KR102169337B1 - Ceramic Bio Media Having Adsorption Of Nitrogen And Phosphorous And Manufacturing Method Of The Same - Google Patents

Abstract

A ceramic microbial carrier adsorbing nitrogen and phosphorus and a method for producing the same are disclosed. In the present invention, ammonia nitrogen adsorption type ceramic microbial carrier, nitrate nitrogen adsorption type ceramic microbial carrier, and phosphorus adsorption type ceramic microbial carrier are used in combination. According to the present invention, the ceramic microbial carrier creates foaming pores so that microorganisms reside in the ceramic carrier that adsorbs ammonia nitrogen, nitrate nitrogen, and phosphorus, so that the adsorbed material reproduces the pore initialization effect through feeding activity for a long time. Can be used.

Description

Ceramic Bio Media Having Adsorption Of Nitrogen And Phosphorous And Manufacturing Method Of The Same {Ceramic Bio Media Having Adsorption Of Nitrogen And Phosphorous And Manufacturing Method Of The Same}

The present invention relates to a ceramic microbial carrier for adsorption of nitrogen and phosphorus and a method for manufacturing the same, and more particularly, to a ceramic microbial carrier for adsorption of nitrogen and phosphorus for purifying the water quality of a terrestrial farm, aquatic aquarium, and aquarium fish About.

The concept of water purification for conventional breeding tanks is to purify water contaminated from ammonia nitrogen, nitrate nitrogen, and phosphorus from excrement or remaining feed from fish, aquatic plants, shellfish, etc.

Methods of purifying water quality can be divided into methods that depend on food activity by microorganisms and adsorbents that adsorb specific substances.

Methods of using the adsorbent include, in detail, a method of removing the adsorbed material using sulfur, a method of removing it by a mechanical device, and a method of removing it using a microorganism.

The method that depends on the feeding activity of microorganisms is to use a carrier using microorganisms, which was initially developed for water purification in sewage and wastewater treatment facilities, and later spread to aquaculture.

The microbial carrier for water purification is manufactured mainly in the form of a form of securing abrasion stability during aeration, creating a microbial habitat space with a siliceous porous body, PP, PVC, and styrofoam spheres, and surface roughness for adhesion.

Microbial carriers are classified into an external attachment type and an internal attachment type depending on where the microorganism is grown. The internally attached carrier is a product with large pores, and the externally attached carrier induces surface attachment to a floating point like styrofoam relief.

The types of microbial carriers vary depending on their shape, such as spherical, disc-shaped, filamentous, square, and honeycomb, and materials such as polyethylene, hard-soft vinyl-based, and siliceous porous ceramic carriers are used.

However, most of the prior art uses ceramic adsorbents that adsorb all of ammonia nitrogen, nitrate nitrogen, and phosphorus, adsorbs ammonia nitrogen and phosphorus, adsorbs ammonia nitrogen and phosphorus, or adsorbs ammonia nitrogen. Products, which cannot be adsorbed, but have a function of inhabiting microorganisms due to a large number of pores are known.

However, conventional water purification products have limitations in long-term use because the adsorption function and the microbial habitat function are separate from each other, or are used in a manner that adsorbs all pollutants.

Korean Patent Application No. 10-2016-0010803 Korean Patent Application No. 10-2014-0010137 Korean Patent Application No. 10-2012-0010361 Korean Patent Application No. 10-2011-0055054 Korean Patent Application No. 10-2006-0000684 Korean Patent Application No. 10-2001-0080797 Korean Patent Application No. 10-2001-0038975 Korean Patent Application No. 10-2006-0017884 Korean Patent Application No. 10-2003-0038416

The present invention was conceived in view of the above-described problems, and its object is to create foam pores so that microorganisms reside in a ceramic carrier that adsorbs ammonia nitrogen, nitrate nitrogen, and phosphorus, and the adsorbed material is pores through feeding activities. It is to provide a ceramic microbial carrier for adsorption of nitrogen and phosphorus and a method for producing the same to reproduce the initialization effect.

