KR101631476B1 - Manufacturing method for grouting chemical liquid agency - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a grouting chemical liquid composition which can be used at all without using one kind of ordinary cement at all or by using a slag and a desulfurization byproduct produced during petro coke combustion .
The method for producing a grouting chemical liquid composition according to the present invention comprises the steps of 1) diluting sodium silicate with water to obtain Solution A; 2) a calcium oxide content of 50 to 80% by weight and a sulfate content of 50 to 80% by weight based on 100 parts by weight of a slag having a calcium oxide content of 30 to 70% by weight and a specific surface area of 3,500 to 8,000 cm ² / 1 to 500 parts by weight of a desulfurization by-product generated in the combustion of petro coke having a sulfate oxide content of 10 to 40% by weight and a specific surface area of 2,000 to 8,000 cm ² / g; 3) mixing water with the binder to obtain liquid B; And 4) mixing the solution A and the solution B to gel.

Description

TECHNICAL FIELD [0001] The present invention relates to a grouting chemical liquid composition,

The present invention relates to a method for producing a grouting chemical liquid composition, and more particularly, to a method for producing a grouting chemical liquid composition which is capable of exhibiting performance equivalent to or superior to that of one kind of ordinary cement by exhibiting the potential hydraulic property of slag by the desulfurization by- The present invention relates to a method for manufacturing a grouting chemical liquid composition, which can prevent a leaching phenomenon by compensating for shrinkage of a molded article.

During the use of civil engineering and architectural structures, it is often necessary to reinforce the foundation and reinforcements due to tunnel construction, expansion or remodeling, change of purpose, increase of load.

The grouting method is used as a method for improving the ground which is expected of these problems and as a means for eliminating the safety problems such as order and reinforcement in constructing any objects.

When the grouting is applied, the chemical solution injection method is to inject water such as cement liquid into the soft ground by the pressure of the pump to fill the voids or cracks in the ground to prevent the water from flowing out or to harden the soft ground layer to harden the ground And a chemical solution such as a cement liquid, a mortar liquid or a water glass liquid is used as an injection material.

Therefore, the chemical solution injection method has a complex effect such as prevention of scarring by increasing the strength of the ground by injecting a solution liquid and a solution-type chemical solution, which originally has fluidity but can be solidified after a predetermined time, Is one of the improvement methods of the ground that expects.

The water-based chemical solution, which occupies the majority of the solution type injection material, has the advantage of excellent permeability as compared with the cement suspension type injection material. However, since it has weak strength and low durability, it is used as a semi-suspension type injection material in combination with the cement suspension type . Cement is used as a main binder in grouting chemical injection method which is generally used. Cement can cause environmental pollution due to strong alkali and hexavalent chromium in the ground, and excessive volume shrinkage occurs during hydration reaction.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide a grouting chemical composition composition capable of preventing shrinkage of a molded body gelled by calcium oxide, which is contained in petroleum coke- Method.

Another object of the present invention is to provide a method for producing a grouting chemical liquid composition capable of exhibiting performance equivalent to or superior to that of one kind of ordinary cement by exhibiting the potential hydraulic property of slag by the desulfurization by-product generated in petro coke combustion.

Another object of the present invention is to provide a method for producing a grouting chemical composition which is excellent in homogeol strength, easy to control the gel time, and excellent in permeability.

According to an aspect of the present invention, there is provided a method for preparing a grouting chemical liquid composition comprising the steps of: 1) diluting liquid sodium silicate with water to obtain solution A; 2) a calcium oxide content of 50 to 80% by weight and a sulfur oxide content of 30 to 70% by weight based on 100 parts by weight of slag having a calcium oxide content of 30 to 70% by weight and a specific surface area of 3,500 to 8,000 cm ² / 1 to 500 parts by weight of a desulfurization by-product generated in the combustion of petro coke having a sulfur oxide content of 10 to 40% by weight and a specific surface area of 2,000 to 8,000 cm ² / g; 3) mixing water with the binder to obtain liquid B; And 4) mixing the solution A and the solution B to gel.

Further, the liquid A is preferably obtained by further mixing 5 to 200 parts by weight of the liquid silica sol with respect to 100 parts by weight of the liquid sodium silicate.

The desulfurization by-product is preferably generated during the desulfurization process of the fluidized-bed boiler using the petro coke as fuel.

The binder may further comprise 5 to 200 parts by weight of cement based on 100 parts by weight of the slag to improve initial strength. The cement may be selected from the group consisting of CSA (Calcium Sulfur Aluminate), alumina cement, ultra fast cement, Cement, three-kind cement, blast-furnace slag cement and fly ash cement, or a mixture of two or more thereof.

