KR102495923B1 - Antimicrobial porous particle composition and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an antibacterial porous body composition and a method for manufacturing the same, and more particularly, by coating inorganic porous bottom ash and at least a portion of the surface of the bottom ash or at least a portion of internal pores of the bottom ash with zinc oxide nanoparticles, It relates to an antibacterial porous body capable of holding air in micropores and adsorbing and removing contaminants in air and aquatic environments, and a manufacturing method thereof.

Description

Antimicrobial porous particle composition and manufacturing method thereof

The present invention relates to an antimicrobial porous body composition and a method for preparing the same, and more particularly, to a porous body composition having antibacterial activity by including bottom ash (bottom ash) and zinc oxide nanoparticles and a method for preparing the same.

Bottom ash (bottom ash) is a type of coal ash generated together with fly ash (fly ash) in the process of burning bituminous and anthracite coal in a thermal power plant. Unlike fly ash, it has the shape of a mass (lump). While fly ash, which accounts for 75 to 85% of the amount of coal ash generated, is recycled as a construction material such as cement substitute and concrete admixture, bottom ash has a problem of causing deterioration in strength performance and durability due to foaming properties.

In general, bottom ash is composed of a large amount of inorganic components such as silica (SiO ₂ ) and alumina (Al ₂ O ₃ ) and bitumen coal components, and is a porous body in which pores are formed as carbon dioxide is released in the process of burning coal at a high temperature during thermal power generation. includes

On the other hand, bottom ash containing such an inorganic porous body not only retains moisture and air in the micropores, but also has the advantage of filtering and adsorbing contaminants. A variety of technologies to be used as ornamental materials are being developed.

As a prior art utilizing the bottom ash, Korean Patent Registration No. 10-0926382 (published on November 11, 2009) discloses a method for manufacturing a water purification material containing bottom ash as a main component. More specifically, in the prior literature, landfill ash aged after being buried for a long time in an ash treatment plant of a power plant is collected, classified, pulverized, powder removal such as fly ash in pores, other salts removed, harmful bacteria removed, and effective microorganism treatment Although a method for manufacturing a water purification material manufactured through a process such as , drying, etc. is proposed, this only discloses a water purification material capable of filtering and adsorbing contaminants of bottom ash containing porous particles, and bacteria or microorganisms in the water to be treated are disclosed. Since there is no component to remove, there is a problem that a separate antibacterial treatment step is required for products requiring antibacterial properties.

In addition, Korean Patent Registration No. 10-1866908 (published on June 15, 2018) discloses a water-permeable block color aggregate for garage painting containing bottom ash, a by-product generated from thermal power plants, but this also has a questionable antibacterial activity. There is, and it has limitations that apply only to blocks for pedestrian roads.

Therefore, as a porous body composition using bottom ash containing micropores, it is required to develop a novel porous body composition having high antibacterial activity by coating the pores in the bottom ash with an antibacterial material and a manufacturing technology thereof. Based on this, It is necessary to develop technology for a method of using an antibacterial porous body capable of removing harmful microorganisms in water or in the surrounding air.

Korean Registered Patent Publication No. 10-0926382 (Announced on November 11, 2009) Korean Registered Patent Publication No. 10-1866908 (2018.06.15. Notice)

In order to solve the above problems, an object of the present invention is a porous body composition using bottom ash containing micropores, which has high antibacterial activity by coating an antibacterial material on at least a part of the bottom ash surface or internal pores. And to provide a manufacturing method thereof.

In addition, another object of the present invention is to provide an ornamental water tank, garland or flower pot capable of removing harmful microorganisms in water or air by including the antibacterial porous body composition.

In order to achieve the above object, the present invention bottom ash; and an antibacterial coating component coated on at least a portion of the surface of the bottom ash or at least a portion of internal pores of the bottom ash, wherein the antibacterial coating component includes zinc oxide nanoparticles, an aqueous emulsion binder, and a pigment. It provides an antimicrobial porous body composition characterized in that.

As an example, the average particle size of the zinc oxide nanoparticles may be in the range of 5 to 900 nm.

