KR100691428B1 - A color aggregate and artificial fish reef comprising binder for industrial wastes, and method of producing the structures - Google Patents

Abstract

In the present invention, the first polymethacrylate aqueous solution (solid content; 40 ± 1%, viscosity; 200 ± 100 cps, specific gravity (20/4 ° C.); 1.12 ± 0.02, pH; 7 ± 1) 10 to 20% by volume, second Polymethacrylate aqueous solution (solid content; 40 ± 1%, viscosity; 250 ± 100 cps, specific gravity (20/4 ° C.); 1.13 ± 0.02, pH; 7 ± 1) 10 to 20% by volume, aluminum sulfate 30% by weight aqueous solution 5 It consists of an industrial waste treatment hardener comprising from 15% by volume to 15% by weight, 5% by weight aqueous solution of calcium oxide, and 45% to 65% by volume water, cement mortar, coal ash, waste foundry sand, slag, waste lime and dredged soil. It relates to any industrial waste selected from the group, colored aggregates containing artificial pigments and artificial reefs, and methods for producing these colored aggregates and artificial reefs.

Since the colored aggregate and artificial reefs according to the present invention are manufactured using industrial waste as a raw material using a specific solidifying agent, the manufacturing cost can be reduced, and the emission of harmful substances can be prevented, so the effect of environmental protection can be expected.

Description

Colored aggregate and artificial fish reef comprising binder for industrial wastes, and method of producing the structures

1 is a process flow diagram for a process for producing colored aggregates from industrial wastes using the solidifying agent for industrial waste treatment of the present invention.

Figure 2 is a process flow diagram for a process of manufacturing a structure by filling the industrial waste with fiber waste using the industrial waste treatment solidifying agent of the present invention.

Figure 3 is a schematic diagram of a structure (walking block) manufactured using industrial waste as a raw material using the solidifying agent for industrial waste treatment of the present invention.

4 is an assembly schematic diagram of a deforestation structure manufactured using industrial waste as a raw material using the solidifying agent for treating industrial waste of the present invention.

5 is a schematic diagram of a deforestation structure manufactured using industrial waste as a raw material using the solidifying agent for treating industrial waste of the present invention.

6 is a schematic view of a sea starch structure in the form of starfish manufactured using industrial waste as a raw material using the solidifying agent for treating industrial waste of the present invention.

7 is a schematic diagram of a deforestation structure manufactured using industrial waste as a raw material using the solidifying agent for industrial waste treatment of the present invention.

8 is an assembly schematic diagram of a deforestation structure manufactured using industrial waste as a raw material using the solidifying agent for treating industrial waste of the present invention.

Figure 9 is a schematic diagram of the deforestation structure produced by filling the industrial shell with industrial waste using the solidifying agent for industrial waste treatment of the present invention.

The present invention relates to colored aggregates and artificial reefs obtained using a solidifying agent for industrial waste treatment, and to a method for manufacturing these structures, more specifically, any one selected from the group consisting of coal ash, waste foundry sand, slag, waste lime and dredged soil. The present invention relates to environmentally friendly colored aggregates and artificial reefs obtained by using industrial solidifying agents for treating certain industrial wastes, and to methods of manufacturing these structures.

Among the industrial wastes, coal ash is generated at about 2 million tons per year in cogeneration plants in Korea, and most of them have been treated so far depending on the landfill. However, the landfill has serious effects on not only environmental pollution but also heavy metal pollution of animals and plants. Therefore, manufacturing the structure using coal ash, an industrial by-product, has a great effect in terms of environmental protection in addition to economic advantages.

The problem with recycling industrial wastes is that it is difficult to obtain the required strength when using a specific structure to make certain structures, and also because industrial wastes, especially mine tailings, which are mine wastes, contain large amounts of harmful heavy metals. Heavy metals may be released from structures manufactured as raw materials, causing secondary environmental pollution.