In addition, the present invention is a mixture of ammonia nitrogen adsorption type ceramic microbial carrier, nitrate nitrogen adsorption type ceramic microbial carrier, and phosphorus adsorption type ceramic microbial carrier at a certain ratio to enable both the adsorption function of ceramic and the characteristics of the feeding activity of microorganisms. It is intended to provide a ceramic microbial carrier for adsorption of nitrogen and phosphorus and a method for manufacturing the same, which can improve the water purification function by providing a rich feeding activity and habitat environment for microorganisms.

The nitrogen and phosphorus adsorption-type ceramic microbial carrier of the present invention for solving the above problems is silica sol 5 to 15 wt%, water 5 to 10 wt%, anhydrous ethanol 20 to 25 wt%, bentonite 10 to 15 wt% %, sodium bicarbonate is 1 to 4% by weight, talc or dolomite is 5 to 15% by weight, zeolite as a main material is 30 to 40% by weight of ammonia nitrogen adsorption type ceramic microbial carrier formed by mixing, molding, drying and firing; Silica sol is 5 to 15% by weight, water is 5 to 10% by weight, anhydrous ethanol is 20 to 25% by weight, bentonite is 10 to 15% by weight, sodium bicarbonate is 1 to 4% by weight, talc or dolomite is 5 to 15 A ceramic microbial carrier adsorbing nitrate nitrogen formed by mixing, molding, drying and sintering 30 to 40% by weight of activated alumina as a main material by weight; And silica sol is 5 to 15% by weight, water is 5 to 10% by weight, anhydrous ethanol is 20 to 25% by weight, bentonite is 10 to 15% by weight, sodium bicarbonate is 1 to 4% by weight, talc or dolomite is 5 to 15% by weight, magnesium oxide, which is the main material, contains a phosphorus adsorption type ceramic microbial carrier formed by mixing, molding, drying and firing 30 to 40% by weight, and the ammonia nitrogen adsorption type ceramic microbial carrier, nitrate nitrogen adsorption type A ceramic microbial carrier and a phosphorus adsorption type ceramic microbial carrier are used in combination.

In the present invention, the size of the ceramic microbial carrier adsorbing nitrogen and phosphorus may have a diameter of 10 mm or more, and a specific surface area of 160 to 200 m ² /g.

The method for preparing a ceramic microbial carrier adsorbing nitrogen and phosphorus according to the present invention for solving the above-described other problems includes 5 to 15% by weight of silica sol, 5 to 10% by weight of water, 20 to 25% by weight of anhydrous ethanol, and bentonite. Ammonia nitrogen adsorption type ceramic microorganism by mixing, molding, drying and firing 10 to 15 wt%, sodium bicarbonate 1 to 4 wt%, talc or dolomite 5 to 15 wt%, and zeolite as the main material 30 to 40 wt% Forming a carrier; Silica sol is 5 to 15% by weight, water is 5 to 10% by weight, anhydrous ethanol is 20 to 25% by weight, bentonite is 10 to 15% by weight, sodium bicarbonate is 1 to 4% by weight, talc or dolomite is 5 to 15 Mixing, molding, drying, and sintering 30 to 40% by weight of zeolite as the main material by weight, forming a nitrate nitrogen adsorption type ceramic microbial carrier; Silica sol is 5 to 15% by weight, water is 5 to 10% by weight, anhydrous ethanol is 20 to 25% by weight, bentonite is 10 to 15% by weight, sodium bicarbonate is 1 to 4% by weight, talc or dolomite is 5 to 15 Mixing, molding, drying, and firing 30 to 40% by weight of zeolite as a main material by weight to form a phosphorus adsorption type ceramic microbial carrier; And mixing the ammonia nitrogen adsorption type ceramic microbial carrier, the nitrate nitrogen adsorption type ceramic microbial carrier, and the phosphorus adsorption type ceramic microbial carrier.

