KR101543523B1 - Solidifying composition for deep mixing method using circulation resource and manufacturing method of the same - Google Patents

Abstract

The present invention relates to a solidifier composition for deep soil stabilization by chemical method in a land and marine using recycled resource and a manufacturing method thereof actively using by-product of industry discharged from an industrial process and, more specifically, to a low cement-based solidifier composition for deep soil stabilization by chemical method in a land and marine using recycled resource and a manufacturing method thereof having solidity of an existing cement-based solidifier or higher when working ground improvement for reinforcement of soft ground and foundation reinforcement of a building.

Description

TECHNICAL FIELD The present invention relates to a fire-fighting composition for deep-well mixing treatment using circulating resources and a method for manufacturing the same,

The present invention relates to a fire-fighting composition for the deep-sea and deep-sea mixed treatment method utilizing the industrial by-products discharged from an industrial process, and more particularly to a fire- And to provide a low cement based fire retardant composition and a method for manufacturing the same, which can exhibit a strength equal to or higher than that of conventional cement fireproofing during an improvement work.

Recently, small cogeneration power generation, which is the core technology of the energy supply system, is gradually increasing in order to realize a low-energy low-carbon city that meets the national energy policy. The demand for low-calorie coal Circulating fluidized bed boilers have attracted attention as a suitable power generation facility. This is because circulating fluidized bed boilers have advantages such as low calorific value utilization, environment friendliness and high efficiency due to large capacity of fluidized bed boiler. Therefore, it has a share of 2% in the coal-fired power plant market in the early 1990s. And it is gradually increasing due to continuous expansion and new investment.

According to the KEPCO subsidiary, the use of low-calorific coal such as bituminous coal is increasing steadily due to the rise in the price of high-calorific coal such as bituminous coal. In order to increase the proportion of low-calorific coal used, low-calorific coal is literally low in calorific value because it is low in calorific value. Currently, power companies are trying to convert power plants designed to use high calorific value of 6000kcal, There is also a place to have a power generation facility which can burn only, or to examine introduction of the facility. Combined cogeneration with a circulating fluidized bed boiler system is effective in using low calorific value coal of about 4000 ~ 5000kcal instead of high calorific value as a fuel and it is advantageous that there is no need for separate desulfurization and denitrification equipment to reduce pollutant discharge. Respectively. In particular, the cogeneration plant is gradually expanding the low cost pet coke produced by pyrolysis of the byproducts generated in the petroleum refining process to reduce the fuel cost in the conventional bituminous coal burning system. As a result, the fuel oil being used is being converted from natural bituminous coal to pet coke coals, And since a single plant has various fly ash quality per process, various problems are posed in processing according to fly ash characteristics. Accordingly, in accordance with the present invention, each fly ash having different characteristics in each process is combined with other stimulants To produce an environmentally friendly low cement based fire.

However, fly ash discharged from a coal-fired power plant using conventional high-calorific bituminous coal as a fuel is recycled as a construction material such as remicon and concrete secondary product as an admixture for concrete, which is a KS standard product, while a low- The ash discharged from the circulating fluidized bed boiler is different from the conventional fly ash in composition and properties and is not recycled because it has no related standard and is being treated as simple waste. In addition, it is expected that the competitiveness of related companies will worsen due to the shortage of landfill waste and the prohibition of waste disposal on the marine dumping site. Therefore, realistic recycling measures are required.

Due to rapid industrialization and expansion of infrastructure, large-scale port construction is being carried out mainly on coastal coasts. Most of these large-scale port works are mostly constructed on soft ground, and efforts to secure the stability of large structures by solving the problems of low strength and high compressibility, which are inherent characteristics of the ground, have been actively carried out. Especially, considering the domestic situation where the land is small, it is necessary to improve the ground and stabilize the marine soils in the first stage. The development of the Saemangeum district land development is an extension of these developments, and stabilization and improvement work of the ground is necessary for large-scale industrial complex and port construction in the future. The port and marine areas of Korea are dominated by weak alluvial clay in geographical or geographical conditions. In order to build structures in these areas, a ground improvement method is required. In most cases, the port construction is not applicable to the soft ground treatment method, which is generally applied on land because of the special nature of underwater construction.

