KR102006574B1 - A water-based natural purification type kaolin ecological block immobilized by coating a composite useful microorganism for algae reduction and purification of water by removal of total phosphorus and total nitrogen and its method for manufacturing - Google Patents

Abstract

The present invention relates to a water-based natural purification type kaolin ecological block immobilized by coating a composite effective microorganism for algae reduction and water purification by removal of total phosphorous and total nitrogen, and a manufacturing method thereof. More specifically, the present invention relates to a water-based natural purification type kaolin ecological block immobilized by coating a composite effective microorganism for purification, restoration and maintenance of water according to a non-point pollution source caused by total phosphorous and total nitrogen and a manufacturing method thereof. The water-based natural purification type kaolin ecological block immobilized by coating a composite effective microorganism, is manufactured by adding at least one of polycarboxylic acid, a first microorganism strain mixture, a second microorganism strain mixture, a denitrification strain, methyl cellulose, starch acetate, slaked lime and water to a base material which is formed by comprising 65 to 79 wt% of dolomite or stone flour, 15 to 25 wt% of OPC or blast furnace slag cement and 6 to 10 wt% of kaolin.

Description

Water-based natural purifying kaolin ecological block and its manufacturing method coated with complex useful microorganisms for the purpose of purifying water by reducing total phosphorus (TP), total nitrogen (TN) and reducing green algae {A WATER-BASED NATURAL PURIFICATION TYPE KAOLIN ECOLOGICAL BLOCK IMMOBILIZED BY COATING A COMPOSITE USEFUL MICROORGANISM FOR ALGAE REDUCTION AND PURIFICATION OF WATER BY REMOVAL OF TOTAL PHOSPHORUS AND TOTAL NITROGEN AND ITS METHOD FOR MANUFACTURING}

The present invention relates to a water-based natural purified kaolin ecological block and a method for manufacturing the same, which are immobilized by coating a complex useful microorganism for the purpose of purifying water by reducing total phosphorus (TP) and total nitrogen (TN) and reducing green algae. The present invention relates to a water-based natural purified type kaolin ecological block immobilized with a coating microorganism for the purpose of water purification and restoration and maintenance according to non-point source caused by total phosphorus and total nitrogen.

Recently, a sustainable and eco-friendly natural purification technology is required as a concept of water-conscious purification. On the other hand, in Korea, various media used for the purification of point sources and nonpoint sources such as domestic sewage, agriculture, livestock waste, and industrial wastewater are used for chemical treatment, physical filtration, etc. Although many methods are used, cement, the main material of ecological blocks, is strong alkali (pH> 12), so that the growth environment of microorganisms is not established. In particular, due to the limitation of the natural purification function of non-point source caused by total phosphorus and total nitrogen, water, ecosystem, and algae phenomena are caused by pollution of natural water system. Therefore, by applying the complex useful microbial coating method to various ecological blocks used in rivers, lakes, lakes, wastewater, and wastewater treatment plants, it is a natural purification technology that is sustainable by immobilization of microorganisms. have. Therefore, the water-based natural purified kaolin ecological block and the manufacturing method thereof can be considered as an alternative to the immobilization of complex useful microorganisms for the purpose of purifying water by total phosphorus (TP), total nitrogen (TN) removal, and green algae reduction. have.

The present invention has been made in view of the above-mentioned, water-based natural purified type kaolin ecological block immobilized with a coating of complex useful microorganisms for the purpose of purifying water by the removal of total phosphorus (TP) and total nitrogen (TN) and green algae reduction; It provides a method for producing the same.

In order to achieve the above object, the present invention is a polycarboxylic acid, the first microorganism strain mixture in the base material formed of dolomite or stone powder 65 ~ 79wt%, OPC or blast furnace slag cement 15 ~ 25wt%, kaolin 6 ~ 10wt% It provides a water-based natural purified kaolin ecological block immobilized by coating the composite useful microorganism, characterized in that the composition of the second microorganism strain, denitrification strain, methyl cellulose, starch acetate, slaked lime, water is added.

In one embodiment, the components added together to the base material is 1 to 4 wt% of the polycarboxylic acid, 1 to 1.5 wt% of the first microbial strain mixture, 1 to 2 second microbial strain mixture relative to the total weight of the base material 1.5wt%, denitrification strain 0.5 ~ 1wt%, methyl cellulose 0.1 ~ 0.5wt%, starch acetate 3 ~ 10wt%, calcined lime 0.1 ~ 0.5wt%, water may be 81 ~ 93.3wt.

