KR101061568B1 - Eco-friendly water-soluble inorganic soil ground hardener and its manufacturing method - Google Patents

Abstract

The present invention relates to an environment-friendly water-soluble inorganic soil ground hardener that can be mixed with soil to reinforce soft ground, and to a method for preparing the same, (a) potassium silicate aqueous solution (potassium silicate); and (b) potassium methyl siliconate (Potassium Methyl) Siliconate) aqueous solution; provides a method for treating by mixing the water-soluble inorganic soil ground hardener and the water-soluble inorganic soil ground hardener to the soil of the soft ground.

Description

Liquid type inorganic hardening agent for a ground of soil and it's treatment method using of the same

The present invention relates to an environmentally friendly water-soluble inorganic soil ground hardener capable of reinforcing soft ground by mixing with soil and a preparation method thereof.

Generally, soil hardeners that mix with soil to solidify or harden soft ground are known as cement hardeners, lime hardeners, water glass hardeners, acrylamide hardeners, and polyurethane hardeners. have.

Cement-based or lime-based hardeners improve soil strength by using a large amount of lime or cement containing heavy metals.They have low water permeability and are not uniformly mixed with the soil particles themselves. There is a problem that this large crack is likely to occur and the secondary pollution of the soil.

In addition, the cement-based solidifying agent has a long time required for solidification, so when used by mixing the solidifying agent and the soil of the soft ground, there is a problem that can not be transported immediately, the volume increases.

Water glass-based hardeners, acrylamide-based hardeners, and polyurethane hardeners are improved by solidifying the soil through curing reactions through initiators or catalysts or polymerization of monomers, but such hardeners are expensive ones. Due to the limitation of the amount of use in the large-scale application or the active use in the right place, there has been a problem that has not been widely used.

On the other hand, in the patent registration No. 10-0521869, "solidified mixed soil using reinforcing solidification and environment-friendly road construction method using the same", etc., the solidification of the soil showed the same compressive strength, but hardly compressive strength There was something in common.

In addition, as described above, the conventional soil hardener has a problem that it takes a long time since the solidification time during the soil coagulation requires a long time until the water of the water-soluble solidifier volatilizes.

Accordingly, the present inventors have attempted to develop an environmentally friendly water-soluble inorganic soil ground hardener which can be low in price and fast in solidification time and exhibit wet compressive strength.

In order to solve the problems of the prior art as described above, an object of the present invention consists of an aqueous solution of potassium silicate (KOH) and an aqueous solution of potassium methyl siliconate to show the wet compressive strength while the price of the soil is low and the condensation time is fast. It is to provide a liquid inorganic soil ground hardener composition.

In addition, another object of the present invention is to provide a preferable method for producing the aqueous potassium silicate solution and aqueous potassium methyl siliconate solution.

In addition, another object of the present invention is to provide a method of treating the two-part inorganic soil ground hardener by mixing the soil of the soft ground.

In order to achieve the above object, the present invention provides an environmentally friendly water-soluble mineral soil ground hardener consisting of (a) aqueous potassium silicate; and (b) aqueous potassium methyl siliconate; .

In addition, in order to achieve another object, the present invention (a) a step of preparing potassium silicate for the binder by reacting a silicon dioxide (SiO2) aqueous solution with a lithium hydroxide and an aqueous potassium hydroxide solution; And (b) reacting methyl silicon trichloride (CH ₃ SiCl ₃ ) with an excess of potassium hydroxide aqueous solution to produce potassium methyl siliconate for film formation. It provides a method of manufacturing.

In addition, in order to achieve another object, the present invention provides a method for treating an environmentally friendly water-soluble inorganic soil ground hardener by mixing the water-soluble mineral soil ground hardener in the soil of the soft ground.

At this time, if there is no other definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art.

Repeated descriptions of the same technical constitution and operation as those of the conventional art will be omitted.

In the present invention, the dry compressive strength refers to measuring the compressive strength of the soil ground hardener of the present invention by mixing it with the soil, compressing it into a mold in a predetermined shape, and drying it, and then drying it.

