KR100628517B1 - Inorganic based admixture for concrete sewer pipe with anti-biotics and high-srength and manufacturing method thereof - Google Patents

Abstract

In order to prevent corrosion caused by sulfated bacteria of concrete used in sewage pipes, the present invention has a strength improvement effect and anti-bacterial properties when used in concrete by using two kinds of tungsten and nickel metals in fly ash, a pozzolanic material. The inorganic admixture for concrete sewer pipes, and its manufacturing method.

Herein, two kinds of metal sources, a nickel source and a tungsten source, were dissolved in water in order to impart antibacterial properties, and 50% by weight to 80% by weight of nickel and 50% by weight to 20% of tungsten were contained in the content ratio of nickel and tungsten. It is generated in the aqueous solution of metal ions by weight% and thermal power plant, and is put in the aqueous metal ion solution to support fly ash of 0.01% by weight to 40% by weight of metal ions, thereby preventing a high growth barrier of thiobarcillus Novellus. In order to distinguish the addition of antiseptics, the antiseptics are prepared by adding a durable inorganic coloring agent to heat and light, and adding the antiseptics to the high-strength mixture to make high-strength sewer pipes with antibacterial properties.

 Antibacterial, Admixture, Sewage Pipe, High Strength Concrete

Description

Inorganic Based Admixture For Concrete Sewer Pipe With Anti-Biotics and High-Srength And Manufacturing Method Thereof}

1 is a flow chart showing a method for producing an inorganic admixture for concrete sewage pipe having antiseptic properties and high strength of the present invention,

Figure 2a is a photograph showing a control sample (Control) plated with thiobacillus Novellus on the medium,

Figure 2b is a photograph of the test result of the test material of [Comparative Example] dropping and cultured using the Broth Microdilution MIC testing method on the control sample of Figure 2a,

Figure 2c is a photograph of the test result of the test material of [Example] dropping and cultured using the Broth Microdilution MIC testing method on the control sample of Figure 2a.

<Description of the symbols for the main parts of the drawings>

S100: Metal ion solution generation step

S110: stirring step S120: heating step

S130: heat treatment step S140: grinding step

S150: Antibacterial manufacturing step S160: High strength mixed material manufacturing step

S170: Mixing Step

The present invention relates to an inorganic admixture for concrete sewage pipes having antiseptic properties and high strength, and more particularly, to the growth of sulfated bacteria which inhabit the sewage pipes to decompose hydrogen sulfide to generate sulfuric acid to promote corrosion of the sewage pipes. In order to suppress, the tube is made by mixing and using a fungicide prepared by supporting tungsten and nickel metal ions in fly ash, but using an inorganic coloring agent to check the addition of the fungicide and using it together with a high strength mixed material. The present invention relates to an inorganic admixture for concrete sewage pipes having antibacterial properties and high strength, and a method of manufacturing the same.

Corrosion reaction of concrete sewer pipe is performed by strong acid produced by sulfated bacteria, and Thiobacillus Novellus is representative of these sulfated bacteria. Typical concrete sewer pipes are composed of granite aggregates and alkaline cement hydrates, which do not react with sulfuric acid because they are inert to acids, but cement hydrates actively react with sulfuric acid to produce inert substances such as gypsum. . As a result of this reaction, the aggregates are peeled off from the tube, and the part where the aggregates fall is exposed to acid, which causes another cement to continuously generate corrosion.

In order to suppress sulfuric acid corrosion of concrete, a method of suppressing the formation of sulfides and a method of suppressing the generation of hydrogen sulfide have been proposed, but a large amount of hydrogen peroxide, chlorine compounds or metal salts such as iron, zinc, lead, copper, etc. in sewage There was a problem about economics because it is added.

There is also a method of reducing the concentration of hydrogen sulfide in sewage pipes by ventilation to suppress the production of sulfuric acid from hydrogen sulfide. However, the occurrence of odor and also satisfactory results have not been obtained. Accordingly, a method of suppressing the production of sulfated bacteria has been developed in practical terms.