In the present invention, the mixing, shaping, drying, and sintering are 10 to 15% by weight of bentonite, 1 to 4% by weight of sodium bicarbonate, 5 to 15% by weight of talc or dolomite and zeolite, activated alumina, or oxidation. Preparing a ceramic powder by mixing 30 to 40% by weight of the main material, which is one of magnesium; Mixing the ceramic powder with silica sol, which is a liquid binder, and water for at least 30 seconds and not more than 5 minutes, adding anhydrous ethanol to complete the mixing within 30 seconds, and forming a mixture in which the precipitate is evenly spread; Performing a molding process of the mixture in the shape of a ceramic microbial carrier molding; A drying step of removing the anhydrous ethanol before firing the molded product at 100° C. or higher for 24 hours or longer; And firing the dried molded product at 500 to 550° C., and a firing step of maintaining the temperature for 1 hour and 8 hours. In the drying step, sodium bicarbonate is separated from carbon dioxide at 65° C. or higher, so that the ceramic molded product may foam.

According to the present invention having the configuration as described above, the ceramic microbial carrier forms foam pores so that microorganisms reside in the ceramic carrier adsorbing ammonia nitrogen, nitrate nitrogen, and phosphorus, and the adsorbed material is pores through the feeding activity. It can be used for a long time by reproducing the initialization effect.

In addition, the present invention is a mixture of ammonia nitrogen adsorption type ceramic microbial carrier, nitrate nitrogen adsorption type ceramic microbial carrier, and phosphorus adsorption type ceramic microbial carrier at a certain ratio to enable both the adsorption function of ceramic and the characteristics of the feeding activity of microorganisms. By using it, it can improve the water purification function by providing abundant feeding activities and habitat environment for microorganisms.

In addition, the present invention is produced by consisting of a material that adsorbs nitrogen and phosphorus in water required for the growth of microorganisms, thereby improving early adhesion of microorganisms and adhering within 10 days, and smooth water quality conditions can be achieved within 1.5 months. It has a self-cleaning effect that consumes nitrogen and phosphorus adsorbed by the growth of adherent microorganisms.

In addition, as the composition of the ceramic microbial carrier of the present invention, it can contribute to reducing raw material purchase cost and recycling resources by utilizing by-products of a coal-fired power plant.

1 is a photograph showing the shape of a ceramic microbial carrier according to an embodiment of the present invention.
2 is a photograph showing a ceramic microbial carrier to be removed from nitrogen according to an embodiment of the present invention.
3 is a photograph showing a ceramic microbial carrier to be removed phosphorus.
4 is a photograph showing an aquarium to which the developed product of Table 5 is applied and an aquarium to which other companies' comparative products are applied to Table 6.

Hereinafter, a ceramic microbial carrier having a function of adsorbing nitrogen and phosphorus according to a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings.

Existing products were specifically developed as adsorption or carriers, and their applications were used differently. Among the adsorption-type microbial carriers, the most similar products are the ammonia nitrogen adsorption-type microbial carriers, which are affected by the applied microbes and aeration.

The ceramic microbial carrier of the present invention has phosphorus adsorption properties and nitrate nitrogen adsorption properties not found in conventional carriers. In addition, by adsorbing nitrate nitrogen and phosphorus, it induces microorganisms to inhabit the pores formed inside. Nitric acid nitrogen and phosphorus that have already been adsorbed by the feeding activity of microorganisms are consumed. Repeated adsorption is possible due to the cleaning effect by consumption.

The ceramic microbial carrier of the present invention is used for a long time by creating foam pores so that microorganisms reside in the ceramic carrier that adsorbs ammonia nitrogen, nitrate nitrogen, and phosphorus, so that the adsorbed material reproduces the pore initialization effect through feeding activities. It has the function to do.

In the present invention, ammonia nitrogen adsorption type ceramic microbial carrier, nitrate nitrogen adsorption type ceramic microbial carrier, and phosphorus adsorption type ceramic microbial carrier are mixed in a certain ratio to enable both the adsorption function of ceramics and the feeding activity of microorganisms. It is to provide a rich feeding activity and habitat environment for microorganisms.