In one embodiment, the particle size of the dolomite or stone powder may be 0.8 ~ 23mm or less.

In one embodiment, the specific surface area of the OPC or blast furnace slag cement may be 4,000 ~ 5,000cm² / g.

In one embodiment, the particle size of the kaolin may be 80% or more of 200mesh passage.

In one embodiment, the first microbial strain mixture, Lactobacillus bacteria (Lactobacillus), An erase Caro My process (Saccharomyces), A also Pseudomonas (Rhodopsedomonas) genus Streptomyces (Streptomyces) lie 0.2 ~ 0.3: 0.18 ~ 0.28: 0.3-0.5: 0.02 weight ratio may be mixed.

In one embodiment, the second microorganism strain mixture, Bacillus (Bacillus) genus of Bacillus megateurium (Bacillus Megatrium), Bacillus poly miksa (Bacillus Polymixa), Bacillus core roasting Alliance (Bacillus Coaguians) is 0.5: 0.3: 0.1 It may be mixed in a ratio of 0.1 by weight.

In one embodiment, the inside of the Bacillus (Bacillus) mesophilic and thermophilic species paper 1 can be mixed with 1 weight ratio.

The present invention, as the additive is added to the base material of dolomite or stone powder, OPC or blast furnace slag cement, kaolin, the composite useful microorganism for the purpose of purifying water by removing total phosphorus (TP), total nitrogen (TN), green algae reduction A water-purified kaolin ecological block immobilized with a coating and a manufacturing method thereof are implemented. In addition, the present invention implements a method for producing a water-based natural purified kaolin ecological block by coating and fixing the composite useful microorganism by the mixing ratio of the additive.

1 is a flow chart showing a method of manufacturing a water-based natural purified kaolin ecological block by immobilizing the coating of the composite useful microorganism according to an embodiment of the present invention.
Figure 2 is a real picture of the water-based natural purification type kaolin ecological revetment block immobilized coating a composite useful microorganism according to an embodiment of the present invention.
Figure 3a is a real picture of the water-based natural purification kaolin ecological bedrock block immobilized coating the composite useful microorganism according to an embodiment of the present invention.
3B and 3C are SEM photographs of the blocks described in FIGS. 2 and 3A.
Figure 4 is a schematic diagram of the water-based natural purified type kaolin ecological retaining wall block of the immobilized coating the composite useful microorganism according to an embodiment of the present invention.
Figure 5 is a schematic diagram of the water-based natural purification type kaolin ecological fishery block coated with a composite useful microorganism according to an embodiment of the present invention.
Figure 6 is a system schematic diagram of the water-based natural purified kaolin ecological block of the coating and immobilized complex useful microorganism according to an embodiment of the present invention.
Figure 7 is a photograph showing the results of the test of the coating complex microorganism strains using the samples prepared in Examples 1 to 2.
8 to 11 is a graph showing the results of performing a complex useful microbial strain individual test using the samples prepared in Examples 1 to 2.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention. The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. The terms "comprises" or "having" in the present application are intended to indicate that there is a feature, number, component, or combination thereof described in the specification, and that one or more other features or numbers, components, or It should be understood that it does not exclude in advance the possibility of the presence or addition of combinations.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art.

Terms such as those defined in the commonly used dictionaries should be construed in accordance with the meanings in the context of the related art, and shall not be construed in an ideal or excessively formal sense unless expressly defined in the present application.

Hereinafter, an embodiment of the present invention will be described. In the context of the present invention, the material of the water-based natural purified kaolin ecological block coated with the composite useful microorganism includes dolomite or stone powder, OPC, or blast furnace slag cement and kaolin base material.

As an example, the base material may be composed of dolomite or stone powder 65-79wt%, OPC or blast furnace slag cement 15-25wt%, kaolin 6-10wt%.

In addition, the base material may be formed by adding at least one of polycarboxylic acid, the first microbial strain mixture, the second microbial strain mixture, microbial denitrification strain, methyl cellulose, starch acetate, slaked lime and water.