In general, various structures used in construction and civil engineering use a method of manufacturing cement concrete in which an appropriate amount of gravel, sand, cement, and water is mixed. Such structures continue to have considerable durability on land after completion of their fabrication, but they can not inhibit the hydration of cement properties after two to three years in water, so that wear progresses rapidly over time. Hydration refers to a phenomenon in which calcium hydroxide (Ca (OH) ₂ ) is generated by the interaction between calcium (Ca) and water (H ₂ O), which are the main components of cement, and the hydrated calcium hydroxide (Ca (OH) ₂ ) Strong alkalis with a pH of 12 to 13 are fatal to aquatic plant growth and cause secondary contamination.

In general, harmful substances generated in cement structures act as a contaminant. Especially, when cement structures are exposed to river water or sea water for a long time, they have a great influence on aquatic flora and fauna, and thus the method of minimizing environmental pollution caused by cement structures. This is required. When sand and gravel are used to make a structure with cement, calcium, the main component of cement, causes hydration reactions to elute strong basic substances, and if the cement structure is exposed to water or sea water for a long time, it not only contaminates the surrounding environment but also the structure. It reduces the strength of the product and shortens its lifespan. Therefore, it is very important to minimize harmful wastes emitted from cement in structures such as sofa blocks (TTP) or artificial reefs that are exposed to seawater for a long time.

Therefore, the technical problem to be achieved by the present invention is to provide colored aggregates and artificial reefs obtained by recycling industrial waste by using a specific solidifying agent.
In addition, another technical problem of the present invention is to provide a method for producing the colored aggregate and artificial reef.

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In order to achieve the above technical problem, the present invention is the first polymethacrylate aqueous solution (solid content; 40 ± 1%, viscosity; 200 ± 100cps, specific gravity (20/4 ℃); 1.12 ± 0.02, pH; 7 ± 1) 10-20% by volume, second polymethacrylate aqueous solution (solid content; 40 ± 1%, viscosity; 250 ± 100 cps, specific gravity (20/4 ° C.); 1.13 ± 0.02, pH; 7 ± 1) 10-20% by volume 5 to 15% by volume aqueous solution of aluminum sulfate, 1 to 10% by volume aqueous solution of 5% calcium oxide, and 45 to 65% by volume water solidifying agent for industrial waste treatment (also called "GRG21"), Provided are colored aggregates containing any one of industrial waste selected from the group consisting of cement mortar, coal ash, waste foundry sand, slag, waste lime, and dredged soil.
In addition, the present invention is the first polymethacrylate aqueous solution (solid content; 40 ± 1%, viscosity; 200 ± 100 cps, specific gravity (20/4 ℃); 1.12 ± 0.02, pH; 7 ± 1) 10 to 20% by volume, 2 polymethacrylate aqueous solution (solid content; 40 ± 1%, viscosity; 250 ± 100 cps, specific gravity (20/4 ° C.); 1.13 ± 0.02, pH; 7 ± 1) 10 to 20% by volume, 30% by weight aluminum sulfate solution Industrial waste treatment hardener comprising 5 to 15% by volume, 5% to 5% by weight aqueous solution of calcium oxide, and 45 to 65% by volume of water, cement mortar, coal ash, waste foundry sand, slag, waste lime and dredged soil One of the industrial wastes selected from the group consisting of is mixed to provide a cured artificial reef in a fiber shell.
In the structure of the present invention, it is preferable that the weight mixing ratio of the solidifying agent, cement and industrial waste for industrial waste treatment is 1: 1: 3.5.

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The present invention to achieve the above other technical problem,

Quantifying and transporting the industrial waste treatment hardener, cement mortar, industrial waste and pigments;

Preparing a mixture by mixing the industrial waste treatment hardener, cement mortar, industrial waste, and a pigment;

Molding and firing the prepared mixture into an assembly having a predetermined size;

It provides a method for producing a colored aggregate comprising the step of pulverizing the calcined mixture.

In addition, the present invention to achieve the above another technical problem,

Quantifying and transporting the industrial waste treatment hardener, cement mortar and industrial waste;

Preparing a mixture by mixing the quantitative industrial waste treatment hardener, cement mortar, and industrial waste;

It provides a method for producing artificial reefs comprising the step of curing the prepared mixture to the fiber shell having a predetermined form.