In addition, the binder preferably further comprises 0.1 to 10 parts by weight of a fluidizing agent relative to 100 parts by weight of the slag in order to improve fluidity.

The fluidizing agent may be any one selected from the group consisting of naphthalene type, melamine type, amine type, lignin type and polycarboxylic type, or a mixture of two or more thereof.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to effectively prevent the leaching phenomenon by compensating for the shrinkage of the molded body gelled by the calcium oxide, which is contained in the petroleum coke desulfurization by-product in large amounts.

In addition, the potential hydraulic properties of the slag are exhibited by the desulfurization by-products generated when the petro coke is burned, and the performance equivalent to or higher than that of the one kind ordinary cement can be exhibited. Therefore, one kind of ordinary cement widely used in the joint material for the grouting chemical solution injection method is not used at all or the use amount thereof can be minimized.

Particularly, it can minimize leaching of harmful components such as hexavalent chromium, which is contained in a large amount in cement, and is superior in homogeol strength, easiness in controlling gel time, and excellent in permeability as compared with a binder for a grouting chemical injection method using cement.

Hereinafter, a method for manufacturing a grouting chemical liquid composition according to the present invention and a method for injecting a chemical solution using the same will be described in detail.

The method for producing a grouting chemical liquid composition according to the present invention comprises the steps of 1) obtaining a solution A, 2) obtaining a binder, 3) obtaining a solution B by mixing the binder and water, and 4) And mixing.

1) First, liquid A is obtained by diluting liquid sodium silicate with water. Alternatively, a liquid silicate sol may be mixed with liquid sodium silicate and then diluted with water to obtain solution A. In this case, it is preferable that the liquid silica sol is incorporated in an amount of 5 to 200 parts by weight based on 100 parts by weight of liquid sodium silicate. If the amount is less than 5 parts by weight, the effect of pH reduction due to the incorporation of silica sol is insufficient. When the amount exceeds 200 parts by weight, the pH reduction effect is excellent, and the effect of preventing the groundwater contamination due to alkali is improved, .

The dilution ratio of the liquid sodium silicate (or the mixture of the liquid sodium silicate and the liquid silica sol) and water is usually about 1: 1, but the mixing amount of water can be appropriately increased or decreased depending on the situation in the field.

2) Next, the composition of the binder will be described in detail. The binder comprises slag, de-by-products resulting from combustion of petro coke, cement and a fluidizing agent.

The slag has a calcium oxide content of 30 to 70% by weight and a specific surface area of 3,500 to 8,000 cm ² / g. The slag may be blast furnace slag, converter slag, electric furnace slag, electric furnace reducing slag, copper slag, , A burned slag, and a KR slag, or a mixture of two or more thereof.

The calcium oxide content of the slag is preferably 30% by weight to 70% by weight. When the amount of the calcium oxide is less than 30% by weight, the calcium silicate hydrate (CSH) , The content of aluminum oxide (Al ₂ O ₃ ) or silica oxide (SiO ₂ ) is relatively lowered, so that it is difficult to produce calcium aluminate hydrate and calcium silicate hydrate, so that the strength is lowered. A specific surface area of 3,500 ~ 8,000cm After grinding for ² / g is preferably together 3,500cm ² / g is less than if the activity is lowered it is difficult to strength 8,000cm ² / g greater than the activity is superior in strength, but enhancement to obtain ultrafine minutes , The production amount is greatly lowered in the dust collecting process.

In addition, the desulfurization by-product generated in the petro coke combustion has a calcium oxide content of 50 to 80% by weight, a sulfate oxide content of 10 to 40% by weight and a specific surface area of 2,000 to 8,000 cm ² / g . Said sulfate oxide refers to sulfur trioxide. The same is applied hereinafter.

Since the desulfurization by-product generated in the petro coke combustion occurs as a by-product of the desulfurization process in the process of mixing petroleum coke or coal with petroleum coke or coal as a fuel in a fluidized bed boiler for combusting limestone for desulfurization in the furnace, It is a material containing ingredients and is very economical.

