KR20190121027A - Composition for filling mine hole and filling method for mine hole using the same - Google Patents

Abstract

The present invention provides a mine filler composition comprising: 3-30 wt% of Portland cement; 10-50 wt% of circulating fluidized bed boiler fly ash (CFBC-FA) where carbon dioxide is not fixed; 20-70 wt% of bottom ash where carbon dioxide is not fixed; 0.01-1.0 wt% of fluidizing agents formed by mixing one or two more selected from naphthalene sulfonate, melamine sulfonate and polycarbonate; 0.01-1.0 wt% of material separation preventing agents formed by mixing one or two more selected from polyehtyleneoxide, polyacrylamide, polymethylethyl cellulose, polyethylpropyl cellulose, carboxymethyl cellulose and modified starch; and 0.01-1.0 wt% of polycarboxylate ether modified polyacrylate-based retaining agents. Accordingly, the present invention can recycle ashes from circulating fluidizing bed boilers of combined heat and power plants without calcium carbonate process, prevent materials from separating while having a high fluidity, and fill mine cavities airtightly.

Description

Mine filler composition and filling method of mine cavity using same {COMPOSITION FOR FILLING MINE HOLE AND FILLING METHOD FOR MINE HOLE USING THE SAME}

TECHNICAL FIELD The present invention relates to the field of construction, and in particular, to a light filler composition.

Most mines that have collected useful minerals remain in the cavities after the abandoned mines, and these cavities are in urgent need for countermeasures such as sinkholes and leachate generation. Charging method is being sought.

On the other hand, the combustion material from the circulating fluidized bed boiler of the cogeneration plant contains a large amount of glass-calcium oxide and the like unlike the combustion material from the conventional thermal power plant.

Korean Patent No. 10-1836372 discloses a technique of stabilizing a composite carbonate by reacting the above glass-calcium oxide with carbon dioxide and then using it as a material for a mine filling material.

However, the carbonation of the hydrated free calcium calcium oxide to produce the complex carbonate wastes the active ingredients such as carbon dioxide and free calcium oxide, incurring extra costs for the carbonation. There is a problem.

Therefore, by utilizing the expansion and initial reaction characteristics of the glass-calcium and solving the problem of fluidity deterioration problem, there is a need for the development of technology to utilize the combustion material itself as a material of the mine filler.

Patent Registration Publication No. 10-1836372

The present invention was derived to solve the above problems, it is possible to recycle the combustion material from the circulating fluidized bed boiler of the cogeneration plant without the need of a separate carbonate process, and the high fluidity does not occur separation of materials. It is an object of the present invention to provide a method for filling a mine cavity using the same, and a mine filler composition capable of tightly filling the mine cavity.

In order to solve the above problems, the present invention Portland cement 3-30% by weight; 10 to 50% by weight of circulating fluidized bed boiler fly ash (CFBC-FA) without carbon dioxide fixed; 20 to 70% by weight of circulating fluidized bed boiler bottom combustion material (CFBC-BA), in which carbon dioxide is not fixed; 0.01 to 1.0% by weight of a fluidizing agent formed by mixing one or two or more selected from naphthalene sulfonate, melamine sulfonate and polycarboxylic acid salts; 0.01 to 1.0 wt% material separation inhibitor formed by mixing one or more selected from polyethylene oxide, polyacrylamide, polymethylethyl cellulose, polyethylpropyl cellulose, carboxy methylcellulose, and modified starch; It proposes a photo-acid filler composition comprising a polycarboxylate ether modified polyacrylate-based 0.01 ~ 1.0% by weight.

It is preferable to further include; 0.1 to 10% by weight of the shrinkage agent formed by one or two or more selected from the light dolomite, desulfurized gypsum, O type expander, and K type expander.

0.01 to 1.0% by weight of a retarder formed by mixing one or two selected from tartaric acid, gluconic acid, citric acid, and formic acid.

It is preferable that the antifoaming agent, silicone-based antifoaming agent, fatty acid-based antifoaming agent, oil-based antifoaming agent, 0.01-1.0 wt% of antifoaming agent formed by mixing one or two selected from antifoaming agent and oxyalkylene antifoaming agent.

The present invention provides a method for filling a mine cavity using the mine filler composition, the foreign material removing step of removing the foreign matter inside the cavity of the mine; An outflow site sealing step of sealing an outflow site of the cavity of the mine so that the photoacid filler composition to be injected is not lost; A degree step of performing a degree of work to prevent leachate on the inner surface of the cavity of the mine; Injection hole drilling step for drilling the injection hole for the injection of the mineral filler composition; After the injection of the mineral filler composition, the injection hole sealing step of sealing the injection hole; suggests a method of filling the mine cavity comprising a.