Antimicrobial materials that suppress these sulfated bacteria are largely classified into organic and inorganic antibacterial materials. Inorganic antimicrobial materials have semi-permanent persistence compared to organic antimicrobial materials, and there is almost no change in performance in external environments such as temperature and humidity. Because of its advantages, it is applied to various kinds of antibacterial products.

Currently developed and commercially available inorganic antibacterial materials are immobilized metal complexes such as silver, copper, zinc and nickel on a carrier such as titanium oxide, apatite, silica gel, calcium phosphate, zeolite, zirconium phosphate, calcium silicate and potassium titanate. Such inorganic antibacterial materials are applied to various fields, including actual stationery, interior decoration.

The antibacterial action of heavy metals is not due to the inherent toxicity and antibacterial properties of metals. It is thought to be due to its surface oxidation and metal ions dissociated in a solution containing a metal.

The antibacterial action of the metal ions is in the order of mercury> silver> copper> zinc but actually depends on the solubility dissociation degree of the metal salt.

The mechanism for the antibacterial action of antimicrobial metal ions is not elucidated but can be explained by the following.

[Denatured Protein by Metal Ions]

Metal ions reach the cell membranes of microorganisms by diffusion and are adsorbed to proteins such as cell membranes, and at the same time, they strongly cause cell destruction. Antibacterial metal adsorbed to proteins such as cell membranes (enzymes) destroys radicals of the S-H group, which are the constituents of cells, prevents microbial energy metabolism, and the metals themselves are converted to sulfides.

[Generation of Active Oxygen by Catalytic Reaction of Metal Ions]

Metal ions partially convert oxygen contained in the carrier around the catalyst into active oxygen (O, O-, O2 +). The active oxygen can act as a strong antibacterial agent in the form of ozone and hydrogen peroxide. Active oxygen diffuses into cells of microorganisms and is adsorbed to proteins such as cell membranes (enzymes) to destroy S-H groups.

Even now, the development of antibacterial inorganic materials is actively progressed by supporting such antibacterial metals on inorganic carriers such as zeolite, water glass, and fly ash.

The antimicrobial tube to which such antimicrobial material is added is not distinguished from general tubes because antimicrobial material is colorless. Therefore, in some cases, the letter or character is written in green to distinguish the anti-bacterial tube from the general tube, but this is also displayed on a part of the tube, so it is difficult for the installer to easily grasp.

Accordingly, the present invention has been made to solve the above problems,

Fly ash, an industrial waste-based pozzolanic material, is used to carry two metal ions, nickel and tungsten, to prevent fly-by-concrete corrosion. The purpose of the present invention is to provide an inorganic admixture for concrete sewage pipes having strength and strengthening antibacterial properties and high strength as well as distinguishing antibacterial pipes from general pipes by preparing and using antimicrobial agents mixed with streams.

Inorganic admixture for concrete sewage pipe having antibacterial property and high strength according to the present invention for achieving the above object,

In the inorganic admixture for concrete sewer pipes, which have anti-bacterial properties against sulfated bacteria causing corrosion of concrete sewer pipes, two kinds of metal sources, nickel source and tungsten source, are prepared by dissolving in water to give anti-bacterial properties. The content ratio of 50% to 80% by weight of nickel and 20% to 50% by weight of tungsten and a metal ion aqueous solution, which is put in the aqueous metal ion solution to support 0.01% to 40% by weight of metal ions It is prepared by mixing the retarded powder with the iron oxide inorganic colorant selected from the group consisting of hematite and margeite in a ratio of 1: 1 (0.1 to 7) and finely divided the remaining material by heating the metal ion aqueous solution containing the support. Fungicides; High strength mixed material consisting of 10 to 50% by weight of fly ash obtained from thermal power plant, 10 to 50% by weight of blast furnace slag, 10 to 30% by weight of anhydrous gypsum, 1 to 10% by weight of CSA-based expanding agent, and 1 to 10% by weight of slaked lime Consisting of, the antimicrobial agent is characterized in that the mixture is made of 0.1 to 5% by weight relative to the high-strength mixture material.