Particularly, the calcium oxide component, which is contained in a large amount in the petroleum coke desulfurization by-product, reacts with water to form Ca (OH) ₂ And the OH ^- component generated in the slag breaks down the acid film of the slag in a short time by the alkali and sulfate compound stimulation to accelerate the release of ions such as Ca ^{2 +} and Al ^{3 +} in the slag and react with them, It increases the initial compressive strength of the cured product by rapidly accelerating the curing by producing a large amount of lean gut. In addition, it is a substance that simultaneously acts as a stimulant and a binding agent to generate calcium silicate hydrate and develop strength as age elapses. When the content of calcium oxide is less than 50% by weight or the content of sulfate oxide is less than 10% by weight, the effect is not sufficiently exhibited. When the content of calcium oxide exceeds 80% by weight or the content of sulfate When the content of the sulfate is more than 40% by weight, the combined effect of alkaline and sulfate complexing is not achieved properly.

Also desulfurization by-product having a specific surface area of 2,000cm ² / g is less than it is difficult to penetrate into the ground when the liquid injector is difficult in the initial strength development, 8,000cm ² / g and the manufacturing cost largely increases in the grinding process when the excess.

On the other hand, in the case of the grouting injection material, if a long time elapses after the gel is formed, if the gelled molded body is gradually shrunk and water contained in the gelled molded body is leached out, it causes leakage, Problems may arise. Particularly, when volume contraction occurs, Na ₂ O component and SiO ₂ When the component is leached, the durability of the groundwater contamination and the injected chemical solution may be lowered.

However, when the calcium oxide component of the desulfurization by-product reacts with water and absorbs, exothermic and expands to form Ca (OH) ₂ , the reaction equation is as follows.

CaO + H ₂ O-> Ca (OH) ₂ + 15.6 kcal mol ^-1

Therefore, in the present invention, the incorporation of the desulfurization by-product is very effective in compensating the shrinkage of the gelled molded body to solve the leaching phenomenon.

As a result, the calcium oxide component of the desulfurization by-product reacts with water to act as an alkali stimulant of slag after transferring to calcium hydroxide. However, due to the increase of temperature due to heat generation, hydration reaction of slag is promoted and volumetric shrinkage of the hardened body is compensated, The effect of preventing the phenomenon is exhibited.

In addition, it acts to improve the soil by absorbing water rapidly in the ground of high functioning state.

Preferably, the desulfurization by-product comprises 1 to 500 parts by weight of the slag, based on 100 parts by weight of the slag. If the amount of the slag is less than 1 part by weight, the strength of the slag does not easily react with the slag. When the amount exceeds 500 parts by weight, the weight of the slag is relatively decreased.

It is preferable to further include cement in the binder in order to improve the initial strength. The cement may be selected from the group consisting of CSA (Calcium Sulfur Aluminate), alumina cement, ultra fast cement, rapeseed cement, first type cement, third type cement, Asbestos cement, or a mixture of two or more thereof.

It is preferable that the cement is incorporated in an amount of 5 to 200 parts by weight based on 100 parts by weight of the slag. When the amount is less than 5 parts by weight, initial strength development is difficult. When the amount exceeds 200 parts by weight, the initial strength is increased, but harmful components such as hexavalent chromium can be eluted and the economical efficiency is also insufficient.

It is preferable to further include liquid and powder type fluidizing agents for improving fluidity and the fluidizing agent is any one or a mixture of two or more selected from the group consisting of naphthalene type, melamine type, amine type, lignin type and polycarboxylic type desirable.

The fluidizing agent is preferably incorporated in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the slag. If the amount is less than 0.1 part by weight, there is no improvement in flowability. If the amount is more than 10 parts by weight, the fluidity may be excessively improved and the material separation may occur.

In addition, since the particles of the binder in the liquid chemical composition according to the present invention exist in a form of a finer particle than the conventional one-kind ordinary cement particles, the particles easily penetrate into the gap between the soil and the soil and the fluidity is improved by the fluidizing agent Excellent permeability compared to grouting solution using cement.

3) Water is mixed with the binder thus prepared to obtain Solution B. At this time, dilution ratio of binder and water is in the range of 1: 1 ~ 5, but this ratio can also be appropriately changed according to the field.

4) Finally, the solution A and the solution B are mixed and gelled to prepare a grouting solution composition.

Hereinafter, preferred embodiments and comparative examples of the present invention will be described. The following examples are intended to illustrate the invention and should not be construed as limiting the scope of the invention.

Comparative Example

To 227 kg of sodium silicate 3, 23 kg of silica sol was added, 250 kg of water was added and diluted to prepare solution A, and 420 kg of water was added to 240 kg of one kind of ordinary Portland cement and mixed to prepare solution B. After gelation with solution A and solution B, gel time and 9 specimens with dimensions of 5 cm × 10 cm were prepared and cured at 20 ° C. to measure the homogeolite strength at 3 days, 7 days, and 28 days of age .