According to the present invention, as a ceramic adsorbent, zeolite for ammonia nitrogen, activated alumina for nitrate nitrogen, and magnesium oxide for phosphorus as main materials have an adsorption function.

Magnesium oxide, which adsorbs phosphorus, is strictly chemically bonded to phosphorus to form crystals. Since the crystals produced by the bonding with phosphorus block the pores, the function is terminated within a short period of time when it is fired after mixing with an adsorbent for removing nitrogen. Because of this problem, a separate ceramic adsorbent is prepared by each composed of zeolite, activated alumina, and magnesium oxide as main materials, and used after installation in one bioreactor (fixed, suspended, filled) or filter.

In the present invention, it is characterized in that three types of adsorption-type ceramic microbial carriers made of each of zeolite, gamma-alunima, and magnesium oxide are mixed in an appropriate ratio and used.

Table 1 shows the component ratio of the ammonia nitrogen adsorbing type ceramic microbial carrier according to a preferred embodiment of the present invention.

division Liquid binder Ceramic powder system
combination
ratio
Silica sol water Anhydrous ethanol sub Total Bentonite Sodium bicarbonate Talc or dolomite Zeolite sub Total 10 5 25 40 10 2 10 38 60 100

The components of the ammonia nitrogen adsorption-type ceramic microbial carrier are silica sol 5 to 15% by weight, water 5 to 10% by weight, anhydrous ethanol 20 to 25% by weight, bentonite 10 to 15% by weight, sodium bicarbonate 1 to 4 wt%, talc or dolomite may be 5 to 15 wt%, and zeolite as a main material may be 30 to 40 wt%.

Table 2 shows the component ratio of the nitrate nitrogen adsorbing type ceramic microbial carrier according to a preferred embodiment of the present invention.

division Liquid binder Ceramic powder system
combination
ratio
Silica sol water Anhydrous ethanol sub Total Bentonite Sodium bicarbonate Talc or dolomite Activated alumina sub Total 10 5 25 40 10 2 10 38 60 100

The components of the nitrate nitrogen adsorption-type ceramic microbial carrier are silica sol 5 to 15% by weight, water 5 to 10% by weight, anhydrous ethanol 20 to 25% by weight, bentonite 10 to 15% by weight, sodium bicarbonate 1 to 4 wt%, talc or dolomite may be 5 to 15 wt%, and activated alumina as a main material may be 30 to 40 wt%.

Table 3 shows the component ratios of the phosphorus adsorption type ceramic microbial carrier according to a preferred embodiment of the present invention.

division Liquid binder Ceramic powder system
combination
ratio
Silica sol water Anhydrous ethanol sub Total Bentonite Sodium bicarbonate Talc or dolomite Magnesium oxide sub Total 10 5 25 40 10 2 10 38 60 100

The components of the phosphorus adsorption-type ceramic microbial carrier are silica sol 5 to 15% by weight, water 5 to 10% by weight, anhydrous ethanol 20 to 25% by weight, bentonite 10 to 15% by weight, sodium bicarbonate 1 to 4% %, talc or dolomite may be 5 to 15% by weight, and magnesium oxide as a main material may be 30 to 40% by weight.

Hereinafter, a method of manufacturing a ceramic microbial carrier having a function of adsorbing nitrogen and phosphorus according to the present invention will be described. The ceramic microbial carrier must be made in such a way that its material and shape are suitable for the characteristics of the microbes, so that a place where microbes can be concentrated and grown must be provided.

The ceramic microbial carrier of the present invention is prepared by mixing a liquid binder and a ceramic component having the components shown in Tables 1 to 3.

(Mixing and molding process)

First, as described above in Tables 1 to 3 and related descriptions, ceramic powder containing main materials (zeolite, activated alumina, and magnesium oxide) is mixed and prepared.

Next, silica sol, which is a liquid binder, and water are first mixed with the ceramic powder for 30 seconds or more and 5 minutes or less, and anhydrous ethanol is added to complete the mixing within 30 seconds, thereby forming a mixture in which the precipitate is evenly spread.