In addition, the method for producing an inorganic admixture for concrete sewage pipe having the antibacterial and high strength,

A metal ion aqueous solution generation step of dissolving two metal sources of a nickel source and a tungsten source in water to generate a metal ion aqueous solution; A stirring step of putting a carrier in the aqueous metal ion solution so that metal ions are supported; A heating step of heating at 90 to 100 ° C. such that water contained in the metal ion aqueous solution is evaporated; A heat treatment step of heat-treating the aqueous metal ion solution in which water is evaporated at 300 to 400 ° C. for 3 to 5 hours to generate a mass; A pulverizing step of pulverizing the agglomerates obtained by heat treatment to 150 mesh or less; and powdered iron oxide (Fe ₂ O ₃ ) inorganic colorant selected from the group consisting of the pulverized fine powder, hematite and margemate 1: (0.1 ~ 7) the antimicrobial manufacturing step of mixing at the ratio; 10 to 50% by weight of fly ash obtained from thermal power plant, 10 to 50% by weight of blast furnace slag, 10 to 30% by weight of anhydrous gypsum, 1 to 10% by weight of CSA-based expanding agent, 1 to 10% by weight of slaked lime A material manufacturing step; Characterized in that it comprises a; mixing step of mixing the antimicrobial agent 0.1 ~ 5% by weight with respect to the prepared high-strength mixture.

The content ratio of nickel and tungsten dissolved in the metal ion aqueous solution generation step is 50% by weight to 80% by weight of nickel and 20% by weight to 50% by weight of tungsten, and 20 ° C. to 50% to promote dissolution. It can be heated to ℃ to shorten the dissolution time.

In addition, as the nickel source of the metal ion aqueous solution generation step, water-soluble nickel dichloride (NiCl ₂ · 6H ₂ O) and nickel sulfate (NiSO ₄ · 7H ₂ O) are used, and as the tungsten source, water-soluble sodium tungstate (Na ₂ WO ₄ ㆍ 2H ₂ O).

In addition, the carrier in the stirring step is added to the metal ion amount of the metal ion solution to 0.01 to 40% by weight, and stirred for 1 to 10 hours at 20 ℃ to 30 ℃.

In addition, the support may be selected from the group consisting of fly ash, zeolite, activated carbon, silica gel, alumina, or the like, or two or more kinds thereof. The support is to coat the metal ions on the shell, the metallic material such as fly ash is to cause the coating is generated by the ionic bond, the porous material zeolite and the like is to be coated with the metal ion by adsorption.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

1 is a flow chart illustrating a method for preparing an inorganic admixture for concrete sewer pipe having antiseptic properties and high strength according to the present invention.

As shown in the present invention, the metal ion aqueous solution generation step (S100), stirring step (S110), heating step (S120), heat treatment step (S130), grinding step (S140), antibacterial manufacturing step (S150), high strength mixing Material manufacturing step (S160), mixing step (S170) is made.

The metal ion aqueous solution generation step (S100) is a step of dissolving metal ions, such as nickel, tungsten, silver, and copper, which have high growth-disturbing activity against thiobacilli, which are sulfated bacteria, in water to generate an aqueous solution. In particular, in the present invention, nickel and tungsten are used as examples, but silver and copper may also be used.

The nickel source for preparing such an aqueous solution includes water-soluble nickel dichloride (NiCl 2 · 6H 2 O) and nickel sulfate (NiSO 4 · 7H 2 O), and the like. As the tungsten source, water-soluble sodium tungstate (Na 2 WO 4 · 2H 2 O) is used. .