The first microorganism strain mixtures herein are Lactobacillus bacteria (Lactobacillus), An erase Caro My process (Saccharomyces), A also Pseudomonas (Rhodopsedomonas) genus Streptomyces (Streptomyces) in one to at least two types of strain mixture Is defined.

On the other hand, the herein second microorganism strain mixture Bacillus (Bacillus) genus of Bacillus megateurium (Bacillus Megatrium), Bacillus poly miksa (Bacillus Polymixa), Bacillus core roasting Alliance that the two kinds of strain mixture of (Bacillus Coaguians) Is defined.

On the other hand, a strain and para Cocos (Paracocuus) in blood of Denny tree construct at least one of a strain belonging to the (Denitrificans) species belonging to the genus of Castle liner (Castellaniella) denitrifying microorganism strain.

Dolomite, a material of the base material, is a sedimentary rock of carbonate minerals containing calcium and magnesium, and the chemical composition is CaMg (CO ₃ ) ₂ and Mg is substituted with Fe, Mn, and the like. The ratio of Ca and Mg is less than 1: 5. White, gray or pink, yellow, brown, green. It is transparent or translucent and has glass luster. Crystal is sometimes pearl luster and has high strength and is a mineral used for timber and construction aggregates. Its particle size is 0.8 ~ 23mm or less. The dolomite is preferably used in the proportion of 65 ~ 79wt%. This significantly lowers the physical properties of the strength when used less than 65wt%, the problem of cost increases due to the high price aggregate when used over 79wt%.

The stone powder is aggregate that is generated as a by-product during the extraction and processing of the rock, the main component is SiO₂ and serves to increase the strength of the physical properties by the hydration reaction, the particle size is used below 0.8 ~ 23mm. The stone powder is preferably used in the proportion of 65 ~ 79wt%. It has a problem of strength deterioration when using less than 65wt% and a cost increase when using more than 79wt%.

OPC, which is a material of the base material, is mainly mixed with calcite and clay raw material, and the fine siliceous and iron oxide raw materials are mixed and pulverized in an appropriate ratio. And the specific surface area is 4,000 ~ 5,000cm² / g, which is made by pulverizing and has the characteristic of causing hydration reaction. The OPC is preferably used in a ratio of 15 to 25wt%. This is because the hydration reaction is lowered when using less than 15wt%, the physical properties are significantly lowered, when using more than 25wt% workability is reduced by the rapid hydration reaction and the problem of cost increase.

Blast furnace slag cement, a material of the base material, is a mixture of blast furnace slag and cement 6: 4 ratio, and the blast furnace slag occupies most of the steel slag generated in the steel mill, and when iron is manufactured in iron blast furnace or ash, Existing SiO ₂ and Al ₂ O ₃ and the like are formed by reacting with lime at a high temperature of 1,350 ~ 1,550 ° C. Since specific gravity is lower than iron, it is separated from pig iron. Quenching the molten blast furnace slag results in thermally unstable glassy slag. The hydration properties of the hydrolyzed slag were discovered by the incorporation of hydrated lime and labeled as latent hydrophobicity. The activity was determined by vitrification rate, chemical composition and powder degree. Vitrification refers to the state of having a possibility of chemical bonding with an external stimulus at any time by preserving high crystallization energy because there is no time for crystallization when cooling after high temperature heating.

The vitrification rate of blast furnace slag increases as the temperature at the time of heating is high and the cooling rate is fast. The vitrification rate of domestic blast furnace slag is more than 99% of the average group is very active. The chemical composition of domestic blast furnace slag is shown in Table 1, and SiO ₂ , Al ₂ O ₃ , CaO, MgO is 98% and the rest is trace amount of TiO ₂ , FeO, MnO, Na ₂ O ₂ , K ₂ O, P ₂ O ₅ and other components. Table 1 shows the chemical composition and physical properties of the domestic blast furnace slag.