Replacement method, vertical drainage method, and preloading method have been applied for soft soil improvement measures for a long time. Especially in Korea, sand compaction pile method is mainly applied as the foundation of offshore structures. Recently, however, environmental conservation has been increasing the depth of improvement due to seawater pollution by dredging, dredging of dredged materials, collection of aggregate on the land, , And expansion of improved areas. Due to these problems, there is an increasing tendency to improve the soft ground in the ground state. Among them, the deep mixing process method (DCM, SRT, SCW, etc.) is being used.

In the deep mixing process, the stabilized material mixed with cement and water is injected into the soft ground with low pressure, mixed and agitated by rotating the special agitator, and solidified by using the curing reaction of cement, The soft soil layer in the range is stable enough to secure the required strength over the required strength, and construction from the minimum 2.0m to 34.0m (depth) is possible. Depending on the admixture, it can be applied to all soft soils such as clay soil, sand soil, organic soil and so on. It is a highly reliable method which can obtain high strength in a short time with little disturbance of pollution and surrounding ground such as vibration.

Due to these advantages, the application of the deep mixing process has been increasing rapidly in recent years, and it is used for the foundation wall of the earth and various soft ground foundation method. The cement and cement fireproofing is applied to the breakwater, have.

The general improvement process of cement fire fighting can be summarized as follows. ① Generate a large amount of ettringite. Etrringite absorbs a large amount of water as binding water to lower the water content, while restricting the migration of the particles and making the material easy to cure. ② Ca ^{2+, which} is eluted from calcium hydroxide, calcium silicate, etc., aggregates the particles. Therefore, the soil particles are coagulated and solidified, and they are close to the sandy soil. ③ Strength increases by the formation of calcium silicate hydrate. ④ In the long term, solubles such as SiO ₂ and Al ₂ O ₃ contained in the soil generate Ca (OH) ₂ and insoluble hydrate and cure. This reaction is a pozzolanic reaction.

However, there is a disadvantage in that the difference in the improvement strength due to the type of soft soil, the water content, and the soil containing organic matter is large. In addition, in the modified soil improved in the existing cement ground, the hexavalent chromium is eluted into the soil at a concentration exceeding the soil environmental standard due to the nature of the cement, and there is a possibility that serious environmental problems are caused. There is a falling problem.

A cement fireproofing product that improves the disadvantages of such cement. This is because a special mixture of calcium sulfoaluminate type binder or a large amount of gypsum is added to produce a large amount of etringingite which is most effective when solidifying soft ground, Do. The reason for this is that, in a fire, a binder such as gypsum combines with a large amount of water to cause a reaction to produce an ettringite mineral which is a needle crystal. However, these binders have excellent effects, but they are not expensive because of the expensive materials.

In order to solve the above-mentioned problems, the present invention provides a fire-extinguishing agent which is an eco-friendly new material that maximizes reactivity by recycling inorganic industrial by-products and other by-products of recycling resources and a method of manufacturing the same.

In order to accomplish the object of the present invention, the present invention provides a cement composition comprising 20 wt% or less of Portland cement, 65 to 85 wt% of a synthetic pozzolanic material and 5 to 15 wt% The present invention also provides a low-cement-based fire-retardant composition and a method for producing the same.

The present invention can contribute to the construction of a resource recycling type recycling system by recycling the inorganic industrial by-products (slag and fly ash) and other circulation resource byproducts generated in the industrial complex. It is also expected to be a stable, eco-friendly, and economical model of recycling resources in industrial parks, which are expected to increase steadily.

As a result of the application of the present invention, it is expected that CO ₂ emissions are reduced by about 17,000 tons when the use amount of 100,000 tons of high fire is used, and the environment-friendly ground stabilization is expected due to application of environment friendly fire. In addition, for economic benefits, it is possible to reduce the reclamation cost of about KRW 900 million per year when recycled as a raw material for high-fire fires.