Hereinafter, the colored aggregate and artificial reef prepared using the solidifying agent for industrial waste treatment of the present invention, and a manufacturing method thereof will be described in more detail. First, the solidifying agent for industrial waste treatment used in the present invention will be described.

The solidifying agent used in the present invention is a solidifying agent developed for use in recycling by-products and wastes, such as industrial waste, dredged soil, which has become a serious social problem in recent years. The solidifying agent solidifies industrial waste through a pozzolanic reaction which reacts with Ca (OH) ₂ produced by the hydration of cement to form calcium silicate hydrate.

In addition, the solidifying agent for industrial waste treatment used in the present invention can be diluted with water, and the coagulation reaction rate can be easily adjusted by changing the concentration. For example, in the case of disasters, military installations, tunnel construction, etc., the solidification agent is used at a high concentration to increase the reaction speed, and in the case of sidewalk blocks and bricks, the reaction rate can be used to reduce the reaction speed.

Industrial waste treatment solidifying agent used in the present invention has a wide reaction temperature range compared to the conventional material because it causes a special hydration reaction, it can be easily applied to the construction work in high temperature, high humidity, cold districts and the like.

In addition, since the solidifying agent for industrial waste treatment used in the present invention reacts with Ca (OH) ₂ generated by the hydration reaction of cement, it causes a pozzolanic reaction to convert aluminum and calcium silicate into a hydrate, thereby improving physical properties of concrete. In addition, the structure manufactured using the hardener exhibits higher strength than general concrete. In terms of economics, the present invention can significantly reduce the manufacturing cost because the structure is manufactured using industrial waste. Industrial waste used in the present invention is any one selected from the group consisting of coal ash, waste foundry sand, slag, waste lime and dredged soil.

The biggest problem in recycling industrial waste is the release of hazardous substances contained in industrial waste. The researchers of the present invention produced an economical and environmentally friendly structure that can minimize the emission of harmful substances by using any one industrial waste selected from the group consisting of the hardener and coal ash, waste foundry sand, slag, waste lime and dredged soil. . In addition, in the case of manufacturing a marine structure by solidifying and curing the solidifying agent and industrial waste in the fiber shell, it is possible to minimize the marine pollution caused by the hydration reaction of the structure.

The first polymethacrylate aqueous solution (solid content; 40 ± 1%, viscosity; 200 ± 100 cps, specific gravity (20/4 ° C.); 1.12 ± 0.02, pH; 7 ± 1), which is the main component of the solidifying agent, is a carboxylic acid copolymer. Is an aqueous solution containing 39 to 41% by weight, and is a product marketed under the product name CP-WB by LG Chemical as a water reducing agent and fluidizing agent for cement. The second polymethacrylate aqueous solution (solid content; 40 ± 1%, viscosity; 250 ± 100 cps, specific gravity (20/4 ° C.); 1.13 ± 0.02, pH; 7 ± 1) also contains 39 to 41% by weight of carboxylic acid copolymer. It is an aqueous solution included and is also marketed under the product name CP-WR by LG Chem as a water reducing agent and fluidizing agent for cement. The first polymethacrylate aqueous solution and the second polymethacrylate aqueous solution induce the dispersion between particles by steric hindrance effect and electrostatic repulsion through physical or chemical adsorption to cement clinker particles, thereby reducing the erosion effect and initial hydration rate. To improve workability.

In the solidifying agent used in the present invention, the first polymethacrylate aqueous solution has a large role as a water reducing agent, preferably 10 to 20% by volume, more preferably 12 to 18% by volume, of 10% by volume. If less than not enough solidification does not occur, it is not preferable, and if it exceeds 20% by volume is rather undesirable because it hinders the increase in manufacturing cost and stabilization of waste due to overuse.

In the solidifying agent of the present invention, the second polymethacrylate aqueous solution has a large role as a fluidizing agent, preferably 10 to 20% by volume, and more preferably 12 to 18% by volume, of less than 10% by volume of the total solidifying agent. This is not preferable because it does not cause sufficient solidification, and if it exceeds 20% by volume, it is not preferable because it hinders the increase in manufacturing cost and stabilization of waste due to overuse.