 Production Category  Iron mill  Pohang  Light quantity  1B / F  2B / F  3B / F  4B / F  2B / F  3B / F  4B / F Chemical properties Chemical composition (%) SiO₂ 33.17 33.31 32.84 33.13 34.92 34.93 35.72 CaO 42.45 41.63 41.15 41.99 44.62 43.63 43.89 Al₂O₃ 14.41 14.60 14.03 14.01 13.94 13.47 13.42 MgO 7.00 7.21 7.79 7.65 4.63 6.38 5.51 FeO 0.38 0.40 0.41 0.33 0.41 0.38 0.40 Cl 0.043 0.006 0.027 0.011 0.074 0.056 0.012 S 0.81 0.82 0.68 0.73 0.81 0.76 0.75 SO₃ 0.074 0.034 0.04 0.04 2.02 1.90 1.87 R2O 0.38 0.48 0.43 0.34 1.06 0.39 0.407 MnO 0.53 0.44 0.39 0.28 0.32 0.32 0.32 TiO₂ 0.86 0.63 1.85 1.46 0.58 0.56 0.57 basicity 1.93 1.90 1.92 1.92 1.815 1.817 1.76 Physical properties Vitrification rate (%) 99.8 99.3 98 99.2 99.9 99.6 99.8  importance 2.91 2.92 2.91 2.94 2.94 2.90 2.92

If the glass content and chemical composition are constant, the activity of the blast furnace slag is determined by the degree of powder. That is, the higher the blast furnace slag powder, the faster the hydration reaction is because the contact area with moisture increases as the specific surface area increases. If blast furnace slag is in contact with pure water, blast furnace slag particles the surface of the hydration so formed acid coating of dense amorphous according to the dissolution of the Ca ^{2 +} suppress the elution of the water penetration and internal ions do not last. At this time, when the addition of cement as alkaline stimulant of as an irregular three-dimensional (-O-Si-O-Al -O-) chain is cut by a combination gangal potassium (pH> 12) Ca ^{2 +} that has been enveloped in the net structure, Mg ^{2 +,} Al ^{3 +,} etc. formula ions are eluted. The eluted ions produce a hydrate. The hydration product of blast furnace slag is different depending on the type of additives and stimulants, but all of them are characterized by producing calcium hydrate (CSH, representative composition C ₃ S ₂ H ₃ ).

It refers to the crushing of the slag of sand-like shaped slag into a certain powder by quenching the molten non-ferrous component contained in the blast furnace, the non-ferrous component contained in the coke and limestone with high pressure water. The blast furnace slag powder is made of a hydraulic material by other materials and additives of the base material to induce a hydration reaction. The blast furnace slag fine powder is determined by the degree of powder when the glass content and chemical composition are constant. That is, the higher the blast furnace slag powder, the more the contact area increases with the increase of the specific surface area, thereby accelerating the hydration reaction.

Therefore, the fineness of the blast furnace slag powder is preferably used having a specific surface area of less than 4,000cm² / g ~ 5,000cm² / g. In addition, the finer the finer the blast furnace slag powder is, the better the specific surface area is, but it is preferable to use less than 5,000cm² / g because of manufacturing difficulties. The blast furnace slag cement is preferably used in a proportion of 15 ~ 25wt%. This is a concern of lowering the properties of long-term strength when using less than 15wt%, there is a problem of cost increase when using more than 25wt%. The kaolin is a rock weathering of the kaolinite in the resulting mineral _{(Kaolinite, Al 2 O 3 .2SiO} 2 .2H 2 O) , and halloysite _{(Halloysite, Al 2 O 3 .2SiO} 2 .4H 2 O) and the bed plate structure It consists of a single mineral or is mixed in various proportions thereof. It contains small amounts of mica, quartz, alum, spectite and various forms of iron and titanium oxides.

The kaolin is a clay mineral whose main component is more than 65% of SiO, and has high viscosity and plasticity when added with moisture, rigidity when dried, and doubles the pozzolanic reaction. Kaolin, which is the base material, is preferably used having a grain size of 200 mesh 80% or more. This is because when the particle size is less than 200 mesh 80% pass rate, the reaction area is small and plasticity and reactivity are poor. The kaolin is preferably used at a rate of 6 ~ 10wt%. This is because when using less than 6wt%, the physical properties are significantly decreased, and when using more than 10wt%, there is a problem of cost increase as expensive raw soil.

Hereinafter, each composition of the additive added to the base material will be described in more detail. The range of content of each composition described below may be an optimum range for maximizing the synergistic effect obtained by mixing each effect and other composition obtained when using each composition.