The present invention can recycle the combustion material from the circulating fluidized bed boiler of the cogeneration plant without the need for a separate carbonate process, high fluidity, no separation of materials, and filling the mine cavity tightly filling the mine cavity It provides a composition and a method for filling a mine cavity using the same.

1 or less relates to an embodiment of the present invention,
1 is a photograph of fly ash material.
2 is a photograph of the floor burning material.
3 is a photograph of the mine filler.

Hereinafter, embodiments of the present invention will be described in detail.

Photoacid filler composition according to the present invention is basically, 3 to 30% by weight of Portland cement; 10 to 50% by weight of circulating fluidized bed boiler fly ash (CFBC-FA) without carbon dioxide fixed; 20 to 70% by weight of circulating fluidized bed boiler bottom combustion material (CFBC-BA), in which carbon dioxide is not fixed; 0.01 to 1.0% by weight of a fluidizing agent formed by mixing one or two or more selected from naphthalene sulfonate, melamine sulfonate and polycarboxylic acid salts; 0.01 to 1.0 wt% material separation inhibitor formed by mixing one or more selected from polyethylene oxide, polyacrylamide, polymethylethyl cellulose, polyethylpropyl cellulose, carboxy methylcellulose, and modified starch; polycarboxylate ether modified polyacrylate-based grease 0.01 ~ 1.0% by weight; comprises.

Portland cement can use ordinary Portland type 1-5 type cement or slag cement as defined in KS, and it is appropriate to incorporate 3-30% by weight of the mineral filler composition.

Less than 3% by weight is difficult to express sufficient strength, when it exceeds 30% by weight excessive strength is not economical.

Sample classification SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O SO3 P2O5 LOI CFBC-FA 19.7 9.06 16.6 25.3 11.2 1.91 0.89 0.15 11.1 3.73 CFBC-BA 20.9 5.19 12.9 23.1 7.94 1.27 0.61 24.7 0.13 2.56

Table 1 shows the components of the circulating fluidized bed boiler fly ash (CFBC-FA) and the circulating fluidized bed boiler bottom combustion material (CFBC-BA).

As shown in the component analysis data above, the combustor contains a large amount of calcium oxide, much of which consists of free calcium oxide.

The free-calcium oxide is transformed into calcium hydroxide by reacting with water, as shown in Formula 1, which promotes the reaction of cement due to the exothermic property and expands in volume.

Therefore, the strength can be initially increased and shrinkage can be prevented, but there is a disadvantage in that the fluidity decreases over time, which negatively affects the filling.

The amount of circulating fluidized bed boiler fugitive combustion material (CFBC-FA) that is not fixed with carbon dioxide is appropriately 10 to 50% by weight based on 100% by weight of the mineral filler composition, and the circulating fluidized bed bottom combustion material (CFBC-BA) with no carbon dioxide fixed. The amount of is used is 20 to 70% by weight with respect to 100% by weight of the mineral filler composition.

Fly ash is a fine powder with an average particle diameter of about 15 μm (FIG. 1). If it is less than 10% by weight, it is difficult to exhibit sufficient expansion characteristics, and if it exceeds 50% by weight, strength may decrease due to excessive water-cement ratio.

The bottom combustion material is a sand-like shape having an average particle diameter of 0.6 mm or less (90% or more) (FIG. 2). If the weight is less than 20 wt%, the replacement effect of sand is insignificant. .

Photoacid fillers are required to have high fluidity by the use of glidants (FIG. 3).

The fluidizing agent uses 0.01 to 1.0% by weight of one formed by mixing one or two or more selected from naphthalene sulfonate, melamine sulfonate and polycarbonate.

If it is less than 0.01% by weight, the fluidity expression characteristics are insufficient, and if it exceeds 1.0% by weight, material separation is greater than an increase in fluidity, which may cause defects.

As the material separation inhibitor, one formed by mixing one or two or more selected from polyethylene oxide, polyacrylamide, polymethylethyl cellulose, polyethylpropyl cellulose, carboxy methyl cellulose, and modified starch is used.

In order to minimize the loss of fluidity and to exert a material separation prevention effect, it is required to select an appropriate viscosity and an appropriate amount of the material separation inhibitor.

The viscosity of the material separation inhibitor is in the range of 200 to 30,000 cps based on a 2% aqueous solution.

Below 200 cps, the effect of preventing material separation is negligible, and above 30,000 cps, the loss of fluidity increases.

The amount of the material separation inhibitor is appropriately 0.01 to 1.0% by weight.

If it is less than 0.01% by weight, the material separation prevention effect is insignificant, and if it exceeds 1.0% by weight, fluidity is difficult to express.

There are two types of fats and oils that inhibit the reaction of alumina and calcium oxide. In the photocatalyst composition, a fat or oil which suppresses the reaction of the latter calcium oxide is more effective. Use the agent.