Therefore, the first and second polymethacrylate aqueous solution is preferably maintained in a balanced ratio as described above for proper solidification and stabilization of industrial waste.

The aqueous solution of 30% by weight of aluminum sulfate coagulates, and is preferably 5 to 15% by volume of the total solidifying agent, and more preferably 8 to 12% by volume, but less than 5% by volume is not preferable because solidification does not occur sufficiently. If not more than 15% by volume, precipitation occurs, which is not preferable.

5% by weight aqueous solution of calcium oxide affects the pozzolan reaction, which is a cement coagulation reaction, to improve physical properties and to adjust pH through calcium hydroxide, preferably 1 to 10% by volume of the total solidifying agent, and 3 to 7% by volume. It is more preferable that the amount is less than 1% by volume, which is not preferable because the aggregation of waste does not occur sufficiently, and when it exceeds 10% by volume, it is not preferable because it hinders physical property improvement and pH control.

Water facilitates the mixing of each component of the solidifying agent and affects waste flocculation, preferably 45 to 65% by volume, more preferably 50 to 60% by volume, and less than 45% by volume of the total amount of the solidifying agent. Not only does the manufacturing cost rise, but the mixing of each component is not smooth, and if it exceeds 65% by volume, it is not preferable because the aggregation of waste does not occur well.

In the manufacture of the structure of the present invention, it is preferable that the weight mixing ratio of the solidifying agent, cement and industrial waste for industrial waste treatment is 1: 1: 3.5, and solidification of the waste occurs effectively at such a mixing ratio, and the strength above a certain level is maintained. .

The components can be adjusted to suit the purpose of the structure, and various types of structures can be manufactured according to the use. Table 1 below shows the features and uses of these structural components.

Structural material Characteristic Usage Solidifying agent Slaked lime Pebble sand cement 10 50 15 15 10 Adjusting agent, waterproof, hardening strength control Artificial reefs, building materials, raft blocks 5 50 10 10 15 Quickness Please install 10 60 10 10 10 Cement, particle decomposition, strength control Offshore structure

1 is a process flow diagram illustrating a process of solidifying industrial waste using a solidifying agent used in the present invention, firing and pulverizing the same, and manufacturing colored aggregates. Colored aggregate produced through this process can be utilized in various civil and construction works, such as gravel for railroad construction, and manufacturing costs are low because industrial waste is recycled.

FIG. 2 is a process flow diagram illustrating a process of mixing a solidifying agent, industrial waste, and cement mortar used in the present invention, and putting the mixture into a fiber shell to form a structure. When the artificial reef is made using the structure manufacturing method according to the present invention as shown in Figure 2, there is an advantage that can significantly reduce the toxic substances emitted from the cement than the existing structure manufacturing method, the spores adhere to within a short time Since it provides an environment in which it can grow naturally, there is an advantage that an eco-friendly effect can be expected.

3 to 9 show the shape of the structure that can be produced in various ways according to the shape of the form and form.

Hereinafter, the present invention will be described in more detail with reference to the following examples. These examples are only for illustrating the present invention, and the protection scope of the present invention is not limited by these examples.

Example

<Production of Solidifying Agent>

Each component was mixed as shown in Table 2 below to prepare a solidifying agent for treating industrial waste (GRG21).

ingredient 1st poly methacrylate aqueous solution 2nd poly methacrylate aqueous solution 30% by weight solution of aluminum sulphate 5% by weight solution of calcium oxide water Concentration (% by volume) 15 15 10 5 55

<Structure Fabrication and Property Measurement>

1,000 kg of coal ash (fly ash and bottom ash) discharged from the power plant as industrial waste, 20 kg of solidifying agent (GRG21) prepared in the ratio of Table 2 and 250 kg of cement mortar (cement: 25 kg) The structure (sample) was produced by mixing with water. The construction and curing of the structure (test specimen) were carried out by the manufacturing method and curing method specified in the Standard Test Method for Cement Mortar Compressive Strength (KSL 5105).