In the present invention, the wet compressive strength is to measure the compressive strength after mixing the soil ground hardener of the present invention with the soil and compressing it into a mold in a predetermined shape and drying it, soaking it in water for 24 hours and removing surface moisture. Say.

In the present invention, the wet compressive strength indicates that the soil ground hardener has an excellent water repellent effect, and means that the soil hardener can be efficiently used even in an area or environment where humidity or humidity is high.

Eco-friendly water-soluble inorganic soil ground hardener of the present invention includes the functions of hardeners and hardeners, which are mixed with soil and used for the purpose of strengthening the soft ground and improving the poor soil quality.

Potassium silicate used in the soil ground hardening agent according to the present invention combines the soil with potassium methyl siliconate without adhesion and serves to form a compressive strength while binding and curing with the soil.

In addition, in the present invention, potassium methyl siliconate (Potassium Methyl Siliconate) when the reaction with the carbon dioxide gas in the air to form a rubbery network of polymer material to form a hydrophobic coating, improving the water repellency of the soil (撥 水力) It plays a role.

The aqueous potassium silicate solution in the water-soluble inorganic soil ground hardener according to the present invention is preferably one obtained by reacting a silicon dioxide aqueous solution with a lithium hydroxide and an aqueous potassium hydroxide solution, and the aqueous potassium methyl siliconate solution is methyl silicon trichloride (CH ₃ Preference is given to using those obtained by reacting SiCl ₃ ) with an excess aqueous solution of potassium hydroxide. This is because it is advantageous in terms of production process, production efficiency and production cost of potassium silicate and potassium methyl siliconate.

In addition, the water-soluble inorganic soil ground hardener according to the present invention is preferably used by mixing an aqueous solution of potassium silicate and potassium methyl siliconate at 4: 1 to 1: 1 (v / v). This is because each of the above-mentioned effects appears most efficiently, and the desired solidification and curing effects appear upon reaction with the soil. Specifically, an aqueous potassium silicate solution may be used in excess of 4 based on the volume of potassium methyl siliconate.

However, the water-soluble soil ground hardener according to the present invention is not limited to the blending ratio of the above-described aqueous solution, and the blending ratio of the component and water is appropriately adjusted according to the environmental factors such as season, region, soil type and soil characteristics. I can regulate it.

In addition, in the present invention, in order to double the soil ground reinforcing effect, it is preferable to further use the adjuvant of the waste fiber or fabric. At this time, the amount of the adjuvant may be used by appropriately adjusting the mixing ratio of the soil and the adjuvant according to the characteristics of the soil and the characteristics of the soil, which will be apparent to those skilled in the art having ordinary knowledge in the field of the present invention.

On the other hand, the preferred method for producing potassium silicate and potassium methyl siliconate according to the present invention is as follows.

[Manufacturing Process of Potassium Silicate Aqueous Solution]

It is prepared by reacting an aqueous silicon dioxide solution with an aqueous lithium hydroxide and potassium hydroxide solution.

At this time, it is prepared by adding 4-5% (w / w) lithium hydroxide and 20-30% (w / w) potassium hydroxide mixed aqueous solution to 20-30% (w / w) silicon dioxide aqueous solution, stirring, and reacting. This is preferable because the production efficiency of potassium silicate is advantageous under the conditions described above. In addition, when the amount of potassium hydroxide is high, the adhesion is improved while the compressive strength is weakened. When the concentration of silicon dioxide is increased, the adhesion is weakened, but the compressive strength and transparency are improved. Therefore, it is most preferable to use it in the concentration range of the above-mentioned components. .

More specifically, an aqueous solution of potassium silicate is obtained through a step including the following steps.