는 Polycarboxylic Acid 와 반응해서

염이 발생하는데, Polycarboxylate 의 Backbone에 붙은 Carboxyl 그룹이 (-) charge를 띄어 시멘트에 포함된

와 같은 (+) charge의 입자들과 전기적인 인력에 의해 결합된다. 시멘트 입자에 붙은 가지 형태의 Carboxyl 기는 시멘트 입자간의 전기적 반발과 입체장애 효과에 의해 반발력을 유도하고, 이를 통해 적은 물의 양으로 시멘트의 유동성을 확보할 수 있고, 이에 따른 제품의 강도에도 효과를 증진하는 물질로서. 폴리카복실산 1~4wt%의 비율로 사용됨이 바람직하다. 이는 1wt% 미만 사용시 시멘트의 유동성 저하로 제품 성형후 부스러지는 문제점이 있으며 4wt% 초과 사용시 시멘트의 유동성 과다로 인한 성형의 문제점과 작업성이 떨어진다. The polycarboxylic acid is generated during the hydration of cement

Reacts with Polycarboxylic Acid

Salt occurs, and the carboxyl group attached to the backbone of polycarboxylate has a negative charge,

It is coupled by electrical attraction with particles of positive charge such as Branched Carboxyl group attached to cement particles induces repulsion by electrical repulsion and steric hindrance effect between cement particles, thereby securing the fluidity of cement with a small amount of water, thereby improving the strength of the product. As a substance. Preference is given to using at a ratio of 1 to 4 wt% polycarboxylic acid. This is a problem that the product is broken after molding the product when using less than 1wt% of the fluidity of the cement, and the problem and workability of the molding due to excess fluidity of the cement when using more than 4wt%.

The Lactobacillus bacteria (Lactobacillus), An erase Caro My process (Saccharomyces), A also Pseudomonas (Rhodopsedomonas) genus Streptomyces (Streptomyces) lie 0.2-0.3: mixed in a weight ratio of 0.02: 0.18 ~ 0.28: 0.3 to 0.5 The composite first microbial strain mixture is preferably used at a rate of 1 to 1.5 wt% based on the base material. It can not be expected to purify the microorganisms when used less than 1wt%, and the use of more than 1.5wt% is an expensive microorganism, which leads to a cost increase.

Is mixed with 1 weight ratio of Bacillus megateurium (BacillusMegatrium), Bacillus poly miksa (Bacillus Polymixa), Bacillus core roasting Alliance (Bacillus Coaguians) is 0.5: The Bacillus (Bacillus) mesophilic species and thermophilic paper 1 for in 0.3: Bacillus genus strains mixed in a weight ratio of 0.1: 0.1, the second microbial strain mixture is preferably used in 1 ~ 1.5wt% ratio with respect to the base material. It can not be expected to purify the microorganisms when used less than 1wt%, the absolute value when used above 1.5wt% is a factor of cost increase.

The microbial denitrification strains, Castle liner (Castellaniella) as strain and para Cocos (Paracocuus) in one Denny tree blood construct (Denitrificans) a compound denitrification strain strain is mixed belonging to the species belonging to the genus, 0.9: to be mixed in a weight ratio of 0.1 Can be. The microbial denitrification strain is preferably used in a proportion of 0.5 ~ 1wt% with respect to the base material. This can not be expected water purification effect of microorganisms when used less than 0.5wt% and expensive complex microbial strain when used above 1wt% is a factor of the cost increase.

)를 함유하고 있으며 구성 당에 존재하는 수산기(-OH)에 메톡실기의 치환정도에 따라 용해도가 변하게 된다. 셀룰로오스는 Back bone 의 수산기에 따른 수소결합의 강한 결합에 의해 물에 용해되지 않지만 에테르화 반응 (Ether reaction)으로 수산기가 메톡실기로 치환되면 수소결합을 방해해 Back bone의 결합을 끊고, 수용성의 성질을 갖게 된다. 상기 메틸셀룰로오스는 0.5~1wt%의 비율로 사용됨이 바람직하다. 이는 0.5wt% 미만 사용시 코팅액의 점도가 떨어져 미생물 개체수의 저하 요인이 있으며 1wt% 초과 사용시는 고가의 천연재료로써 원가상승의 문제점이 있다. The methyl cellulose is a methyl ester type methoxyl group (-

) Solubility changes depending on the degree of substitution of the methoxyl group in the hydroxyl group (-OH) present in the constituent sugar. Cellulose is not dissolved in water due to the strong bonding of hydrogen bonds to the hydroxyl groups of the back bone, but when the hydroxyl group is replaced by methoxyl group by ether reaction, it interrupts the hydrogen bonds and breaks the bond of the back bone. Will have The methyl cellulose is preferably used in a proportion of 0.5 ~ 1wt%. This is a viscosity of the coating liquid is lowered when using less than 0.5wt% causes a decrease in the number of microorganisms, when using more than 1wt% there is a problem of cost increase as an expensive natural material.

