JP3095431B2 - Hardener composition for preparing ground injection chemical, method of preparing ground injection, and method of injecting chemical into ground - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilized hardener composition for preparing a ground injection liquid and a method for preparing a ground injection liquid using such a stabilized hardener composition. About. Further, the present invention relates to a method for injecting a chemical solution into the ground using the ground injection chemical solution prepared as described above.

[0002]

2. Description of the Related Art Conventionally, a grouting method has been widely known in which a ground injection chemical called a grouting agent is injected into the ground and gelled in the ground in order to strengthen soft ground or stop water from leaking ground. As a ground injection chemical,
Sodium silicate-hardening agent suspension type, which is a mixture of an aqueous sodium silicate solution (hereinafter referred to as solution A) as a main ingredient and an aqueous suspension of a water-insoluble curing agent (hereinafter referred to as solution B). Are variously known.

As the curing agent contained in the liquid B, for example, a combination of gypsum and lime, a combination of gypsum, lime and cement, a combination of gypsum and cement, etc. are well known. In any of these hardeners, in the form of an aqueous suspension, the viscosity increases due to the hydration reaction, the permeability decreases, or the obtained homogel strength decreases, and finally, the solution B itself gels. Various methods have heretofore been proposed to enhance the stability of the liquid B, since the liquid does not function as a curing agent liquid.

For example, Japanese Patent Publication No. Sho 62-31759 proposes to use a condensed phosphate as a stabilizer for a liquid B comprising calcium sulfate and a hydroxide of an alkaline earth metal. According to this method, although the stability of the solution B is enhanced, before the preparation of the solution B, the condensed phosphate and the curing agent are filled together in a bag, that is, if the solution is left in a single pack, the condensed phosphorus Since the acid salt gradually undergoes a chemical change and eventually does not function as a stabilizer, the condensed phosphate and the curing agent must be separately filled in a bag, stored, and separately transported to the injection site. Thus, storage and transportation are complicated.

Further, Japanese Patent Publication No. 62-9155 discloses that as a stabilizer for solution B comprising gypsum and lime,
It has been proposed to include a nonionic or anionic surfactant. This method also enhances the stability of Liquid B, however, the surfactant does not dissolve simultaneously with or in the presence of gypsum, lime,
In preparing the liquid, the surfactant is dissolved in water in advance, and gypsum and lime must be added to the solution. Thus, as described above, the surfactant and the curing agent cannot be made into a one-pack, There is a great practical inconvenience that the surfactant and the curing agent have to be separately brought to the site.

[0006]

The object of the invention is to solve the present invention, conventional systems
B in ground injection chemicals mainly containing aqueous sodium acid solution
It has been completed as a result of intensive studies on problems relating to the stabilization of a liquid, especially on a curing agent composition capable of stably maintaining a curing agent together with a stabilizer in a one-pack packaged state. That is, the alkali metal salt of oxycarboxylic acid can not only suppress the hydration reaction of the curing agent and stabilize the solution B, but also stabilize the alkali metal Since the salt does not react with the curing agent, they can be stably packed into one pack, and furthermore, the stabilized curing agent composition containing such a stabilizer is simply added to water and mixed. A highly stable B solution can be obtained, and this B solution is mainly used.
The injection liquid obtained by mixing with the liquid A , which is an agent, has excellent permeability because of its low viscosity, and has found that it is possible to obtain a ground injection liquid liquid with an improved uniaxial compressive strength of its homogel, This has led to the present invention.

[0007] The present invention has been pre-mixed one-packed, it stabilized consisting stabilizer powder and a curing agent powder Ke
It is an object of the present invention to provide a curing agent composition containing sodium iodate as a main component . Further, in the present invention, a liquid B is prepared using such a stabilized curing agent composition, and the liquid B is used as a main ingredient.
The present invention aims to provide a method for preparing a ground injection chemical solution which is excellent in permeability into the ground by mixing with a liquid A, and which provides a homogel having a significantly improved uniaxial compressive strength.
I do. Another object of the present invention is to provide a method of injecting a chemical solution into the ground using such a chemical solution.

[0008]

According to the present invention, there is provided a mixture of a powder of a curing agent as a component (a) and a powder of a stabilizer as a component (b).
The present invention provides a stabilized hardener composition for preparing a ground injection chemical solution to be used as an agent. (A) Component: At least one selected from cement and lime and gypsum (b) Component: Alkali metal salt of oxycarboxylic acid.