This has the effect of inhibiting the initial reactivity of the free-calcium oxide, and thus serves to prevent the initial fluidity loss of the photofiller composition.

The oil is used in 0.01 ~ 1.0% by weight, but less than 0.01% by weight, the effect of the oil is insignificant, if it exceeds 1.0% by weight, the effect of increasing the performance of the oil is not great, and the cause of the price increase of the mining filler This may not be desirable.

Since the circulating fluidized bed boiler combustor contains a large amount of free calcium oxide, it shows the expansion characteristics as described above, but the expansion effect may be different according to the change of temperature by season, especially at low temperature in winter. Can be.

Since the mine filler is intended for the full filling of the mine cavity, it is preferable to use a gastric shrinkage agent in order to obtain an optimized expansion effect despite the low temperature.

To this end, the mine filler composition according to the present invention further comprises a shrinkage preventing agent formed by mixing one or more selected from light dolomite, desulfurized gypsum, O-type expander, K-type expander (type of KS L 5217 expanded hydraulic cement). Can be.

The amount of the shrinkage preventing agent is appropriate in the range of 0.1 to 10.0% by weight with respect to 100% by weight of the light filler composition, but less than 0.1% by weight is insufficient in the expansion effect, if it exceeds 10% by weight is concerned about the strength decrease due to excessive expansion.

The photoacid filler composition according to the present invention contains a fat and oil as described above, so that sufficient pot life can be secured. However, since the reaction of free-calcium oxide proceeds rapidly at a high temperature such as a cold season, it is possible to secure a sufficient pot life only with the fat and oil. It can be difficult.

Therefore, in such a case, it is preferable to use a fat and oil in parallel.

To this end, the photoacid filler composition according to the present invention may further include a retarder formed by mixing one or two selected from tartaric acid, gluconic acid, citric acid, formic acid.

The amount of the retardant used is 0.01 ~ 1.0% by weight is appropriate, but less than 0.01% by weight, the reaction delay effect is insignificant, and when the content exceeds 1.0% by weight may cause excessive strength delay.

If excessive entrained bubbles such as bubbles occur in the mine filler composition injected into the mine cavity, it may interfere with the full filling of the mine cavity and cause a decrease in strength, so that an appropriate amount of air is contained by the use of an appropriate antifoaming agent. It is desirable to.

To this end, the mineral filler composition according to the present invention, 0.01 to 1.0 weight of the antifoaming agent formed by mixing one or two selected from an alcohol-based defoamer, a silicone-based defoamer, a fatty acid-based defoamer, an oil-based defoamer, an ester-based defoamer, an oxyalkylene-based defoamer More preferably;

Filling method of the mine cavity using the mine filler composition according to the present invention is as follows.

Foreign matter inside the cavity of the mine (ceiling, wall, floor) is removed with a high pressure washer and the like, and a leakable part of the cavity of the mine (such as an entrance to the mine) is sealed so that the mine filler composition to be injected is not lost.

In order to prevent the leachate of the inner surface (ceiling surface, wall surface, bottom surface) of the cavity of a mine, a water repellent is applied, such as a water repellent.

Perforate the injection hole for injection of the photoacid filler composition.

After the injection of the photoacid filler composition through the injection hole, the injection hole is sealed.

Hereinafter, examples and experimental results for demonstrating the physical properties of the present invention will be described.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 OPC 12.0 12.0 12.0 12.0 12.0 CFBC-FA 30.0 30.0 0.0 30.0 30.0 CFBC-BA 57.2 55.0 0.0 57.4 57.8 Carbonated CFBC-FA 0.0 0.0 30.0 0.0 0.0 Carbonated CFBC-BA 0.0 0.0 55.0 0.0 0.0 Maintenance agent 0.2 0.2 0.2 0.0 0.2 Glidants 0.5 0.5 0.5 0.5 0.0 Material Separation Preventer 0.1 0.1 0.1 0.1 0.0 Shrinkage inhibitor 0.0 2.0 2.0 0.0 0.0 Retardant 0.0 0.1 0.1 0.0 0.0 Antifoam 0.0 0.1 0.1 0.0 0.0 system 100.0 100.0 100.0 100.0 100.0

Table 2 shows the components and contents of Examples 1,2 and Comparative Examples 1 to 3 of the present invention.

Specifically, Example 1 is Portland cement, a circulating fluidized bed boiler fly ash (CFBC-FA), in which carbon dioxide is not fixed, a circulating fluidized bed bottom combustion material (CFBC-BA), in which carbon dioxide is not fixed, a fluidizing agent, a material separation inhibitor, and a holding An agent is mix | blended within the range of the above-mentioned compounding.

Example 2 incorporates an antishrink agent, a retardant, an antifoaming agent in addition to the formulation of Example 1.