The technology to be developed through the present invention is a technology for recycling inorganic industrial by-products (slag and fly ash) and other circulation resource byproducts generated in an industrial complex. As a by-product of this inorganic industry, there are ash generated from circulating fluidized bed boilers among circulating resources.

Circulating Fluidized Bed Combustion (CFBC) incorporates limestone to remove sulfur generated by combustion of fuel at combustion conditions between about 850 and 900 ° C. This desulfurizing limestone and fossil fuel (bituminous coal, Petro Cokes Etc.) are circulated while the suspended particles are circulated together, and the steam is produced by the heat of combustion generated in the boiler, and this steam drives the turbine generator to produce electricity.

The circulating fluidized-bed cogeneration plant also has a bottom ash that reacts with circulating fuel and limestone suspended particles such as fly ash discharged from coal-fired power plants, and bottom ash that falls to the bottom of the combustion furnace, and fly ash Fly ash).

Since the circulating fluidized bed boiler ash is generated by the desulfurization process and the combustion process in the furnace, the characteristics of fly ash are different from those of general coal fired power plant. In addition, since the main minerals exist in the form of Lime (CaO) and Gypsum (CaSO ₄ ), they are highly valuable as an effective ingredient of fire-fighting. Here, CaO reacts with water in the ground to lower the water content by the exothermic reaction, and CaSO ₄ contributes to the formation of a large amount of etchringite needle crystals. By this action, it is considered that it will exert an excellent effect even in high water content or high organic matter soil.

In other words, utilizing the component characteristics of circulating fluidized bed boiler ash, which is a circulating resource, it is possible to manufacture and supply economical products in addition to the effective recycling of resources through the development of high value-added high- We think that it can be competitive compared to products.

In the present invention, the characteristics of ash (desulfurization gypsum) discharged from Hyundai Oilbank Co., Ltd. are actively utilized. As a result of evaluation of basic properties, the following chemical components were confirmed. Chemical composition of ash (BA: bottom ash, FA: fly ash) of circulating fluidized bed boiler ash is as follows.

division Chemical Analysis (%) SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ CaO MgO SO ₃ LOI I.R moisture BA 4.69 0.15 0.43 56.87 0.91 31.92 4.87 2.49 0.00 FA 7.90 0.17 0.29 54.18 1.05 24.52 11.75 2.31 0.15

The desulfurization gypsum from the circulating fluidized bed boiler of Hyundai Oilbank Co., Ltd., which uses 100% of Petro Cokes fuel, confirms that unreacted CaO and CaSO _4, which has completed the desulfurization process reaction, are the main components, and other impurities are present Respectively. These two components were found to be an important component for the effective function of fire - fighting and could be substituted for expensive lime or natural anhydrite.

In the present invention, the circulating fluidized bed boiler is not limited to the use of specific raw materials. You can use ash from a variety of low-grade bituminous coal or from a circulating fluidized-bed boiler using Petro Cokes with some confluence (within 15%). In the present invention, various ash generated from the circulating fluidized bed boiler can be used, but preferably fly ash can be used.

The present invention relates to a low cementitious mortar for deep-sea mixing treatment process characterized by comprising 20 wt.% Or less of Portland cement, 65 to 85 wt.% Of synthetic pozzolan material having developed material characteristics, and 5 to 15 wt. Thereby providing a fire-retardant composition.

In one embodiment of the invention, the Portland cement comprises up to 20% by weight of Portland cement. Generally, there is a proportional relationship in which the compressive strength value increases with increasing amount of Portland cement (OPC). However, considering the strength characteristics and economical aspects, it is considered that the addition amount of Portland cement is less than 20%.

In one embodiment of the present invention, the synthetic pozzolanic material comprises in the range of 65 to 85 wt%, and the synthetic pozzolanic material comprises 45 to 55 wt% blast furnace slag and 10 to 30 wt% fly ash . When the respective components are included in the above range, the desired effect can be obtained in the present invention. In the present invention, fly ash uses obtained from the circulating fluidized bed boiler described above.