In addition, in the step of dissolving the nickel source and tungsten source, the two kinds of metal sources in water to produce a metal ion aqueous solution, it is possible to shorten the dissolution time by heating to 20 ℃ ~ 50 ℃.

In the case of producing the aqueous metal ion solution, the amount of tungsten is used in an amount of about 20% by weight to about 50% by weight relative to 50% by weight to 80% by weight of nickel. In consideration of economics, it is preferable to use 20% by weight of tungsten with respect to 80% by weight of nickel.

In addition, silver (Ag) as described above may be added to impart antimicrobial properties separately during the preparation of the aqueous metal ion solution.

Meanwhile, a fly ash is put in the metal ion aqueous solution prepared as described above so that the metal ions are coated or adsorbed, and then stirred at 20 ° C. to 30 ° C. for 1 to 10 hours to form a stirring step (S110).

The support may be selected from the group consisting of fly ash, zeolite, activated carbon, silica gel, alumina, and the like, or a kind or two or more, preferably using a fly ash obtained from a thermal power plant, and the amount to be supported is a metal ion aqueous solution. It is preferable that the content of the metal ions to be supported on the 0.01 to 40% by weight, especially 1 to 30% by weight. When the content of the metal ions is less than 0.01% by weight, it is difficult to show the growth impairment effect on the thiobacilli Novellus, and even if more than 40% by weight, it is difficult to expect the improvement of the growth impairment effect on the thiobacilli Novellus and economically. Not desirable

When the stirring is completed, a heating step (S120) of evaporating by applying heat of 90 ° C. to 100 ° C. is performed to evaporate the moisture contained in the metal ion aqueous solution.

In addition, a heat treatment step (S130) is formed by applying heat to the residue remaining after evaporation in the heating step at 300 to 400 ° C. for 3 to 5 hours to form the residue as a mass, wherein the heat treatment temperature is higher than the temperature described. The heat treatment time may be shortened by forming.

As such, the pulverization step (S140) of pulverizing the agglomerated mass by the heat treatment to 150 mesh or less is performed, and the pulverized fine powder and the inorganic colorant are mixed to prepare a fungicide (S150).

Inorganic coloring agent mixed with the antimicrobial agent is used for coloring and strength using hematite (α-Fe ₂ O ₃ ) or margeite (Maghemite, Γ-Fe ₂ O ₃ ) iron oxide (Fe ₂ O ₃ ) It is preferable to be provided at the same time, the mixing ratio is mixed in a ratio of 0.1 to 7 parts by weight relative to the ground fine powder 1. That is, when the mixing ratio of the inorganic coloring agent is mixed at 0.1 or less, almost no distinction between the general tube and the coloring is obtained, and when mixing at 7 parts by weight or more, the strength may be increased, but the bonding strength may be lowered.

On the other hand, in the high-strength mixed material manufacturing step (S160) in the step of mixing fly ash, blast furnace slag powder, anhydrous gypsum, CSA-based expansion agent, calcined lime 10 ~ 50% by weight of the fly ash obtained from the thermal power plant and blast furnace slag fine powder 10 ~ 50% by weight, anhydrous gypsum 10 to 30% by weight, CSA-based expansion agent 1 to 10% by weight, calcined lime 1 to 10% by weight to prepare a high-strength mixture.

The high strength admixture prepared as described above is to prepare an inorganic admixture for concrete sewer pipe having final antibacterial property and high strength by mixing with the prepared antibacterial agent (S170), and the mixing condition is an antimicrobial agent for the high strength admixture. 0.1 to 5% by weight to mix.

EXAMPLE

After dissolving 186.5 g of nickel dichloride (NiCl 2 · 6H 2 O) in 2 L of water, and dissolving 110 g of sodium tungstate (Na 2 WO 4 · 2H 2 O), 200 g of fly ash was added to an aqueous metal ion solution and stirred at 20 ° C. for 10 hours. All the water was evaporated at 100 ° C., and the mass obtained by heat treatment at 350 ° C. for 4 hours was pulverized to obtain a passage of 150 mesh or less. After that
A fungicide was prepared by adding an iron oxide inorganic colorant selected from the group consisting of hematite (α-Fe ₂ O ₃ ) and margeite (Γ-Fe ₂ O ₃ ).