As an example, the content of the zinc oxide nanoparticles may be in the range of 0.3 to 9% by weight, preferably 0.7 to 9% by weight, when the total of the zinc oxide nanoparticles, the aqueous emulsion binder and the pigment is 100% by weight. It may be in the range of 5% by weight.

As an example, the pigment may be at least one selected from carbon black and a transition metal oxide, and the content of the pigment is 1 to 100% by weight when the total of zinc oxide nanoparticles, the aqueous emulsion binder, and the pigment is 100% by weight. It may be in the range of 10% by weight.

In addition, the antibacterial porous body composition according to the present invention may be provided in a wreath, flowerpot, or water tank.

In addition, the present invention (a) bottom ash; preparing a bottom ash-antibacterial coating component mixture by mixing and stirring; and zinc oxide nanoparticles, an antibacterial coating component including a water-based emulsion binder and a pigment; and (b) drying the bottom ash-antibacterial coating component mixture to prepare an antimicrobial porous body composition.

In addition, the present invention can provide an ornamental water tank containing the antibacterial porous body composition, and also can provide an ornamental flower pot containing the antimicrobial porous body composition, and the present invention also provides an antibacterial porous body composition. An ornamental wreath can be provided.

The antibacterial porous body composition according to the present invention is coated with zinc oxide nanoparticles on at least a part of the surface or internal pores of the bottom ash, which is an inorganic porous body including micropores, so that the zinc oxide nanoparticles are used as an antibacterial component on the surface or in the internal pores. By being contained, it is possible to remove contaminants in the surrounding air and / or aquatic environment, and also exhibit a reduction rate of 99 % or more, preferably 99.9% or more, in microbial propagation.

Therefore, the antibacterial porous body composition can be used to replace soil for plant growth or applied to an aquarium for fish species growth.

In addition, it is easy to adsorb pigments, etc., and can show various colors, so it has an additional advantage of improving aesthetics through ease of management and various expressions when it is included in a flowerpot, wreath, water tank, etc.

1 is a flow chart showing a method for manufacturing an antimicrobial porous body composition according to an embodiment of the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is one well known and commonly used in the art.

Terms such as “comprise”, “include” or “having” described in this specification indicate that there is a feature, numerical value, step, operation, component, part, or combination thereof described in the specification. It does not rule out the possibility that other features, figures, steps, operations, components, parts, or combinations thereof may exist or be added that have not been described.

Coal is the cheapest and richest fuel on earth, and the use of coal-fired power plants has increased the amount of landfill ash, and recently more than 6 million tons of landfill ash has been generated annually. Looking at it, in the case of fly ash, a large amount is recycled as a concrete admixture, etc., but in the case of bottom ash, only a small part is recycled as a raw material for stock materials, and the rest is disposed of and disposed of in a landfill (ash treatment plant). Although it is very important both physically and industrially, it is a reality that many studies have not been done. However, the present inventors focused on this problem and coated zinc oxide nanoparticles on the surface or internal pores of the bottom ash to obtain a porous body with maximized antibacterial properties. It has been found that the composition can be prepared.

The antibacterial porous body composition of the present invention is bottom ash; and an antibacterial coating component coated on at least a portion of the surface of the bottom ash or at least a portion of internal pores of the bottom ash, wherein the antibacterial coating component includes zinc oxide nanoparticles, an aqueous emulsion binder, and a pigment. do.

Here, the bottom ash is an industrial by-product generated after pulverized coal used in coal-fired power plants is burned, and landfill ash (ash remaining after coal is burned) is usually bottom ash (bottom ash) depending on the place of occurrence. ) and fly ash (fly ash). Bottom ash is an ash that falls to the bottom of a boiler furnace of a power plant and may have a form of molten irregular slag like volcanic stone. Since it is collected, it can have a fine powder form. In addition, the generation ratio of the fly ash and the bottom ash varies depending on the power plant, but generally may have a range of about 75 to 90% by weight: about 10 to 25% by weight.