In one embodiment of the present invention, the activator material comprises in the range of 5 to 15 wt%, and the activator comprises 5 wt% or less of natural anhydrous gypsum, 5 to 15 wt% of desulfurized gypsum, and 5 wt% Refining slag, and the like. The active material promotes the strength of the fire, and when the respective components are contained within the above range, the desired effect of the present invention can be obtained.

Hereinafter, the present invention will be described in detail with reference to examples of the present invention.

Example:

The fire-fighting composition according to the present invention and comparative examples thereof were prepared at the blending ratios shown in Table 2 below.

division Compounding ratio (% by weight) OPC SP FA Chungmu Desulfurization plaster Refining slag Example 1 20 47 20 - 10 3 Example 2 20 48 20 5 7 0 Comparative Example 1 20 44 20 3 10 3 Comparative Example 2 20 42 30 5 - 3 Comparative Example 3 20 52 20 5 - 3 Comparative Example 4 10 52 30 5 - 3

Experimental Example: Compressive Strength Test of Solid Soil

As the target clay, a marine clay having a water content of 45% and a wet unit volume weight of about 1,700 kg / m3 was used. Each 300 kg / m3 of the fireproof fabric prepared by the examples and comparative examples of the present invention was added, and mixed for about 5 minutes at a water-binder ratio of 100%. Then, a cylinder mold having a diameter of 70 mm and a height of 140 mm was produced Respectively. The specimens were cured at 23 ± 1 ℃ during the ages (7 and 28 days) and then uniaxial compressive strength was measured by KS F 2329 method.

division Uniaxial compressive strength (kg / cm2) 7 days 28th Example 1 19.0 36.4 Example 2 22.0 32.6 Comparative Example 1 20.6 26.9 Comparative Example 2 14.6 25.7 Comparative Example 3 15.2 30.4 Comparative Example 4 10.0 18.7

As a result of the analysis, it was confirmed that Compressive Strength Example 1 according to the present invention exhibited a compressive strength equal to or higher than Comparative Examples 1 to 4. The results of Example 2 according to the kind and amount of the activator showed excellent strength at 28 days of age.

Although the present invention has been described with reference to the above embodiments, the present invention is not limited thereto. It is to be understood that the above-described embodiments may be modified or changed without departing from the spirit and scope of the present invention, and those skilled in the art will recognize that such modifications and changes are also within the scope of the present invention.

Claims (4)

20 wt% or less of Portland cement, 65 to 85 wt% of a synthetic pozzolanic material, and 5 to 15 wt% of a strength promoting activating material,
The synthetic pozzolanic material comprises 45 to 55 weight percent blast furnace slag and 10 to 30 weight percent fly ash,
The activator material comprises not more than 5% by weight of natural anhydrous gypsum, 5 to 15% by weight of desulfurizing gypsum and not more than 5% by weight of refining slag,
Wherein the desulfurized gypsum is generated from a circulating fluidized bed boiler using 100% petro cokes as fuel, and contains lime (CaO) and gypsum (CaSO ₄ ) as minerals. Fire fighting composition.
delete delete 20 wt% or less of Portland cement, 65 to 85 wt% of a synthetic pozzolanic material, and 5 to 15 wt% of a strength-promoting active material,
The synthetic pozzolanic material comprises 45 to 55 weight percent blast furnace slag and 10 to 30 weight percent fly ash,
The activator material comprises not more than 5% by weight of natural anhydrous gypsum, 5 to 15% by weight of desulfurizing gypsum and not more than 5% by weight of refining slag,
The desulfurization gypsum is generated in a circulating fluidized bed boiler using 100% of petro cokes as a fuel, and comprises low-cement system for deep-sea mixing treatment method characterized by containing lime (CaO) and gypsum (CaSO ₄ ) A method of manufacturing a fire composition.