① First process

Process of preparing by sealing with 510-1110g of water in 1800 ~ 2400g of 30 ~ 40% (w / w) silicon dioxide aqueous solution and sealing it with agitation at 70 ~ 75 ℃

② Second process

Process of preparing by reacting by stirring while adding potassium hydroxide 270 ~ 275g to 5 ~ 6% (w / w) of lithium hydroxide aqueous solution 820 ~ 830g prepared by dissolving lithium hydroxide

③ Third process

After stirring and dividing the aqueous solution of the ② process into the aqueous solution of the ① process, and maintaining the bath temperature stepwise 83-84 ° C., the reaction was continued by stirring for 80 to 100 minutes, allowed to stand, and then cooled, Process of manufacturing by replenishing water so that the weight is from 4,000 to 4,013 g

The potassium silicate aqueous solution prepared according to the present invention is used after a product evaluation with a crack or not after cracking after drying with a brush on a stainless steel sheet.

[Potassium methyl  Siliconeate aqueous solution manufacturing process]

A methyl silicon chloride (CH ₃ SiCl) compound was prepared by reacting silicon extracted from sand with methyl chloride (CH ₃ Cl) in a molar ratio of 1: 1, and methyl silicon trichloride selected from the compounds was reacted with an excess of potassium hydroxide solution. The aqueous solution containing potassium methyl siliconate Manufacture. At this time, the excess potassium hydroxide refers to an amount larger than the reaction material methyl silicon trichloride, usually 1.5 times or more of the theoretical reaction amount.

In addition, the method for producing a preferred soil ground hardener of the present invention is as follows.

[Soil ground of the present invention Solidifying agent  Manufacture process]

In this invention, it is preferable to mix and use the said potassium silicate and potassium methyl siliconate aqueous solution just before application to soil.

At this time, the potassium silicate and potassium methyl siliconate aqueous solution is preferably used by mixing 1: 1 (v / v). This is because mixing each aqueous solution at 1: 1 (v / v) results in the most desirable solidification and curing effects in the reaction with soil.

Therefore, the soil ground hardener of the present invention is stored in the form of an aqueous potassium silicate solution and an aqueous potassium methyl siliconate solution, respectively.

In addition, the potassium silicate aqueous solution and the potassium methyl siliconate aqueous solution prepared according to the above-described preferred manufacturing process of the present invention are preferably used by diluting 1: 1 (v / v) in water, respectively. This is because diluting water with each component can reduce the cost of use while showing the efficacy of potassium silicate and potassium methyl siliconate described above.

In addition, the treatment method applied to the preferred soil of the present invention is as follows.

[Soil Treatment Process]

Soil ground hardener prepared by the above method is treated by mixing in the soil of the soft ground.

At this time, the soil ground hardener prepared according to the present invention is preferably treated by mixing 20 to 60% (w / w) relative to the soil weight. This means that the solidification and hardening effect of the present invention is reduced when less than 20% (w / w) is used, and the soil reinforcing effect is not large compared to the excess usage when the treatment exceeds 60% (w / w). Since it becomes high, it is preferable to use a soil ground hardener within the above-mentioned use range. However, the present invention is not limited to the blending ratio of the above-mentioned solidifying agent and the soil, and the mixing ratio of the soil ground hardening agent to the soil weight appropriately according to the environmental factors such as season, region, soil type, and soil characteristics. You can also adjust

In addition, the soil ground hardener according to the present invention can be applied to both neutral and acidic soils, and exhibits a very good effect even in the wet compressive strength of the compressive strength of the solidification or hardening of the soil after treatment.

As described above, the water-soluble inorganic soil-based solidifying agent according to the present invention is to provide an effect that can be solidified and quickly solidify the soil and maintain the water repellency and water permeability, unlike the existing soil solidification.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, this is intended to facilitate an easier understanding of the present invention, but is not intended to limit the present invention through these.

Soil ground Solidifying agent  Produce

1. Preparation of aqueous potassium silicate solution Ⅰ

Ⓐ 510 g of water was added to 2,400 g of 30% (w / w) silicon dioxide aqueous solution, completely sealed, and stirred uniformly with a water bath in a 70 ° C. water bath. At this time, it stirred, checking the intermediate temperature.