In the case of the bottom ash used in the present invention, the average particle size thereof may range from 0.5 to 50 mm, and preferably, the obtained bottom ash may be pulverized and used to have a range from 2 to 20 mm. If the average particle size is less than 0.5 mm, there is a problem in using it because it is scattered like dust, and if it exceeds 50 mm, there is a problem that the internal pores may decrease and the antibacterial properties in the antibacterial coating component may deteriorate. Use bottom ash of the above particle size range It is desirable to do

On the other hand, in the case of bottom ash, it has a low radon content, so it can have better utility as an interior and consumer product compared to porous body compositions of other ceramic components such as ocher ball, zeolite ball, and hydro ball.

On the other hand, in the case of the bottom ash, if necessary, it may undergo a washing process with water or air before coating with the antibacterial coating component. At this time, the washing process may be performed by washing by spraying high-pressure air or high-pressure water, washing by stirring after inputting fine bottom ash into the water tank, etc., but is not limited thereto.

On the other hand, in the present invention, the antibacterial coating component coated on at least a part of the bottom ash surface and / or internal pores is a liquid slurry containing zinc oxide nanoparticles, an aqueous emulsion binder and a pigment, and the antibacterial coating component and the bottom ash After preparing the bottom ash-antibacterial coating component mixture through mixing, zinc oxide nanoparticles, aqueous emulsion binder and pigment are uniformly coated on at least a part of the bottom ash surface and/or internal pores through a drying process, which is a subsequent process. It is possible to form a porous body composition having a structured structure.

On the other hand, the zinc oxide nanoparticles as a component in the antimicrobial coating component according to the present invention is a material that releases soluble zinc ions having antibacterial activity against microorganisms, wherein the soluble zinc ions are reactive oxygen species (ROS, Reactive Oxigen species) to induce oxidative stress or to be adsorbed on the cell wall to affect the membrane transport of microorganisms, thereby inducing the death of bacteria.

In the case of a porous body containing only bottom ash as a main component according to the present invention, since it does not have antibacterial properties, it is necessary to impart antibacterial properties to it in order to use it for applications such as pots containing flowers, garlands, or aquariums in which fish will live.

In addition, it is preferable to include various pigments in order to additionally impart various colors as sculptures in addition to the antibacterial properties, and accordingly, antibacterial materials and pigments can be coated on the surface or internal pores of the bottom ash and they can be coated on the bottom ash. It is possible to prepare a porous body composition that combines antibacterial properties and aesthetics at the same time by coating with an antibacterial coating component containing a binder component.

Here, the zinc oxide nanoparticles may have an average particle size of 5 to 900 nm, preferably 6 to 100 nm, and more preferably 10 to 30 nm. Here, when the average particle size of the zinc oxide nanoparticles is less than 5 nm, there is a problem in that the bottom ash is not uniformly coated due to excessive aggregation between the zinc oxide nanoparticles, and when the average particle size exceeds 900 nm, antimicrobial activity is reduced. there is

In the present invention, the content of the zinc oxide nanoparticles may be 0.3 to 9% by weight, preferably 0.7 to 5% by weight, when the total of the zinc oxide nanoparticles, the aqueous emulsion binder and the pigment is 100% by weight there is.

Here, when the content of the zinc oxide nanoparticles is less than 0.3% by weight, the bottom ash is not uniformly coated, resulting in a decrease in antibacterial activity, and when the content exceeds 9% by weight, the antibacterial activity of the zinc oxide added There is a problem that the degree of increase is insignificant and the economic feasibility is low.

In addition, the water-based emulsion binder in the present invention can be used regardless of its type as long as it is a water-soluble material that serves as an adhesive so that the components included in the antibacterial coating component can be coated on the bottom ash, and exemplarily urethane-based, acrylic-based, polyol At least one binder selected from an ethylene-vinyl acetate copolymer (EVA) may be used, but it is not limited thereto, and various known aqueous emulsion binder components may be used.

At this time, the content of the binder in the present invention is 81 to 98 wt%, preferably 85 to 95 wt% when the total of the zinc oxide nanoparticles, the aqueous emulsion binder and the pigment is 100 wt%. Can be used there is.

At this time, in the antibacterial coating component, as components other than the zinc oxide nanoparticles, emulsion binder and pigment, an aqueous solution may optionally be included, the content of which is 5 to 95 wt% relative to the total weight of the antimicrobial coating component, Preferably, it can be used in the range of 10 to 90 wt% .