Comparative Example 1 is to apply a carbonated combustion material in place of the circulating fluidized bed boiler combustion material in which the carbon dioxide is not fixed in Example 1 of the present invention, Comparative Example 2 does not contain a maintenance agent, unlike Example 1 of the present invention, In Comparative Example 3, unlike Example 1 of the present invention, a fluidizing agent and a material separation inhibitor are not used.

The flow, bleeding rate, expansion height, and compressive strength were tested by the test method of KS F4044_2004 'Hydraulic Cement Non-Shrink Grout Material', and the water-filler ratio was 50%.

Item Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Flo
(mm) 0 min 310 305 305 305 295 30 minutes 290 280 295 265 275 60 minutes 260 245 270 190 245 % Bleeding 0 0 0 0 1.6 Inflation height (%) 0.03 0.06 -0.06 0.02 -0.01 Compressive strength
(N / mm2) 3 days 2.4 1.8 2.3 3.2 2.6 7 days 4.3 4.4 3.9 4.6 3.9 28 days 8.6 9.2 8.2 8.4 7.8

Table 3 shows the physical property test results for Examples 1 and 2 and Comparative Examples 1 to 3 of the present invention described above.

Example 1 was shown to have excellent physical properties compared to Comparative Examples 1 to 3, as described below.

In the case of Example 2 (incorporation of an antishrink agent, a retardant, and an antifoaming agent in Example 1), the expansion height was slightly increased compared to that of Example 1 by the addition of the antishrinkant, and the initial age ( The compressive strength of 3 days) was slightly decreased, but the strength was slightly increased in the long-term age, so the use of retardant in the long term had little effect on the strength.

In Comparative Example 1 (incorporating the carbonated combustion material in Example 1), the flow characteristics were slightly higher than those of Example 1, but the expansion height contracted at 28 days of age.

This may cause settlement of the upper ground after filling the mine cavity, which may cause the mine sinking after filling.

In the case of Comparative Example 2 (combination excluding the fat and oil in Example 1), it was found that the flow loss over time was larger than that of Example 1.

This may be a deterioration factor of the filling effect of the mine cavity.

In the case of Comparative Example 3 (combination except the fluidizing agent and the material separation inhibitor in Example 1), the initial and long-term fluidity was reduced, and the material separation tended to be more severe than in Example 1.

This may cause settlement and strength degradation due to material separation.

Since the above has been described only with respect to some of the preferred embodiments that can be implemented by the present invention, the scope of the present invention, as is well known, should not be construed as limited to the above embodiments, the present invention described above It will be said that both the technical idea and the technical idea which together with the base are included in the scope of the present invention.

Claims (5)

3-30% by weight of Portland Cement;
10 to 50% by weight of circulating fluidized bed boiler fly ash (CFBC-FA) without carbon dioxide fixed;
20 to 70% by weight of circulating fluidized bed boiler bottom combustion material (CFBC-BA), in which carbon dioxide is not fixed;
0.01 to 1.0% by weight of a fluidizing agent formed by mixing one or two or more selected from naphthalene sulfonate, melamine sulfonate, and polycarbonate salts;
0.01 to 1.0% by weight of a material separation inhibitor formed by mixing one or more selected from polyethylene oxide, polyacrylamide, polymethylethyl cellulose, polyethylpropyl cellulose, carboxy methylcellulose, and modified starch;
0.01 ~ 1.0 wt% of polycarboxylate ether modified polyacrylate
A photoacid filler composition comprising a. The method of claim 1,
0.1-10 wt% of shrinkage agent formed by mixing one or more selected from light dolomite, desulfurized gypsum, O type inflator, and K type inflator;
Photoacid filler composition, characterized in that it further comprises. The method of claim 1,
0.01 to 1.0% by weight of a retarder formed by mixing one or two selected from tartaric acid, gluconic acid, citric acid and formic acid;
Photoacid filler composition, characterized in that it further comprises. The method of claim 1,
0.01 to 1.0% by weight of an antifoaming agent, a silicone antifoaming agent, a fatty acid antifoaming agent, an oil antifoaming agent, an ester antifoaming agent, or an oxyalkylene antifoaming agent formed by mixing one or two of them;
Photoacid filler composition, characterized in that it further comprises. As a method for filling a mine cavity using the mine filler composition according to any one of claims 1 to 4,
Foreign substance removal step of removing foreign substances in the cavity of the mine;
An outflow site sealing step of sealing an outflow site of the cavity of the mine so that the photoacid filler composition to be injected is not lost;
A degree step of performing a degree of work to prevent leachate on the inner surface of the cavity of the mine;
Injection hole drilling step for drilling the injection hole for the injection of the mineral filler composition;
After the injection of the mineral filler composition, the injection hole sealing step of sealing the injection hole;
Charging method of a mine cavity, characterized in that it comprises a.

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