However, in the case of specimen samples A and B, the content was adjusted so that the content of fly ash in the total coal ash was 90% or more, and in the case of specimen samples C and D, the content of the bottom ash was adjusted to be 90% or more.

Compressive strength test specimens were prepared by twenty four (12) for the mixing ratio of solidifying agent and water at 1: 200 and 1: 300, respectively. After 28 days, the compressive strength was measured by the compressive strength test (KSL 5105). Was measured. The measurement results are shown in Table 3 and Table 4. Table 3 shows the compressive strength (kg / cm ² ) of the specimen (mixture ratio 1: 200).

sign A A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 burglar 120.4 128.3 129.4 111.6 194.1 190.1 179.5 199.2 110.3 107.5 111.5 110.0

As shown in Table 3, when the mixing ratio is 1: 200, the maximum compressive strength was 199.2kg / cm ² (A-8), the minimum compressive strength was 107.5kg / cm ² (A-10), and the average compressive strength was 141.4. kg / cm ² . From the results in Table 3, it can be seen that the variation in compressive strength is severe depending on the sampling location. Table 4 below shows the compressive strength (kg / cm ² ) of the specimen (mixing ratio 1: 300).

sign B-1 B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9 B-10 B-11 B-12 burglar 118.7 102.4 99.9 110.5 125.9 122.8 120.8 124.5 120.4 119.5 121.5 124.5

As shown in Table 4, when the mixing ratio is 1: 300, the maximum compressive strength was 125.9kg / cm ² (B-5), the minimum compressive strength was 99.9kg / cm ² (B-3), and the average compressive strength was 117.6 kg / cm ² . Comparing the results of Table 3 and Table 4, it can be seen that when the mixing ratio of the hardener and water is 1: 300, the variation in compressive strength is relatively smaller than that of 1: 200.

In addition, various types of cube molds (210 × 100 × 60m ³ ) were prepared according to KSF4004, and then the compressive strength (kg / cm ² ), absorption (%) and unit weight (kg / cm ² ) of the specimens were measured. The results are summarized in Table 5, Table 6 and Table 7.

Sample C 1: 200 Sample C-1 C-2 C-3 C-4 C-5 C-6 burglar 279 280 274 255 267 273 Sample D 1: 300 Sample D-1 D-2 D-3 D-4 D-5 D-6 burglar 264 250 255 226 234 229

sign C-1 C-2 C-3 C-4 C-5 C-6 Absorption amount 3.99 4.60 3.50 3.59 4.23 3.04

sign C-1 C-2 C-3 C-4 C-5 C-6 Unit weight 1.974 1.945 1.950 1.840 1.795 1.820

As a result of the experiment as described above, the quality of coal ash discharged from the power plant was determined to be relatively good physical properties and chemical components. Hardener: Cement: Coal ash optimum weight ratio of 1: 1: 3.5 was found to be appropriate.

The specimen without the solidifying agent was suspended in various materials during curing, resulting in suspended solids and 30-50% lower than the compressive strength. In addition, since the quality of the sample used is a problem in which the variation in the specimen strength is 20 to 30%, it was determined that uniform quality work of coal ash is required in advance in preparing the cured product.

Component dissolution analysis was performed using an infrared spectroscopy (FT-IR) method and analyzed by a JIR-100 type instrument. As a result, no toxic components Cd, Pb, Cr, T-Hg, P-Hg, As, O-P, CN, etc. were eluted.

Meanwhile, in the process of manufacturing the structure, the air particles in the water combine with cement hydrate bonded to the aggregate to reduce the fluidity of the structure, and the hydrate is generated in the space inside the structure. In this process, a volume change of about 1.45 to 2.05 was observed depending on the ratio of water and cement.

As described above, by manufacturing the structure by solidifying the industrial waste by using the industrial waste treatment solidifying agent according to the present invention, it is possible to significantly reduce the hydration reaction of calcium can prevent environmental pollution due to the release of harmful substances. However, maintaining the strength of the structure can extend the life of the structure. In addition, by recycling industrial waste is not only environmentally friendly, but also has the advantage of reducing manufacturing costs. In addition, when fabricating and installing marine structures using fiber shells, emissions of toxic components can be reduced compared to existing concrete structures, and environmentally friendly effects can be expected as they provide an environment in which spores adhere and aquatic plants and plants grow in a short period of time. have.