In addition, in the present invention, in the antibacterial coating component Pigments are components that enhance aesthetics by displaying various colors on the surface of a porous body, and are classified into inorganic pigments and organic pigments according to components, and white pigments, black pigments, and red pigments according to colors.

The pigment may be selected considering the color and chemical properties of the antibacterial coating component, and preferably, an inorganic pigment may be used considering that the chemical property of the antimicrobial porous body composition in the present invention is an aqueous composition.

The inorganic pigment includes at least one transition metal salt selected from Ti, Fe, Cr, Cu, Ba, Pb, and Sb, and the transition metal salt is selected from among oxides, hydroxides, sulfides, chromates, silicates, phosphates, sulfates, and carbonates. can be one or more. In addition, as the inorganic pigment, carbon black having a carbon component and metal oxides including titanium dioxide and iron oxide may be used as the inorganic pigment.

Preferred examples of the pigment in the antibacterial coating component according to the present invention include carbon black; ferrocyanide; transition metal oxides selected from Ti, Fe, Cr, Cu, Ba, Pb and Sb; Any one or a mixture thereof selected from may be used, and more preferably, carbon black is used, or as a transition metal oxide, at least one selected from iron oxide (Fe ₂ O ₃ ) and titanium dioxide (TiO ₂ ) is used. Here, the content of the pigment is 0.5 to 10 wt%, preferably 0.7 to 5 wt%, when the total of the zinc oxide nanoparticles, the aqueous emulsion binder and the pigment is 100 wt%. there is.

In addition, the present invention, in addition to the zinc oxide nanoparticles, the emulsion binder and the pigment, the dispersant is optionally included in the range of 0 to 8 wt% relative to 100 wt% of the total weight of the zinc oxide nanoparticles, the aqueous emulsion binder and the pigment The dispersant can improve the dispersion of the pigment and zinc oxide nanoparticles in the antibacterial coating component, thereby enhancing the uniform coating of the porous body, and as a wet dispersant, one of organic or inorganic dispersants for pigment You can choose.

On the other hand, the present invention can provide a novel manufacturing method of the antimicrobial porous body composition according to the present invention described above.

More specifically, the present invention in preparing an antibacterial porous body composition, (a) bottom ash; and an antibacterial coating component including zinc oxide nanoparticles, an aqueous emulsion binder, and a pigment; preparing a bottom ash-antibacterial coating component mixture by mixing and stirring; and (b) drying the bottom ash-antibacterial coating component mixture to prepare an antimicrobial porous body composition.

Here, looking in more detail at each step of the manufacturing method of the antimicrobial porous body composition according to the present invention, the step (a) includes bottom ash; and an antibacterial coating component including zinc oxide nanoparticles, a water-based emulsion binder, and a pigment; mixing and stirring to prepare a bottom ash-antibacterial coating component mixture, as a mixing ratio of the bottom ash and the antibacterial coating component, bottom ash: The weight ratio of the antibacterial coating component may range from 100:1 to 100:30, preferably from 100:2 to 100:20.

In addition, stirring may be performed to make the mixing of the bottom ash and the antibacterial coating component more uniform, and at this time, if the stirring method is a method that can achieve uniform mixing of the liquid antibacterial coating component dispersion and the solid bottom ash, the type It can be used without limitation, and a mechanical stirrer can be used in general.

By mixing and stirring the bottom ash and the liquid antibacterial coating component according to step a), the antibacterial coating component including zinc oxide nanoparticles, an aqueous emulsion binder and a pigment is immersed in the surface and internal pores of the bottom ash or inside It is contained in the pores, so that each component can be uniformly coated on the surface or pores of the bottom ash.

On the other hand, the step (b) in the manufacturing method of the antimicrobial porous body composition according to the present invention is a step of drying the bottom ash-antibacterial coating component mixture prepared in step (a), and the aqueous solution component in the aqueous emulsion of the antibacterial coating component is dried. It corresponds to the step of removing and fixing the zinc oxide nanoparticles and pigments in the antibacterial coating component to the bottom ash by an emulsion binder.