Example  One

Except that the specific surface area was 3,360 cm ² / g and the calcium oxide content was 67% by weight with respect to 100 parts by weight of the blast furnace slag having a specific surface area of 4,130 cm ² / g instead of the first cement. And 90 parts by weight of PetroCokes desulfurization by-product, which is 24% by weight of sulfate oxide, were homogeneously mixed to prepare a binder.

The thus prepared solutions A and B were mixed and gelated, and then the gel time and homogeel compressive strength were measured.

Example  2

The comparative examples and all of the conditions are the same, but this, 100 parts by weight of blast furnace slag cement, having a specific surface area with respect to the kite has a specific surface area of 4,370cm ² / g 100 parts by weight of slag in place of one kind of cement and 3,360cm ² / g calcium oxide 80 parts by weight of Petrocoke desulfurization by-product having a calcium oxide content of 67% by weight, sulfate oxide of 24% by weight, and 2 parts by weight of naphthalene-based fluidizing agent powder were homogeneously mixed to prepare a binder.

The thus prepared solutions A and B were mixed and gelated, and then the gel time and homogeel compressive strength were measured.

Test result

Table 1 below shows the results of visually observing the gel time, the compressive strength of homogeol by age and the leaching phenomenon after one month according to the type of binder.

division Gel time (sec) Homo-gel Compressive Strength (MPa) After 2 months
Leaching phenomenon 3 days 7 days 28th Comparative Example 32 1.25 2.25 3.65 Many occur Example 1 36 2.13 3.83 5.83 Not at all Example 2 37 2.15 3.53 5.68 Small amount

The gel time did not show a significant difference depending on the type of binder, and the use of the binder according to the present invention showed no significant difference from the comparative example using conventional cement as a binder. Therefore, even if the present invention replaces the conventional cement in the liquid injection method, the gel time is not greatly influenced, and thus it is considered that there is no great difficulty in using the cement in the field. In this case, the release of harmful components such as hexavalent chromium, which is contained in a large amount in the cement, can be minimized.

Compressive strength of homogeol was higher in all ages than in the case of using cement as compared with the comparative example. Therefore, it can be seen that the present invention can improve the ground effect, the ground subsidence reduction effect, and the ability to secure the bearing capacity, as compared with the conventional method using the cement.

It was confirmed that the leaching phenomenon was significantly reduced in the embodiment of the present invention compared with the conventional leaching method after two months. In the case of the grouting material, when the gel is formed for a long time after the gel is formed, the gelled molded body gradually shrinks and the water contained in the gelled molded body leaks out to cause leakage, causing the elasticity to be lost, The use of the binder according to the present invention compensates for the shrinkage of the gelled body caused by the desulfurization by-product, and it is understood that the leaching of the grouting molded body after gelation hardly occurs.

It is also confirmed that the elasticity is excellent and the problems of the conventional grouting material can be sufficiently overcome.

Claims (6)

1) diluting liquid sodium silicate with water to obtain solution A;
2) The calcium oxide content is 50 to 80% by weight and the sulfur oxide content is 3% by weight based on 100 parts by weight of slag having a calcium oxide content of 30 to 70% by weight and a specific surface area of 3,500 to 8,000 cm ² / 1 to 500 parts by weight of a desulfurization by-product generated in the combustion of petro coke having a specific surface area of 2,000 to 8,000 cm ² / g;
3) mixing water with the binder to obtain liquid B; And
4) mixing the solution A and the solution B to gel,
The desulfurization by-product is generated in a desulfurization process in which limestone is mixed for petroleum desulfurization in a fluidized bed boiler using petro coke alone as fuel or petroleum coke and coal as fuel,
The desulfurization by-product stimulates alkali and sulphate so as to exhibit latent hydraulic properties of the blast furnace slag, generates calcium silicate hydrate to exhibit strength,
Further comprising 5 to 200 parts by weight of cement based on 100 parts by weight of the slag in order to improve initial strength,
The cement is any one or a mixture of two or more selected from the group consisting of CSA (Calcium Sulfur Aluminate), alumina cement, ultrafast cement, ultramodern steel cement, first type cement, third type cement, blast furnace slag cement and fly ash cement Of the grouting solution.
The method according to claim 1,
Wherein the liquid A is obtained by further mixing 5 to 200 parts by weight of liquid silica sol with respect to 100 parts by weight of the liquid sodium silicate.
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