Claims (7)

delete delete  1st polymethacrylate aqueous solution (solid content; 40 ± 1%, viscosity; 200 ± 100cps, specific gravity (20/4 ° C.); 1.12 ± 0.02, pH; 7 ± 1) 10-20% by volume, second polymethacryl Rate aqueous solution (solid content; 40 ± 1%, viscosity; 250 ± 100 cps, specific gravity (20/4 ° C.); 1.13 ± 0.02, pH; 7 ± 1) 10 to 20% by volume, 5 to 15% by volume aqueous solution of aluminum sulfate %, Calcium oxide 5% by weight aqueous solution 1 to 10% by volume, 45 to 65% by volume of water for the treatment of industrial wastes, cement mortar, coal ash, waste foundry sand, slag, waste lime and dredged soil selected from the group consisting of Colored aggregate containing any one industrial waste and pigment | dye.  1st polymethacrylate aqueous solution (solid content; 40 ± 1%, viscosity; 200 ± 100cps, specific gravity (20/4 ° C.); 1.12 ± 0.02, pH; 7 ± 1) 10-20% by volume, second polymethacryl Rate aqueous solution (solid content; 40 ± 1%, viscosity; 250 ± 100 cps, specific gravity (20/4 ° C.); 1.13 ± 0.02, pH; 7 ± 1) 10 to 20% by volume, 5 to 15% by volume aqueous solution of aluminum sulfate %, Calcium oxide 5% by weight aqueous solution 1 to 10% by volume, 45 to 65% by volume of water for the treatment of industrial wastes, cement mortar, coal ash, waste foundry sand, slag, waste lime and dredged soil selected from the group consisting of Artificial reefs made by mixing any industrial waste and putting it in a fiber shell. 5. The artificial reef as claimed in claim 4, wherein the weight mixing ratio of the solidifying agent, cement and industrial waste for industrial waste treatment is 1: 1: 3.5.  1st polymethacrylate aqueous solution (solid content; 40 ± 1%, viscosity; 200 ± 100cps, specific gravity (20/4 ° C.); 1.12 ± 0.02, pH; 7 ± 1) 10-20% by volume, second polymethacryl Rate aqueous solution (solid content; 40 ± 1%, viscosity; 250 ± 100 cps, specific gravity (20/4 ° C.); 1.13 ± 0.02, pH; 7 ± 1) 10 to 20% by volume, 5 to 15% by volume aqueous solution of aluminum sulfate Quantifying and transporting the industrial waste treatment solidifying agent, cement mortar, industrial waste and pigment, including%, 1-10% by volume aqueous solution of calcium oxide 5% by weight, and 45-65% by volume of water; Preparing a mixture by mixing the industrial waste treatment hardener, cement mortar, industrial waste, and a pigment; Curing and firing the mixture into granules of a predetermined size; Method for producing a colored aggregate of claim 3, comprising the step of pulverizing the calcined mixture.  1st polymethacrylate aqueous solution (solid content; 40 ± 1%, viscosity; 200 ± 100cps, specific gravity (20/4 ° C.); 1.12 ± 0.02, pH; 7 ± 1) 10-20% by volume, second polymethacryl Rate aqueous solution (solid content; 40 ± 1%, viscosity; 250 ± 100 cps, specific gravity (20/4 ° C.); 1.13 ± 0.02, pH; 7 ± 1) 10 to 20% by volume, 5 to 15% by volume aqueous solution of aluminum sulfate Quantifying and transporting the industrial waste treatment solidifying agent, cement mortar, industrial waste including 1% to 10% by volume of calcium oxide 5% by weight aqueous solution and 45% to 65% by volume of water; Preparing a mixture by mixing the industrial waste treatment hardener, cement mortar, and industrial waste; A method of manufacturing artificial reefs according to claim 4, comprising the step of curing the mixture into a fiber shell having a predetermined form.

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