Here, the drying step may use hot air drying or drying by an oven, and the drying temperature may be in the range of 80 to 250 ° C, preferably 100 to 200 ° C, and the drying time may vary depending on the drying temperature. However, the antimicrobial porous body composition can be finally prepared by drying for typically 5 minutes to 5 days, preferably 8 minutes to 24 hours, and more preferably 10 minutes to 12 hours.

On the other hand, each component and content of the bottom ash and antibacterial coating component used in the manufacturing method of the antimicrobial porous body composition according to the present invention is the same as described above.

The antibacterial porous body composition prepared by the manufacturing method according to the present invention contains zinc oxide nanoparticles as an antibacterial component on the surface and / or internal pores of bottom ash, which is an inorganic porous body, to remove pollutants in the surrounding air and / or aquatic environment It can also exhibit a reduction rate of 99% or more, preferably 99.9% or more, in microbial propagation.

Therefore, the antibacterial porous body composition can be used as a substitute for soil for growing plants indoors and included in pots. In this case, since the conventionally supplied water is filtered and discharged to the lower part in addition to the antibacterial effect, a water support is not required, and the water is left unattended for a long time to prevent contamination.

In addition, the antibacterial porous body composition according to the present invention is provided in a wreath, etc., and can have an effect of preventing contamination of flowers in the wreath by removing contaminants in the surrounding air through antibacterial activity.

In addition, the antibacterial porous body composition may be used for decoration in a tank or for growing fish species. In this case, by adsorbing and removing contaminants in the aquatic environment and exhibiting antibacterial activity, the amount of dissolved oxygen (DO) is increased, and the amount of chemical and biological oxygen (BOD and COD) is reduced to grow fish species in the tank. It has the effect of providing an optimal aquatic environment.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as being limited by these examples.

<Examples 1 to 3>

A bottom ash-antibacterial coating component mixture was prepared by mixing and stirring 30 g of antibacterial coating component with 1 kg of bottom ash having an average particle size of 3 mm, and the antibacterial coating component was zinc oxide nanoparticles, aqueous emulsion as shown in Table 1 below Contains 0.5 to 4% by weight of zinc oxide nanoparticles with an average particle size of 10 to 20 nm, 5% by weight of carbon black, and components of the acrylic emulsion (based on solid content) shown in Table 1, based on the total weight of 100% by weight of the total weight of the binder and pigment , 25 g of water as an additional component was mixed to prepare a bottom ash-antibacterial coating component mixture, and then the obtained bottom ash-antibacterial coating component mixture was dried at a temperature of 150° C. for 1 hour to obtain an antimicrobial porous body composition.

<Comparative Examples 1 to 2>

Except for changing the content of zinc oxide nanoparticles or the content of the binder in the antibacterial coating component of Example 1 as shown in Table 1, the bottom ash-antibacterial coating component mixture was prepared under the same conditions as in Example 1. prepared and dried in the same way.

Composition of coating ingredients Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Carbon black (% by weight) 5 5 5 5 5 Zinc Oxide Nanoparticles (% by weight) 0.5 One 4 0 0.1 Binder (% by weight) 94.5 94 91 95 94.9

<Experimental example>

A microbial antibacterial activity test was performed using the antimicrobial porous body compositions of Examples 1 to 3 and Comparative Examples 1 to 2. At this time, the microorganisms subject to the antibacterial activity test are Escherichia coli (E.coli) and Staphylococcus aureus (S.aureus), and the antibacterial activity test results for each microorganism are shown in Tables 2 and 3 below.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Inoculum E. coli concentration (CFU/mL) 2.4*10^6 B ₀ (CFU/mL) ^* 2.4*10^6 B ₂₄ (CFU/mL) ^** 8.4*10^6 A ₂₄ (CFU/mL) ^*** 2.5*10^4 <10 <10 8.4*10^6 8.1*10^5 Decrease rate (%) ^**** 99.7 >99.9 >99.9 0 90.4

*B ₀ : E. coli concentration right after inoculation (0 hour later) of microbial medium (standard sample) that does not contain antibacterial porous body composition