Ⓑ After stirring at high speed while dividing 48 g of lithium hydroxide into 780 g of water little by little, stirring was continued uniformly while dividingly adding 270 g of potassium hydroxide. At this time, because the endothermic reaction was cooled and worked to confirm that completely dissolved proceeds to the next step.

Ⓒ Injecting the solution of ⓑ into the reactor of ⓐ while dividing the solution of ⓑ while stirring the ⓐ reaction stirrer and injecting it over 20 to 25 minutes. At this time, the reactor temperature was raised to 70 ~ 75 ℃ step by step in the water bath temperature to maintain 83 ~ 84 ℃ and continued stirring for about 90 minutes.

After cooling the solution proceeded to ⓓ ⓒ process, the weight was measured and the water was added to adjust the total weight to 4,000g and then mixed to complete the aqueous potassium silicate solution of the present invention.

2. Preparation of Aqueous Potassium Silicate Solution II

1,110 g of water was added to 1,800 g of 40% (w / w) silicon dioxide aqueous solution, completely sealed, and stirred uniformly with a water bath in a 70 ° C water bath. At this time, it stirred, checking the intermediate temperature.

Ⓑ After stirring at high speed while dividing 48g of lithium hydroxide into 780g of water, stirring was continued uniformly while dividingly adding 275g of potassium hydroxide. At this time, the endothermic reaction occurred, so that the solution was completely dissolved by working in a bath and then proceeded to the next step.

Ⓒ Injecting the solution of ⓑ into the reactor of ⓐ while dividing the solution of ⓑ while stirring the reaction stirrer ⓐ was injected over 20 to 25 minutes. At this time, the reactor temperature was raised to 70 ~ 75 ℃ step by step in the water bath temperature to maintain 83 ~ 84 ℃ and continued stirring for about 90 minutes.

After slowly cooling the solution which proceeded up to ⓓ ⓒ process, the weight was measured, and water was added to adjust the total weight to 4,013 g, followed by mixing, to complete the aqueous potassium silicate solution of the present invention.

3. Potassium methyl  Manufacture of Silicate Solution

Methyl chloride (CH 3 Cl) was reacted with silicon (Si) extracted from sand by heating at 50 to 80 ° C. in a molar ratio of 1: 1 to prepare methyl silicon chloride (CH ₃ SiCl). In addition, methyl silicon trichloride is selected from the compounds, and an excess amount of potassium hydroxide solution is added thereto, followed by reaction while raising the reactor temperature to 110 to 150 ° C / 1.5 to 3 atm to pressurize the potassium methyl siliconate of the present invention. The aqueous solution containing was completed.

4. Soil ground of the present invention Solidifying agent  Manufacture Ⅰ

The aqueous potassium silicate solution prepared in Example 1 was diluted 1: 1 with water (v / v).

In addition, the mixing ratio of 1: 1 (v / v) was gradually stirred in the potassium silicate dilution solution of the potassium methyl siliconate aqueous solution prepared in Example 3 and water diluted 1: 1 (v / v). After slowly adding and sealing a little after stirring for 30 minutes, the soil ground hardener of the present invention was prepared.

5. Soil ground of the present invention Solidifying agent  Manufacture Ⅱ

In the same manner as in Example 4, the potassium silicate dilution solution and the potassium methyl siliconate dilution solution were mixed at a mixing ratio of 80:20 (v / v) for 30 minutes to prepare a soil ground hardener of the present invention.

[ Experimental Example ]

1. Effect by concentration

The effect of the solidifying agent prepared in Example 4 was added to the soil by concentration of 20 to 60% by weight relative to the weight of the soil having an acidity of neutrality.

As a result, it was visually confirmed that the water solidified slowly as evaporated, and it was found that the soil solidified within 1 to 2 minutes.

2. Effect of Supplements

30% (w / w) of the solidifying agent prepared in Example 4 was added to the soil, and 20% (v / v) of the waste fiber was added to the waste fiber cut into 4 × 4 cm 2. Then, the mixture was stirred and the solidification effect of the soil was confirmed.

As a result, it was possible to confirm the solidification efficacy of the soil.