According to the present invention, the following A solution and B solution
The method for preparing a ground injection chemical solution comprising:
Solution B was prepared by adding a stabilized curing agent composition comprising a mixture of a powder of a curing agent as a component and a powder of a stabilizer as a component (b) to water, and the solution B was combined with the solution A. There is provided a method for preparing a ground injection chemical solution characterized by mixing. Liquid A: sodium silicate aqueous solution Liquid B: An aqueous suspension comprising a curing agent as the following component (a) and a liquid B stabilizer as the component (b).

(A) Component: at least one selected from cement and lime and gypsum (b) Component: Alkali metal salt of oxycarboxylic acid. Further, according to the present invention, there is provided a method for injecting a chemical solution into the ground, which injects the ground injection chemical solution prepared as described above into the ground. In the present invention, the stabilized curing agent composition comprises a mixture of the curing agent powder as the component (a) and the stabilizer powder as the component (b) . Here, as the hardening agent, at least one selected from cement and lime is used.
A mixture of seed and gypsum is used, and as a stabilizer, an alkali metal salt of oxycarboxylic acid is used.

As the gypsum, gypsum dihydrate, gypsum hemihydrate,
Type III anhydrous gypsum, type II anhydrous gypsum and the like are used, and hemihydrate gypsum or type III anhydrous gypsum is particularly preferably used.
Hemihydrate gypsum refers to α-hemihydrate gypsum or β-hemihydrate gypsum, and type III anhydrous gypsum refers to type III α-anhydrite or type III β-anhydrite. This type III β-anhydrite is also referred to as soluble anhydrite and has a chemical formula of CaSO ₄ , for example, is produced from natural dihydrate gypsum (CaSO ₄ .2H ₂ O) or so-called chemical gypsum be able to.

As the lime, quick lime or slaked lime is used, but slaked lime is preferably used. Furthermore,
As the cement, jet cement, Portland cement, alumina cement, blast furnace cement and the like are used, but Portland cement is particularly preferably used.

[0013] In these gypsums, limes and cements, the finer the particles, the shorter the gel time of the injection liquid obtained and the faster the development of the homogel strength.
It is preferably not more than μm, more preferably not more than about 30 μm. Hydraulic raw powders other than those described above may be used together as long as the permeability to the ground and the uniaxial compressive strength of the homogel are not significantly reduced.

Examples of the alkali metal salt of oxycarboxylic acid as the stabilizer include alkali metal salts of oxy acids such as citric acid, tartaric acid, malic acid, glyconic acid and lactic acid. Preferred alkali metal salts are as follows. Is
Examples include sodium salts and potassium salts. Alkali metal salts of oxycarboxylic acids as these stabilizers,
The finer the particle, the better, so that it can be dissolved in a short time when poured into water and stirred to improve the preparation of the drug solution. Depending on the type of stabilizer, especially the particle size is about 100 μm
Hereinafter, when it is about 50 μm or less, the solubility in water is good, so that there is an advantage that workability is good by itself, and further, for example, during dissolution of the stabilizer, the type III gypsum in the gypsum It is preferable in that it does not deteriorate into II-type gypsum, and the hemihydrate gypsum does not deteriorate into dihydrate gypsum, thereby lowering the gel strength.

In the curing agent composition according to the present invention, the alkali metal salt of oxycarboxylic acid is generally used in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the curing agent (a). . When the amount of the stabilizer is 10
When the amount is less than 0.1 part by weight with respect to 0 part by weight, the effect of stabilizing the solution B is poor. That is, when a curing agent composition, which is a mixture of a curing agent and a stabilizer, is added to water and stirred to prepare solution B, the curing agent undergoes a hydration reaction in solution B, and
When the viscosity of the solution rises or when the stirring of the solution B is stopped, the precipitate hardens, causing inconvenience such as difficulty in redispersion, and it becomes difficult to inject the chemical solution into the ground. is there. Further, as described above, the strength of the homogel obtained by mixing the liquid B with the liquid A in which the curing agent partially hardens may be remarkably reduced. However, when the stabilizer is used in an excessively large amount, the development of the homogel strength of the drug solution obtained by mixing the solution A and the solution B is undesirably slow.

The hardener composition according to the invention is thus a mixture of hardener powder and stabilizer powder,
In the one-pack packaged state in the packaging bag, the curing agent is stably maintained for a long period of time, and if the one-pack curing agent and the stabilizer are simultaneously put into water and stirred, the curing agent becomes stable. The agent easily dissolves in water to give solution B, and functions as a stabilizer for solution B.