Next, the mixture is subjected to a molding process in the shape of a ceramic microbial carrier molded product using a molding machine.

(Mixing and molding process)

First, as described above in Tables 1 to 3 and related descriptions, ceramic powder containing main materials (zeolite, activated alumina, and magnesium oxide) is mixed and prepared.

Next, silica sol, which is a liquid binder, and water are first mixed with the ceramic powder for 30 seconds or more and 5 minutes or less, and anhydrous ethanol is added to complete the mixing within 30 seconds, thereby forming a mixture in which the precipitate is evenly spread.

Next, the mixture is subjected to a molding process in the shape of a ceramic microbial carrier molded product using a molding machine.

(Drying and foaming process)

Next, the drying process of the molded product is performed. Since anhydrous ethanol was used for the liquid binder, it was dried at 100° C. or higher for 24 hours or longer to remove the anhydrous ethanol before firing.

In addition, in the drying process, sodium bicarbonate is separated from carbon dioxide at 65°C or higher, and the ceramic molded product foams. After that, the silica sol completes the coating, which increases the strength of the product. The surface of the carrier thus prepared has various combinations of small pores of about 0.001 mm to 0.05 mm and micro pores of about 0.1 μm to 1 μm, so that water permeability is good and various microorganisms can live according to their size or shape. There is a feature that is made to be able to.

Since the blending of the present invention does not use an organic binder at all, the foaming is achieved by applying sodium bicarbonate for foaming. In the case of conventional adsorbents or carriers, organic binders are mostly used, but since the present invention uses sodium bicarbonate, it is foamed in a drying process of 100°C or higher.

(Firing process)

The dried product is sintered at 500~550℃, and the temperature is raised for 1 hour and maintained for 8 hours.

If the calcination temperature exceeds 550°C and is sintered for a long time, the structure of the zeolite is collapsed and ammonia nitrogen cannot be adsorbed.

In the present invention, since organic substances are not mixed, it is preferable to extend the holding time to 8 hours or longer.

In addition, in the present invention, the strength of bentonite and dolomite or talc is combined with the silica sol to improve strength, but after firing, the strength is increased. During aeration for nitrification of ammonia nitrogen contained in land aquaculture, the ceramic microbial carrier must flow and secure a stable strength of 1 MPa or more or a wear rate of 10% or less against damage caused by collision between groups caused by flow.

1 is a photograph of a ceramic microbial carrier according to an embodiment of the present invention.

Referring to FIG. 1, the size of the ceramic microbial carrier finally prepared after firing is 10 mm or more in diameter, and the specific surface area is 160 to 200 m ² /g.

FIG. 2 is a photograph showing the shape of a ceramic microbial carrier to be removed from nitrogen according to an embodiment of the present invention, and FIG. 3 is a photograph showing the shape of a ceramic microbial carrier to be removed from phosphorus.

Hereinafter, the function of purifying water of the ceramic microbial carrier according to the present invention will be described.

In terrestrial aquaculture farms, ornamental fish aquariums, and aquatic aquariums that raise marine products, the rates of nitrogen and phosphorus generation differ depending on the breeding target.

Accordingly, the ceramic microbial carrier of the present invention can be used by setting different usage ratios depending on the amount of ammonia nitrogen, nitrate nitrogen, and phosphorus generated according to the bioreactor, the filtration tank, and the filter.

Table 4 shows the state of improving water quality after the adsorption experiment by differently mixing the adsorption-type ceramic microbial carriers prepared according to the ratios of Tables 1 to 3.

division
Complex adsorption type ceramic membrane microbial carrier mixing ratio Adsorption rate (%) Ammonia nitrogen adsorption type ceramic microbial carrier Nitric acid nitrogen adsorption type ceramic microbial carrier Phosphorus adsorption type ceramic microbial carrier system NH ₄ -N T-N PO ₄ -P T-P 1 eye 2 7 One 10 100 100 100 100 2 eyes 2 6 2 10 100 95.6 100 100 3 eyes 2 5 3 10 100 91.3 100 100 4 eyes One 7 2 10 100 100 100 100 5 eyes One 6 3 10 100 96.7 100 100 6 eyes One 5 4 10 100 92.4 100 100

As shown in Table 4, the mixing ratio of eye 1 and eye 4 showed the highest adsorption rate.