**B ₂₄ : E. coli concentration after 24 hours of culture in a microbial medium (standard sample) that does not contain an antimicrobial porous body composition

***A ₂₄ (Antibacterial processed sample): E. coli concentration after 24 hours of cultivation of the microbial medium (antibacterial processed sample) containing the antibacterial porous body composition

**** Reduction rate: (B ₂₄ -A ₂₄ )/(B ₂₄ )*100 (%)

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Inoculation Staphylococcus aureus concentration (CFU/mL) 2.1*10^8 B ₀ (CFU/mL) ^* 2.1*10^5 B ₂₄ (CFU/mL) ^** 7.3*10^6 A ₂₄ (CFU/mL) ^*** <10 <10 <10 7.3*10^6 4.9*10^6 Decrease rate (%) ^**** >99.9 >99.9 >99.9 0 32.9

*B ₀ : Concentration of Staphylococcus aureus right after inoculation (0 hour later) of microorganism medium (standard sample) that does not contain antibacterial porous body composition

**B ₂₄ : Concentration of Staphylococcus aureus after 24 hours of culture in a microbial medium (standard sample) that does not contain an antibacterial porous body composition

***A ₂₄ (Antibacterial processed sample): Concentration of Staphylococcus aureus after 24 hours of cultivation of the microbial medium (antibacterial processed sample) containing the antibacterial porous body composition

**** Reduction rate: (B ₂₄ -A ₂₄ )/(B ₂₄ )*100 (%)

As shown in Table 2 and Table 3, the antibacterial porous body composition prepared by Examples 1 to 3 according to the present invention has an excellent antibacterial effect compared to the porous body composition in Comparative Examples 1 and 2, and as a result , The porous body composition prepared according to the present invention is judged to have high applicability because it can exhibit antibacterial activity of 99% or more.

Claims (9)

bottom ash; and an antibacterial coating component coated on at least a portion of the surface of the bottom ash or at least a portion of internal pores of the bottom ash;
The antibacterial coating component includes zinc oxide nanoparticles, an aqueous emulsion binder and a pigment,
The content of the zinc oxide nanoparticles is in the range of 0.7 to 5% by weight when the total of the zinc oxide nanoparticles, the aqueous emulsion binder and the pigment is 100% by weight,
The average particle size of the zinc oxide nanoparticles ranges from 5 to 900 nm,
The antimicrobial porous body composition, characterized in that the content of the binder is in the range of 85 to 95 wt% when the total of the zinc oxide nanoparticles, the aqueous emulsion binder and the pigment is 100 wt%.
delete delete According to claim 1,
The pigment is at least one selected from carbon black and transition metal oxide,
The antimicrobial porous body composition, characterized in that the content of the pigment is in the range of 1 to 10% by weight when the total of the zinc oxide nanoparticles, the aqueous emulsion binder and the pigment is 100% by weight.
According to any one of claims 1 and 4,
The antimicrobial porous body composition is an antibacterial porous body composition, characterized in that provided in a wreath, flowerpot or water tank.
In preparing an antibacterial porous body composition,
(a) bottom ash; preparing a bottom ash-antibacterial coating component mixture by mixing and stirring; and zinc oxide nanoparticles, an antibacterial coating component including a water-based emulsion binder and a pigment; and
(b) preparing an antimicrobial porous body composition by drying the bottom ash-antibacterial coating component mixture;
The content of the zinc oxide nanoparticles is in the range of 0.7 to 5% by weight when the total of the zinc oxide nanoparticles, the aqueous emulsion binder and the pigment is 100% by weight,
The average particle size of the zinc oxide nanoparticles ranges from 5 to 900 nm,
The content of the binder is in the range of 85 to 95 wt% when the total of the zinc oxide nanoparticles, the aqueous emulsion binder and the pigment is 100 wt%. Method for producing an antimicrobial porous body composition according to claim 1.
An ornamental water tank comprising the antibacterial porous body composition according to claim 5.
An ornamental flower pot comprising the antibacterial porous body composition according to claim 5.
An ornamental wreath comprising the antibacterial porous body composition according to claim 5.

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