The one-pack of the curing agent composition according to the present invention may be obtained by filling a packaging bag as a uniform or non-uniform mixture of a curing agent and a stabilizer at a predetermined ratio. The packaging bag does not deteriorate during the long-term storage due to exposure to rain or absorption of atmospheric moisture (for example, type III anhydrous gypsum or hemihydrate gypsum changes to dihydrate gypsum). like,
Those made of a water-resistant material are preferred. For example, kraft paper whose inner surface or outer surface is coated with a water-resistant material such as synthetic resin such as polyolefin or asphalt or tar, or a wrapping material formed by joining a plurality of papers through these water-resistant materials Is preferred from the viewpoint of water resistance and handleability. More specifically, examples of the packaging material include the second type kraft paper specified in JIS P3401 and tarpaulin paper specified in JIS Z1503.

As described above, when the curing time and the strength of the homogel are changed by forming the curing agent and the stabilizer into one pack, each component can be easily increased or decreased, and the workability at the injection site of the chemical solution can be improved. Is significantly improved. According to the present invention, the one-packed curing agent composition is added to water as it is to prepare a liquid B as a suspension, and the liquid B is mixed with the liquid A to obtain a chemical for ground injection. Can be prepared.

The sodium silicate as the liquid A is JI
No. 1, No. 2 or No. 3 specified in SK 1408 are preferably used, but No. 3 is particularly preferably used. In the method for preparing such a chemical solution, the amount of sodium silicate used is appropriately selected depending on the state and purpose of the ground to be injected,
In 400 l of the drug solution, an aqueous solution defined by the above-mentioned JIS is usually in a range of 60 to 160 l, particularly 70 to 140 l.
A range of 1 is preferred.

In the method of injecting a chemical solution into the ground according to the method of the present invention, the solution A and the solution B are prepared in separate tanks as described above, and these are conventionally established as injection methods. For example, it is injected into a required ground by a single pipe injection method, a double pipe injection method, or the like. When shortening the gel time of a chemical solution or increasing the homogel strength, A
If the concentration of sodium silicate in the solution is to be increased and the amounts of the hardener and the stabilizer in one pack should be increased, on the other hand, if the gel time of the chemical solution is to be increased or the homogel strength is to be reduced, the solution A And the amounts of the one-pack curing agent and stabilizer may be reduced.

[0021]

(Blending of curing agent and stabilizer)

Weigh the curing agent and stabilizer at the ratios shown in Tables 1 and 2,
After uniformly mixing to obtain a curing agent composition, the mixture was sealed in a water-resistant bag made of polyethylene-laminated kraft paper (laminate of a polyethylene sheet between kraft paper and kraft paper). The sample was allowed to stand at room temperature for the period described in “Neglecting days”.

The particle sizes of the β-hemihydrate gypsum and slaked lime used were about 10 μm, the particle diameter of the cement was about 30 μm, and the particle diameter of the stabilizer was about 75 μm. [Time until the curing agent in liquid B solidifies (liquid B stability)] The above-mentioned curing agent composition was charged into 176 g of compounding water at 30 ° C at a ratio shown in Tables 1 and 2, and stirred for 5 minutes. Thereafter, the mixture was left to stand, and the time required for the sedimented curing agent to solidify was measured. The results are shown in Tables 1 and 2. [Gel time of drug solution] The mixing ratio according to the composition of the solution A shown in Tables 1 and 2 was 3
No. sodium silicate and water were mixed to prepare solution A. Separately,
The curing agent composition was added to 176 g of water at the compounding ratio shown in Tables 1 and 2, and stirred for 5 minutes to prepare Liquid B.

The solutions A and B were each adjusted to 20 ° C., mixed, and the gel time was measured. The results are shown in Tables 1 and 2. [Uniaxial Compressive Strength of Homogel] Separately, after adjusting each of the liquid A and the liquid B to 20 ° C., they are mixed to form a cured product, that is, a homogel, and cured at 20 ° C. for 1 day. Was measured. The results are shown in Tables 1 and 2. In addition, this measurement was performed only about the thing with high stability of B liquid.

In Examples 1 and 3 according to the present invention,
The solution B was prepared by uniformly mixing a curing agent and a stabilizer to form a composition, and allowing the mixture to stand for 6 hours. Liquid temperature is 30 ℃
However, it has been shown that solution B is stable for 6 hours, and thus such solution B
Can be practically used. Further, the strength of the homogel is practically sufficient.