The starch acetate is a kind of modified starch, which is a material that is used to process part of the starch to change its original structure or physical properties. It is used for gelling agent, coating agent, etc., and the starch acetate is 3 ~ 10wt%. Preferably used. This is because the gelation of the microbial coating solution and the coating effect is lowered when using less than 3wt%, there is a deterioration factor of the surface coating, and when using more than 10wt%, the progress of gelation is faster, which leads to a problem of coating construction.

The slaked lime provides a gelling agent and a coating agent reaction. Slaked lime is a crystal produced by hydration and digestion of quicklime. The crystallinity formed by the change of temperature has different forms. CaO + H ₂ O → Ca (OH) ₂ + 15.6kcal mol ^-When digested at high temperature, the amount of nuclei is formed and crystals are formed at a high rate. Therefore, the density due to the reduction of particle diameter is reduced, and the porosity and specific surface area are increased. Therefore, the stimulating effect on the gel and film formation is excellent. High purity contains 72 ~ 74% CaO and 23 ~ 24% water, and low purity contains 40 ~ 48% CaO, 25 ~ 34% MgO and 15 ~ 27% water.

Since the solubility decreases the solubility with increasing temperature but maintains high pH value, when it is used as a stimulant for gel and encapsulation, small amount is added so that it can rapidly destroy the acid film formed by contact with moisture. The initial viscosity increases with increasing acceleration. The slaked lime is preferably used in a ratio of 0.1 to 0.5wt% with respect to the base material. This is a gel, when using less than 0.1wt%, there is a deterioration factor of the film forming action and when using more than 0.5wt% there is a problem that the fast solidification.

The water is neutral to pH 7-8 as tap water or groundwater, it is preferred to use water 81 ~ 93.3wt%. This is because when using less than 81wt% can not expect the effect of the coating by the surface tension and when using more than 93.3wt% the workability of the coating due to the high viscosity is reduced.

Hereinafter, a water-based natural purified kaolin ecological block immobilized with a coating of complex useful microorganisms for the purpose of reducing total green phosphorus (TP), total nitrogen (TN), and green algae produced using the above materials. It will be described in more detail with reference to the drawings.

1 is a water-based natural purified type kaolin ecological block immobilized with a coating of a composite useful microorganism for the purpose of purifying water by reducing total phosphorus (TP) and total nitrogen (TN) according to an embodiment of the present invention, and reducing green algae. Figures 2 to 3a is a flow chart showing a method, a physical picture showing an embodiment of the water-based natural purified kaolin ecological block and the manufacturing method products of the coating and immobilized complex useful microorganisms related to the present invention, Figures 4 to 5 Schematic diagram of a water-based natural purified kaolin ecological block coated with a composite useful microorganism according to the present invention and a method for manufacturing the same. FIG. 6 is a water-based natural purified kaolin ecological coated with a mixed useful microorganism according to an embodiment of the present invention. System schematic of the block.

Figure 7 is a photograph showing the results of the composite useful microbial strain individual test of the coating liquid using the samples prepared in Examples 1 to 2. 8 to 11 is a graph showing the results of performing a complex useful microbial strain individual test using the samples prepared in Examples 1 to 2.

First, a base material is prepared (S201). The base material may be formed by mixing dolomite or stone powder 65-79wt%, OPC or blast furnace slag cement 15-25wt%, kaolin 6-10wt%.

Next, at least one of polycarboxylic acid, complex useful microorganism, methyl cellulose, starch acetate, and slaked lime is added to the base material as an additive (S202).

Next, the material to which the additive is added to the base material is added to the stirrer (Mixer) with water and stirred (S203).

Finally, through the process of mold molding, curing, and coating immobilization of the stirred material, a water-based natural purified kaolin ecological block obtained by coating and immobilizing the composite useful microorganism is completed (S204).