The growth inhibitory effect on the thiobarcillus novelus was tested by the Broth Microdilution MIC testing method by selecting the inorganic antimicrobial agent obtained in the above [Example] and RCF-95 [Comparative Example], currently sold by Pozolis.

Figure 2a is a photograph showing a control sample (Control) plated with thiobacillus Novellus on the medium.

First, as shown in FIG. 2A, thiobacilli Novellus was suspended in 0.85% saline to have a concentration of 4 × 10 8 / ml, and then plated on Nutrient agar, which is an appropriate medium of thiobacilli Novellus.

Figure 2b is a photograph of the test result of the test material of [Comparative Example] dropping and cultured using the Broth Microdilution MIC testing method on the control sample of Figure 2a, Figure 2c is Broth Microdilution MIC testing method on the control sample of Figure 2a The test result photograph in the state of dropping and culturing the test substance of Example is used.

As shown in Fig. 2a, 2b, 2c, 20ul of the test substance was added dropwise onto the thiobacillus Novellus smeared medium, and incubated at 30 ° C for 2 days. The diameter (mm) of the clear zone after culture was measured, and all tests were repeated three times. Here, the concentration of the test substance was used by suspending 1 g of each substance in 1 ml of sterile water.

Test Example 1: Broth Microdilution MIC testing results

In both examples of [Example] and [Comparative Example], the inhibitory effect of Thiobacillus Novellus (KCTC 2845) is illustrated through FIGS. 2A-2C and summarized in Table 1 again.

Test Example 2: The compressive strength of the inorganic antibacterial agent obtained in Example

The compressive strength of concrete was compared and tested for the inorganic antibacterial agent obtained in Example. In order to prepare the test specimen of concrete, cement was used as a common type 1 portland cement with a specific gravity of 3.15 powder and 3,300cm2 / g. The fine aggregate was 2.60, the coarse aggregate was 2.64, and the maximum aggregate size was 13mm. The material mix ratio of the concrete specimens is shown in [Table 2], and the compressive strength results are shown in [Table 3]. The cement, aggregate, and the corresponding amount of water and the mixed material of the mixing ratio described in Table 2 were mixed uniformly using a mixer, and then the concrete mixture was prepared. Ø 10 × 20cm specimens were prepared in accordance with KS F 2403 compressive strength test specimens.

Concrete specimens were initially cured for 2 to 3 hours under atmospheric pressure, and then heated up to 20 ° C. or less every hour to reach a temperature of 60 ° C. to 70 ° C., and then maintained at 90% relative humidity for 4 to 8 hours. Compressive strength was measured for 1, 7, 28 days of the product cured under the above conditions.

As described above, the present invention prevents corrosion of concrete by sulfated bacteria and thereby increases the life of concrete products and increases the strength and chemical resistance of secondary concrete products by using pozzolanic materials such as fly ash and blast furnace slag. For example, many advantages can be obtained, such as improvement in durability by preventing cracking due to the reduction of heat of hydration of concrete obtained by replacing cement, and reduction of production cost obtained by replacing relatively expensive cement and reduction of pollution problem by recycling industrial waste.

In addition, since the iron oxides are mixed and used as a colorant, color is given to the manufactured tube, and thus, it is possible to provide an antimicrobial tube that can be easily distinguished from the general tube.