The water quality of the test water used in the experiment was 19.462 ppm for ammonia nitrogen (NH ₄ -N), 64.246 ppm for nitrate nitrogen (TN), 2.36 ppm for phosphorus phosphate (PO ₄ -P), and 6.49 for total phosphorus (TP). ppm.

The adsorption test for each ratio of the composite adsorption-type ceramic microbial carrier was conducted for 1 day, and Table 4 shows the removal rate for each item.

After mixing the composite adsorption-type ceramic microbial carrier in a ratio of 1, it was applied to the breeding tank of 100 guppies for performance comparison with other products, and the results are shown in the table below.

4 is a photograph showing an aquarium to which a developed product is applied and an aquarium to which a comparative product of another company is applied.

Referring to FIG. 4, it can be seen that the water quality of the aquarium to which the developed product of the present invention is applied is remarkably improved.

The present invention described above is not limited by the above drawings and detailed description, and various modifications and changes by those skilled in the art within the scope not departing from the spirit and scope of the present invention described in the following claims. It is of course also included within the scope of the present invention.

Claims (5)

delete delete Silica sol is 5 to 15% by weight, water is 5 to 10% by weight, anhydrous ethanol is 20 to 25% by weight, bentonite is 10 to 15% by weight, sodium bicarbonate is 1 to 4% by weight, talc or dolomite is 5 to 15 Mixing, molding, drying, and sintering 30 to 40% by weight of zeolite as a main material by weight to form an ammonia nitrogen adsorbing ceramic microbial carrier;
Silica sol is 5 to 15% by weight, water is 5 to 10% by weight, anhydrous ethanol is 20 to 25% by weight, bentonite is 10 to 15% by weight, sodium bicarbonate is 1 to 4% by weight, talc or dolomite is 5 to 15 Mixing, molding, drying, and sintering 30 to 40% by weight of activated alumina as a main material by weight to form a nitrate nitrogen adsorption type ceramic microbial carrier;
Silica sol is 5 to 15% by weight, water is 5 to 10% by weight, anhydrous ethanol is 20 to 25% by weight, bentonite is 10 to 15% by weight, sodium bicarbonate is 1 to 4% by weight, talc or dolomite is 5 to 15 Mixing, molding, drying, and sintering 30 to 40% by weight of magnesium oxide as a main material by weight to form a phosphorus adsorption-type ceramic microbial carrier; And
Including the step of mixing the ammonia nitrogen adsorption type ceramic microbial carrier, nitrate nitrogen adsorption type ceramic microbial carrier, and phosphorus adsorption type ceramic microbial carrier,
The mixing, molding, drying, and firing,
The bentonite is 10 to 15% by weight, sodium bicarbonate is 1 to 4% by weight, talc or dolomite is 5 to 15% by weight and zeolite, activated alumina, or magnesium oxide is mixed with 30 to 40% by weight of the main material Preparing a powder;
First mixing silica sol and water as a liquid binder to the ceramic powder, adding anhydrous ethanol to complete the mixing, and forming a mixture in which the precipitate is evenly spread;
Performing a molding process of the mixture in the shape of a ceramic microbial carrier molding;
A drying step of removing the anhydrous ethanol before firing the molded product at 100° C. or higher for 24 hours or longer; And
A method of producing a ceramic microbial carrier adsorbing nitrogen and phosphorus comprising a firing step of firing the dried molded product at 500 to 550° C. and maintaining the temperature for 1 hour and 8 hours. delete The method of claim 3,
In the drying step, sodium bicarbonate is a method for producing a ceramic microbial carrier adsorbing nitrogen and phosphorus, characterized in that the carbon dioxide is separated at 65° C. or higher to form a ceramic molded product.

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