In this case, the material to which the at least one is added to the base material introduced into each stirrer is at least one of a cylindrical rotary stirring method and an impeller co-rotating rotary stirring method and the water supply is at least one of a shower supply method and a mist spraying method. It can be stirred by a method and the method of forming the stirred material may be molded by at least one of a tilting rotation method, a dry vibration hydraulic method, a mold wet method, the curing method of the molded ecological block is a heat source Cured by at least one method of a dry drying method, a wet drying method or a natural drying method, and the method of immobilizing the coating on the cured ecological block can be prepared by at least one method of a brush, roller, spray gun. have.

2 to 3a show actual products of ecological relieving blocks or ecological riverbed protection blocks produced by the method described above. Figure 2 shows the ecological relief block and Figure 3a shows the ecological riverbed protection block. Ecological revetment block or ecological riverbed protection block produced by the above method can be preferably used as the water-based natural purification type kaolin ecological block immobilized composite useful microorganism below the strength of national standards, especially the elution of harmful substances.

Hereinafter, an embodiment of an ecological relief block or an ecological river protection block manufactured by the above method will be described.

By the composition and manufacturing method of each material described above, the ecological relief block or ecological river protection block may be composed of the following components. Ecological revetment block material according to an embodiment of the present invention, based on the total weight of dolomite 65 ~ 79wt%, OPC 15 ~ 25wt%, kaolin 6 ~ 10wt% of the base material, polycarboxylic acid 1 ~ 4wt%, the first microorganism strain Mixture 1 ~ 1.5wt%, 2nd microbial strain mixture 1 ~ 1.5wt%, denitrification strain 0.5 ~ 1wt%, methyl cellulose 0.1 ~ 0.5wt%, starch acetate 3 ~ 10wt%, calcined lime 0.1 ~ 0.5wt%, water 81 ~ It may be made of 93.3wt%. It can be used for the use of the ecological relief block products consisting of the above components.

The material of the ecological riverbed protection block according to an embodiment of the present invention is 1 to 4 wt% of polycarboxylic acid, based on the total weight of dolomite 65 to 79 wt%, blast furnace slag cement, and 6 to 10 wt% of kaolin, 1 to 1.5 wt% of the first microbial strain mixture, 1 to 1.5 wt% of the second microbial strain mixture, 0.5 to 1 wt% of denitrifying strain, 0.1 to 0.5 wt% of methyl cellulose, 3 to 10 wt% of acetic acid starch, 0.1 to 0.5 wt% of slaked lime It may consist of 81 ~ 93.3wt% of water. It can be used for the use of the ecological riverbed protection block products consisting of the above components.

Example 1

65 wt% of dolomite having a particle size of 13mm or less, 25 wt% of OPC having a specific surface area of 4,000cm² / g, 10wt% of kaolin having a grain size of 200mesh 80%, and 1wt% of polycarboxylic acid based on the total weight of the base, the first microorganism strain Impeller rotating method was supplied by supplying 1wt% of mixture, 1wt% of second microbial strain mixture, 0.5wt% of denitrifying strain, 0.1wt% of methyl cellulose, 3wt% of starch acetate, 0.1wt% of hydrated lime, and 93.3wt% of water. Stirred and mixed by a shower supply method into a mold of 1,000x1,000x250mm size, ecological relief block was produced by a tilting rotary molding method, natural drying, spray gun coating method (see Fig. 2).

Example 2

79 wt% of stone powder with a particle size of 13 mm or less, blast furnace slag cement with a specific surface area of 4,000 cm² / g, 15 wt% of blast furnace slag, 6 wt% of kaolin having a grain size of 200 mesh and 80%, and 4 wt% of polycarboxylic acid based on the total weight of the base material. Impeller rotating by supplying 1.5wt% of microbial strain mixture, 1.5wt% of second microbial strain mixture, 1wt% of denitrifying strain, 0.5wt% of methyl cellulose, 10wt% of starch acetate, 0.5wt% of slaked lime and 81wt% of water The method was mixed by stirring and shower supply method into the mold of 1,000x1,000x250mm size, and the ecological bed protection block was manufactured by the tilting rotational molding method, the natural drying, and the spray gun coating method (see FIG. 3a).