3. Compressive Strength Experiment

The soil ground hardener of the present invention prepared in Example 4 was mixed in 250 g of kaolin by concentration, and put into a circular mold having a diameter of 11 cm to make a specimen by pressing at 10 kg / cm ² .

After drying this, the dry compressive strength and the dried specimens were immersed in water for 24 hours, the surface moisture was removed, and the wet compressive strength was measured and shown in Table 1 below.

As a result, as shown in Table 1, the more the addition of the solidifying agent of the present invention to the kaolin was found to increase the compressive strength. In addition, the wet compressive strength was immersed in water for 24 hours to remove moisture from the surface of the specimen, and the compressive strength was measured, the dry compressive strength showed a strength of 30 ~ 40% level. However, the specimens not treated with the solidifying agent of the present invention showed no wet compressive strength at all.

In addition, after the specimen was made and dried in the same manner as the kaolin using 250 g of waste gypsum powder, the compressive strength and the wet strength were measured, respectively, and are shown in Table 2 below.

As a result, as shown in Table 2, the increase in the strength of the solidifying agent of the present invention showed an increase in compressive strength. However, in the wet compressive strength, the specimen without adding the solidifying agent of the present invention showed no wet compressive strength, and the 25 ml added specimen showed a compressive strength of 40-50% of the dry compressive strength. It is judged that the wet compressive strength test shows a proportional increase in the water repellency of the present invention when the wet compressive strength is increased as the amount of solidifying agent of the present invention is increased in the wet compression strength test. In addition, since the wet compressive strength is partially lower than the dry compressive strength, the solidifying agent of the present invention is judged to have lowered the compressive strength of the soil by permeating a certain amount of water in the solidification portion of the soil, which is treated according to the present invention. Soil, unlike the existing cement-based hardeners, can be said to have water permeability (透水性).

On the other hand, when comparing the compressive strength of kaolin and gypsum, the compressive strength according to the solidifying agent concentration of the present invention came out a little different, which is considered to represent different compressive strength values according to the characteristics of the soil material. However, the increase in dry compressive strength and wet compressive strength according to the increase of the solidifying agent according to the present invention is considered to play a role as soil ground hardening agent in any material.

On the other hand, as shown in Table 2, when the solidifying agent of the present invention to the gypsum base, it showed a phenomenon that immediately solidified after about 100 seconds, a phenomenon that the moisture contained in the gypsum immediately solidified.

This phenomenon is caused by the reaction of acid (sulphate group) of calcium sulfate (CaSO ₄ ) of gypsum with alkali of potassium silicate (potassium silicate) of the present invention to form a silica gel and a fine porous body of silica gel. The excess moisture is absorbed into the surface, and the surface moisture is quickly lost.

However, it was found that there was no such phenomenon in the neutral kaolin tested earlier.

4. Solidification Effect of Acid Soil

In this Experimental Example, acidified by adding 5% sulfuric acid solution to neutral kaolin, and stirring the soil ground hardener of the present invention prepared in Example 5 with 250 g of acid-treated kaolin and stirred, respectively, After making, the soil solidification effect was confirmed.

As a result, as soon as the soil solidified immediately after 100 seconds exhibited a phenomenon that the excess moisture is immediately absorbed, its dry compressive strength is shown in Table 3 below.

5. Effect of Potassium Silicate Concentration

In addition, the dry compressive strength using the potassium silicate aqueous solution concentration 6.25ml (solidifying agent addition amount 12.5ml) in the components of the water-soluble water-repellent adhesive used shown in Table 1 in Experimental Example 3 is 50.6kg / cm ² , the present invention used in Table 3 The dry compressive strength using 20 ml of potassium silicate aqueous solution (5 ml of potassium methyl siliconate aqueous solution) in the soil hardener component of was 72.2 kg / cm ² . As a result, it is thought that potassium silicate plays a big role in showing compressive strength.