Claims (7)

In the inorganic admixture for concrete sewer pipes, which have anti-bacterial properties against sulfated bacteria causing corrosion of concrete sewer pipes, In order to provide antibacterial properties, two kinds of metal sources, nickel source and tungsten source, are dissolved in water, and the content ratio of nickel and tungsten is 50% to 80% by weight of nickel and 20% to 50% by weight of tungsten. A fine powder obtained by pulverizing the remaining material by heating a metal ion aqueous solution, a carrier loaded in the aqueous metal ion solution and carrying 0.01 to 40% by weight of metal ions, and a metal ion aqueous solution containing the carrier. Antimicrobial agent prepared by mixing the iron oxide inorganic coloring agent selected from the group consisting of hematite and margemate in the ratio of 0.1 ~ 7); High strength mixed material consisting of 10 to 50% by weight of fly ash obtained from thermal power plant, 10 to 50% by weight of blast furnace slag, 10 to 30% by weight of anhydrous gypsum, 1 to 10% by weight of CSA-based expanding agent, and 1 to 10% by weight of slaked lime Consisting of The antibacterial agent is an inorganic compound admixture for concrete sewage pipes having anti-bacterial and high strength, characterized in that the mixture is made of 0.1 to 5% by weight relative to the high-strength mixed material. The method of claim 1, The carrier is a fly ash, zeolite, activated carbon, silica gel, alumina and the like selected from the group consisting of one or more selected from the group consisting of inorganic sequestrant having a high strength and antibacterial. Generating a metal ion aqueous solution by dissolving two metal sources of a nickel source and a tungsten source in water (S100); A stirring step of putting the carrier in the aqueous metal ion solution so that the metal ions are coated (S110); A heating step of heating at 90 to 100 ° C. such that water contained in the aqueous metal ion solution is evaporated (S120); A heat treatment step (S130) of heat-treating the metal ion aqueous solution in which water is evaporated at 300 to 400 ° C. for 3 to 5 hours to generate a mass; A pulverization step (S140) of pulverizing the mass obtained by heat treatment to 150mesh or less; and The antimicrobial agent manufacturing step (S150) of mixing the pulverized fine powder and hematite and margemate used iron oxide (Fe ₂ O ₃ ) inorganic colorant in a ratio of 1: (0.1 ~ 7); 10 to 50% by weight of fly ash obtained from thermal power plant, 10 to 50% by weight of blast furnace slag, 10 to 30% by weight of anhydrous gypsum, 1 to 10% by weight of CSA-based expanding agent, 1 to 10% by weight of slaked lime A material manufacturing step (S160); Method for producing an inorganic admixture for concrete sewage pipes having anti-bacterial and high strength characterized in that it comprises a; mixing step (S170) is 0.1 to 5% by weight of the antimicrobial agent for the prepared high-strength mixture. The method of claim 3, wherein The content ratio of nickel and tungsten dissolved in the metal ion aqueous solution generation step (S100) is 50% by weight to 80% by weight of nickel and 20% by weight to 50% by weight of tungsten relative to the amount of dissolution. Method for producing an inorganic admixture for concrete sewage pipes having anti-bacterial and high strength by heating to ℃ ~ 50 ℃ to shorten the dissolution time. The method of claim 3, wherein The nickel source of the metal ion aqueous solution generation step (S100) is water-soluble nickel dichloride (NiCl ₂ .6H ₂ O) and nickel sulfate (NiSO ₄ .7H ₂ O), and the tungsten source is water-soluble sodium tungstate ( Na ₂ WO ₄ ㆍ 2H ₂ O) A method for producing an inorganic admixture for concrete sewage pipe having antiseptic properties and high strength. The method of claim 3, wherein In the stirring step (S110), the carrier is added to the amount of metal ions of the metal ion solution to 0.01 to 40% by weight, and concrete having antibacterial and high strength, characterized in that for 1 to 10 hours stirring at 20 ℃ ~ 30 ℃ Inorganic admixture for sewage pipes. The method according to claim 3 or 6, wherein The carrier is a fly ash, zeolite, activated carbon, silica gel, alumina selected from the group consisting of at least one or more selected from the group consisting of inorganic anti-bacterial admixture for a sewer pipe having high strength.

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