Samples of ecological revetment blocks and ecological riverbed protection blocks were taken as 50 x 50 x 50 mm standards by the method of Examples 1 to 2, respectively, and their strengths and absorption rates are shown in Table 2, and as comparative examples, KS standard KS F The 4419 test items represent the standard values of the Korea Institute of Construction and Living Environmental Testing.

Test Items unit Test Methods KS Standard Test result Compressive strength N / mm² KS F 4419 21 or more 35 Water absorption % KS F 4419 below 10  6

In addition, the SEM image test SEM x200 of the structure photographed by the electron microscope results of the KS I 0051 test method is shown in Figures 3b and 3c.

Table 3 below is a test carried out by the Korea Institute of Chemical Convergence Testing, it can be seen that as described above, it is harmless as the heavy metal dissolution test results of ecological protection and ecological riverbed protection block.

Inspection items unit Designated Waste Level result Test Methods Hexavalent chrome mg / L 1.5 or more Not detected Waste Process Test 2008 Lead Content 3 or more Cadmium content 0.3 or more Arsenic content 1.5 or more Mercury content 0.005 or more Copper content 3 or more Trichloroethylene 0.3 or more Tetrachlorethylene 0.1 or more Cyan content 1 or more Organophosphorus compounds 1 or more Oil content % 5 or more 0.00

 Table 4 below shows the results of experiments conducted by the Department of Environmental Engineering, the University of Seoul, showing the high efficiency as a result of the water purification test of the ecological block. Experimental results show that the population is high.

division unit CODcr T-N T-P Control mg / L 31.34 7.32 0.624 Implementation mg / L 15.22 0.6 0.053 Removal efficiency % 51.5 91.8 91.5

division Number of individuals Test Methods Complex useful microorganisms 1x10cfu / mg Petridish

According to the test results, it can be seen that the samples of the ecological revetment block and the ecological river protection block produced by the method of Examples 1 to 2 exhibited excellent results of KS standard, such as strength and water absorption rate, and water purification efficiency. . Therefore, the ecological revetment block or ecological retaining wall block of the present invention may be utilized as an aqueous natural purification block.

In the detailed description of the present invention described above with reference to preferred embodiments of the present invention, those skilled in the art or those skilled in the art having ordinary knowledge of the present invention described in the claims to be described later It will be understood that various modifications and changes can be made in the present invention without departing from the spirit and scope of the invention.

Claims (10)

In the water-based natural purified type kaolin ecological block, which is immobilized with a coating of a composite useful microorganism which is formed in the form of a raft block or a bed protection block,
Dolomite or stone powder 65 ~ 79wt%, OPC or blast furnace slag cement 15-25wt%, kaolin 6-10wt%, based on the total weight of the base material 1-4wt% polycarboxylic acid, the first microbial strain mixture 1 ~ 1.5wt%, 1 ~ 1.5wt% 2nd microbial strain mixture, 0.5 ~ 1wt% denitrification strain, 0.1 ~ 0.5wt% methyl cellulose, starch acetate 3 ~ 10wt%, calcined lime 0.1 ~ 0.5wt%, water 81 ~ 93.3 wt is added to the composition,
The dolomite or stone powder has a particle size of 0.8 ~ 23mm,
The first microorganism strain mixture, Lactobacillus bacteria (Lactobacillus), An erase Caro My process (Saccharomyces), A also Pseudomonas trick 0.2 ~ 0.3 (Rhodopsedomonas) genus Streptomyces (Streptomyces): 0.18 ~ 0.28: 0.3 ~ 0.5: Mixed at a weight ratio of 0.02,
The second microorganism strain mixture, Bacillus (Bacillus) genus of Bacillus megateurium (Bacillus Megatrium), Bacillus poly miksa (Bacillus Polymixa), Bacillus core roasting Alliance of at least two kinds of said strains is blended in (Bacillus Coaguians) Water-based natural purified kaolin ecological block coated with complex useful microorganisms. delete delete The method of claim 1,
The OPC or blast furnace slag cement has a specific surface area of 4,000 ~ 5,000 cm² / g of a composite aqueous microbial coating immobilized water-based natural purified type kaolin soil block. The method of claim 1,
The kaolin is a water-based natural purified kaolin ecological block immobilized coating the composite useful microorganism, characterized in that the particle size is 200mesh pass rate 80% or more. delete delete delete delete delete

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