6. Potassium methyl  Siliconate concentration Water repellent  effect

In this experimental example, in order to examine the effect of water repellency on the soil of potassium methyl siliconeate in the soil hardener of the present invention, a soil hardener having a different content of potassium methyl siliconate solution was applied to the soil and wet compression of the dried specimens. Intensity was analyzed.

First, 250 g of kaolin was treated by mixing the soil hardener prepared in Example 4 and dried, and the wet compressive strength thereof was measured. At this time, 1.56 ml, 3.13 ml, and 6.25 ml of potassium methyl siliconate concentrations were prepared using a solidifying agent prepared by mixing the same amount of an aqueous potassium silicate solution.

As a result, as can be seen in Table 4, as the concentration of potassium methyl siliconate increased, the wet compressive strength was shown to increase. It is believed that the concentration of potassium methyl siliconate in the soil hardener of the present invention is involved in the wet compressive strength.

As such, the soil-based hardener according to the present invention, unlike the conventionally known soil hardener, was found to have characteristics of exhibiting excellent wet compressive strength while rapidly solidifying the soil.

Claims (9)

delete (a) an aqueous solution containing potassium silicate obtained by reacting an aqueous silicon dioxide solution with a lithium hydroxide and aqueous potassium hydroxide solution; And
(b) an aqueous solution containing potassium methyl siliconate obtained by reacting methyl silicon trichloride (CH ₃ SiCl ₃ ) with an aqueous potassium hydroxide solution;
Eco-friendly water-soluble inorganic soil ground hardener, characterized in that consisting of. The method of claim 2,
The aqueous solution containing potassium silicate of (a)
It is prepared by adding 4-5% (w / w) lithium hydroxide and 20-30% (w / w) potassium hydroxide mixed aqueous solution to a 20-30% (w / w) silicon dioxide aqueous solution and stirring and reacting. Eco-friendly water-soluble mineral soil ground hardener. The method of claim 3, wherein
The aqueous solution containing potassium silicate of (a)
Iv) 30 to 40% (w / w) 510 to 1,110 g of water in 1800 to 2400 g of silicon dioxide aqueous solution, and sealing and preparing by stirring uniformly while boiling at 70 ~ 75 ℃;
Ii) stirring 5 to 6% (w / w) of lithium hydroxide aqueous solution 820 to 830g prepared by dissolving lithium hydroxide to dissolve 270-275 g of potassium hydroxide while stirring and reacting to prepare it; And
Iv) the solution of ii) is added to the aqueous solution of iii) while stirring and maintained, and the bath temperature is maintained at 83-84 ° C stepwise, followed by stirring for 80 to 100 minutes to allow the reaction to stand, and to cool. Preparing to replenish water so as to have a total weight of 4,000 to 4,013 g;
Eco-friendly water-soluble mineral soil ground hardener, characterized in that obtained through the step consisting of. The method of claim 2,
The aqueous solution containing potassium methyl siliconate of (b)
A methyl silicon chloride (CH ₃ SiCl) compound was prepared by reacting silicon with methyl chloride (CH ₃ Cl) in a molar ratio of 1: 1, and methyl methyl trichloride selected from the compounds was reacted with an excess of potassium hydroxide solution. Eco-friendly water-soluble mineral soil ground hardener, characterized in that. Environment-friendly water-soluble mineral soil ground hardener which mixes and processes the soil ground solidification agent of (a) potassium silicate aqueous solution and (b) aqueous solution of potassium methyl siliconate of any one of Claims 2-5 in the soil of a soft ground. Treatment method. The method according to claim 6,
A method for treating an environmentally friendly water-soluble inorganic soil ground hardener, characterized in that the aqueous solution of (a) and (b) is mixed and treated at 4: 1 to 1: 1 (v / v). The method of claim 7, wherein
Soil ground hardener is a method for treating environmentally friendly water-soluble inorganic soil ground hardener, characterized in that the treatment by adding 20 ~ 60% (w / w) of the soil by weight and mixing. The method of claim 8,
A method for treating two-part inorganic soil ground hardener, characterized in that the treatment further comprises adjuvant of waste fibers or textiles.