter autoclave with a stirrer (manufactured by Toyo Koatsu Co., Ltd.) was placed in an ultrasonic transmitter (Model Nippon Seiki Seisakusho, Model US-600).
T) was installed. Next, crushed rice plant 1
0 kg and 20 liters of about 4N sodium hydroxide aqueous solution were mixed and heated with stirring to obtain an eluate containing a silicate component. The silicon-containing powder (silica content 95% by weight) obtained by spray drying the eluate containing the silicate component
0 g and 300 ml of a washing waste liquid of an aluminum mold having an aluminum concentration of 10,000 ppm with an aqueous sodium hydroxide solution (about 3 N) are put into the reaction vessel of Example 1 (at a balun ratio of about 3), and the lid is closed. At 25
Heating was performed while transmitting a kHz ultrasonic wave, and heating was performed until the internal temperature reached 80 to 90 ° C. After maintaining this state for 3 hours, the mixture was allowed to cool, washed with water and air-dried, and then supported on a white powdery reaction product in the form of a combination of copper ion, silver ion, zinc ion, copper ion and benzalkonium chloride. Then, an antibacterial agent was prepared. The proportion when the antibacterial agent was added to the cement and the conditions when preparing the concrete block were the same as in Example 1.

[0041]

[Test Example of Antibacterial Property] The antibacterial property of concrete was determined by cutting a concrete block (1 cm) prepared by curing a concrete block containing the above antibacterial agent in different proportions for one month.
× 1 cm × 0.5 cm), embedded in an agar medium, inoculated with sulfur oxidizing bacteria and sulfuric acid producing bacteria respectively in the above-mentioned medium, and cultured in an incubator (at a culture temperature of 3).
(6 ° C., culturing days 5 days), and the size of the growth inhibition zone was measured. As a result, in the case where the antibacterial agent was blended by 10% or more based on the weight of cement, a growth inhibition zone was recognized on the agar medium, and the antibacterial property of the concrete was confirmed.

[0042]

As described above, according to the present invention, a waste containing a silicate component and an aluminum component, or a waste containing either a silicate component or an aluminum component, A mixture of waste containing at least one of the components is mixed with an alkaline aqueous medium, and reacted by heating or pressurizing in a pressure-resistant reaction vessel. By compounding one or both of the organic substances in the cement, it is possible to suppress the growth of sulfur oxidizing bacteria and sulfuric acid producing bacteria that cause deterioration of the concrete structure, and to reduce the useful life of concrete structures such as clay pipes. Can be extended. Furthermore, it will provide a new technology for effective use of waste.

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Claims (3)

[Claims] 1. A mixture of a waste containing a silicic acid component and an aluminum component and a waste containing at least one of a silicic acid component and an aluminum component at a desired silicate ratio, mixed with an alkaline aqueous medium. , Heating or pressurizing and reacting while adding ultrasonic oscillation in a pressure-resistant reaction vessel,
A method for producing an antibacterial concrete, comprising mixing the obtained reaction product with one or both of an antibacterial cation and an antibacterial organic substance in a cement. 2. A mixture of a waste containing at least one of a silicic acid component and an aluminum component and a waste containing one or both of a silicic acid component and an aluminum component at a desired silicate ratio is treated with an alkaline aqueous solution. Mixed with a medium and heated or pressurized while applying ultrasonic oscillation in a pressure-resistant reaction vessel, and the resulting reaction product carries one or both of an antibacterial cation or an antibacterial organic substance A method for producing an antibacterial concrete, characterized by blending with a cement. 3. A waste containing a silicate component and an aluminum component, a waste containing either a silicate component or an aluminum component, and a waste containing at least one of a silicate component and an aluminum component. Is mixed with an alkaline aqueous medium, and heated or pressurized while adding ultrasonic oscillation in a pressure-resistant reaction vessel, and the resulting reaction product is subjected to antibacterial activity. What is claimed is: 1. A cement composition for an antibacterial concrete, comprising a cement loaded with one or both of a cation and an antibacterial organic substance.