In Examples 2, 4 and 6 according to the present invention, a curing agent and a stabilizer were uniformly mixed to form a composition, and the mixture was allowed to stand for 90 days to prepare a solution B. Also in this case, the solution B is stable, and the gel time and the uniaxial compressive strength of the homogel are not changed as compared with the previous examples. In Examples 6 and 7, in the preparation of the curing agent composition, sodium tartrate and potassium citrate were used instead of sodium citrate as a stabilizer, but the same as in the case of using sodium citrate The results are shown to be obtained.

On the other hand, in Comparative Example 1, sodium tripolyphosphate was used instead of sodium citrate as a stabilizer when adjusting the curing agent composition. Although there is no problem in practicality in injecting the chemical solution into the ground, the stability of the solution B is slightly lowered. Comparative Examples 2 and 3
In, after sodium tripolyphosphate and a curing agent are uniformly mixed to form a curing agent composition, the mixture is left for 90 days,
It is prepared by adjusting the B liquid. The stability of Solution B is remarkably low, indicating that sodium tripolyphosphate chemically changes due to contact with the curing agent and does not function as a stabilizer of Solution B. Therefore, it is shown that sodium tripolyphosphate cannot be mixed with a curing agent to form a composition, packed in a single package, and stored.

Comparative Example 4 is a case where a lignin sulfonate was used as a stabilizer when adjusting the curing agent composition. Even when this curing agent composition is put into water and stirred, the lignin sulfonate does not dissolve in water, and the curing agent in the liquid B solidifies in 30 minutes. When injecting a chemical solution into the ground, it usually takes about 1 to 2 hours after the mixing of the liquid A and the liquid B until the injection is completed. Is difficult to use.

[0028]

[Table 1]

[0029]

[Table 2]

Example 8 Instead of a water-resistant bag made of polyethylene-laminated kraft paper, a bag made of double kraft paper was used, and the curing agent was sealed and allowed to stand.
Solution B and A having the same composition by the completely same procedure as in Example 2.
The solution was adjusted, and the uniaxial compressive strength of the homogel when the two solutions were mixed was measured. The result was 10 kg / cm ^2, which was lower than that of Example 2 (absorbed moisture within 90 days, It is presumed to have been altered).

[0031]

The curing agent composition according to the present invention has the above-mentioned composition.
The powder of the curing agent as the component (a) and the component (b)
It is a mixture with a powder of a stabilizer, and can stably store a curing agent for a long time in a one-pack state in a packaging bag. Moreover, such a stabilized curing agent composition gives a highly stable liquid B simply by putting it in water and mixing, so that the workability is extremely excellent, and the gel time and strength can be easily changed. is there. In addition, the liquid B has excellent stability, and the injection liquid obtained by mixing the liquid B and the liquid A has a low viscosity, and thus has excellent permeability, and
By injecting into the ground, a homogel with improved uniaxial compressive strength is produced and the ground is improved. Furthermore, since the hydration reaction of the curing agent in the solution B is suppressed, the gel time is stable and the homogel strength is excellent.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09K 17/12 C09K 17/06 C09K 17/14 C09K 17/48

Claims (3)

(57) [Claims] 1. A mixture comprising a hardener powder as a component (a) and a stabilizer powder as a component (b) ,
A stabilized hardener composition for preparing a ground injection chemical solution mainly containing an aqueous solution of sodium iodide . (A) Component: At least one selected from cement and lime and gypsum (b) Component: Alkali metal salt of oxycarboxylic acid 2. A process for the preparation of solution A and ground injection drug solution consisting of solution B the following, (a) From consisting components curing agent powder and a (b) a powder mixture of components a is stabilizer < The formulated curing agent composition is added to water to prepare a liquid B,
A method for preparing a ground injection chemical solution, comprising mixing the solution B with the solution A. A solution: aqueous solution of sodium silicate solution B: Ru (b) component der and the curing agent is below the component (a)
Aqueous suspension consisting of a stabilizer component (a): at least one and plaster component (b) is selected from cement and lime: alkali metal salts of oxycarboxylic acid 3. A method of injecting a liquid for ground injection into the ground, which comprises mixing a liquid A and a liquid B below into a ground, wherein a powder of a curing agent as the component (a) and a powder of the component (b) are used. A stabilized hardener composition comprising a powder and a mixture of a certain stabilizer is added to water to prepare a liquid B, and the liquid B is mixed with the liquid A to prepare a liquid for ground injection. Method of injecting chemicals into the ground, characterized by injecting water into the ground. A solution: aqueous solution of sodium silicate solution B: Ru (b) component der and the curing agent is below the component (a)
Water suspension consisting of a stabilizer. (A) Component: At least one selected from cement and lime and gypsum (b) Component: Alkali metal salt of oxycarboxylic acid