JP3104128B2 - Ground injection material, its manufacturing apparatus and injection method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for soil injection obtained by subjecting water glass to a dealkalization treatment by electrolytic dialysis and an apparatus for producing the same. To a soil injection material having a low content of acid radicals obtained by desalting the mixed solution of the above by electrolytic dialysis and an apparatus for producing the same, and a ground injection method of injecting these soil injection materials into the ground, together exhibit strength, excellent durability because of low shrinkage, and it is possible to use over a long period of time for the ion-exchange membranes used in electrodialysis does not require regeneration, even a high SiO ₂ concentration of water glass The above-described material for soil injection, a production apparatus and an injection method thereof, which can be subjected to a dealkalization or a desalination treatment, and further efficiently consolidate the ground in accordance with any ground condition To.

[0002]

2. Description of the Related Art Conventionally, as a ground injection material for injecting into soft ground or the like and consolidating the ground, an injection material mainly containing water glass and an injection mainly using an aqueous solution of acidic silica sol comprising water glass and an acid. Materials and materials for injection mainly using neutral colloidal silica are known.

[0003]

Any of the above-mentioned injection materials contains a large amount of alkali or salt. If the content of alkali or salt is large, the physical properties of the consolidated body are affected,
Not only does the strength of the compact decrease, but the alkali or salt is released or deviates from the compact within a long period of time, and the compact shrinks, thereby affecting the durability.

In order to improve such disadvantages, in recent years,
A method has been adopted in which water glass is passed through and contacted with an ion exchange resin to remove alkali components in the water glass.
In the material for ground injection using such water glass, the above-mentioned disadvantages are solved because the content of alkali or salt is reduced.

However, the alkali removal method using an ion exchange resin cannot be used for a long time because the resin needs to be regenerated, and water glass having a high SiO ₂ concentration cannot be used in the ion exchange resin. It cannot be treated because of gelation, and waste acid is discharged when the ion exchange resin is regenerated.

Accordingly, it is an object of the present invention to provide a soil injection material obtained by subjecting water glass to a dealkalization treatment by electrolytic dialysis using an ion exchange membrane, a manufacturing apparatus therefor, and a method for mixing the soil injection material with an acid. Or an acidic soil injection material having a low acid content obtained by desalting a mixed solution of water glass and an acid by electrolytic dialysis using an ion exchange membrane, and an apparatus for producing the same, and the soil injection material are injected into the ground. The purpose of the present invention is to provide a method for injecting soil into the ground. In particular, it exhibits high consolidation strength, has excellent durability due to low shrinkage, and has a long life because the ion exchange membrane used for electrodialysis does not require regeneration. it is possible to use for, resulting de alkali or desalting also high water glass with a SiO ₂ concentration, further, solid efficiently ground adapted to any ground situation Was obtained by improving the drawbacks existing in the prior art described above, or in the prior art do not exist ground infusion timber, and to provide a manufacturing apparatus and soil injection method.

[0007]

In order to achieve the above-mentioned object, according to the material for ground injection of the present invention, an alkali content obtained by subjecting water glass to electrolytic dialysis using an ion exchange membrane as a diaphragm and subjecting to alkali removal treatment. Characterized in that it is made of an aqueous solution of dealkalized water glass having a reduced content.

Furthermore, in order to achieve the above-mentioned object, according to the material for ground injection of the present invention, the alkali content obtained by subjecting water glass to electrolytic dialysis using an ion exchange membrane as a diaphragm and dealkalization treatment is reduced. It is characterized by comprising an acidic water glass aqueous solution having a low acid content obtained by mixing an alkali-free aqueous glass solution and an acid.

Further, in order to achieve the above-mentioned object,
According to the material for ground injection of the present invention, an acidic silica sol obtained by mixing water glass and an acid is subjected to electrolytic dialysis using an ion exchange membrane as a diaphragm, and an aqueous solution of an acidic water glass having a low content of acid radicals obtained by desalting. It is characterized by becoming.

In order to achieve the above object, according to the manufacturing apparatus of the present invention, an electrolytic dialysis tank, a pair of anodes and cathodes respectively arranged on both opposite end surfaces inside the tank, and a space between these positive and negative electrodes An anion exchange membrane is located on the most anode side, and a cation exchange membrane is located on the most cathode side, comprising positive and anion exchange membranes arranged alternately and so as to form a plurality of compartments. Of the plurality of compartments, the compartments where the anode and the cathode are located are filled with water, the other compartments are alternately filled with a water glass aqueous solution and water, respectively, and a current is supplied between the positive and negative electrodes. Thereby, Na ⁺ ions in the aqueous solution of water glass are permeated and released through the cation exchange membrane into the water filled in one of the adjacent compartments via the cation exchange membrane, and OH ^- ions are passed through the anion exchange membrane. Adjacent Through the membrane into the water filled in the other compartment, whereby the aqueous water glass solution is subjected to a dealkalization treatment to obtain a dealkalized aqueous solution having a reduced alkali content.

Further, in order to achieve the above-mentioned object, according to the manufacturing apparatus of the present invention, an electrolytic dialysis tank, a pair of anodes and cathodes respectively arranged on both opposite end surfaces inside the tank, and An anion-exchange membrane on the anode side between the electrodes and a cation-exchange membrane on the cathode side, which are arranged so as to form three parallel and spaced compartments. By filling the central compartment of these three compartments with the aqueous solution of water glass and the compartments at both ends with water, and passing an electric current between the positive and negative electrodes, the Na ⁺ ions in the aqueous solution of water glass become Water was permeated and released through the membrane into one of the adjacent compartments through the cation exchange membrane, and OH ^- ions were loaded into the other adjacent compartment through the anion exchange membrane. Through the membrane in water The water glass aqueous solution in the central compartment is subjected to a dealkalization treatment to obtain a dealkalized water glass aqueous solution having a reduced alkali content.

Further, in order to achieve the above-mentioned object, according to the production apparatus of the present invention, an electrolytic dialysis tank, a pair of anodes and cathodes respectively disposed on opposite end surfaces inside the tank, and An anion exchange membrane is located on the most anode side between the electrodes, and a cation exchange membrane is located on the most cathode side, and are arranged alternately and so as to form a plurality of compartments. Of the plurality of compartments, the compartments where the anode and the cathode are located are filled with water, and the other compartments are alternately mixed with an aqueous solution of acidic silica sol obtained by mixing water glass and acid, and water. and stuffing, and by energizing a current between Hikage electrode through the membrane to Na ⁺ ions in the acidic aqueous silica sol solution is stuffing the compartment on one side of the adjacent through the cation exchange membrane water Over-released, and the acid radicals are permeated and released through the anion exchange membrane into the water filled in the adjacent compartment on the other side, whereby the acidic silica sol aqueous solution is desalted to reduce the acid radical content. It is characterized by obtaining a small amount of aqueous acidic water glass solution.

Further, in order to achieve the above-mentioned object, according to the production apparatus of the present invention, an electrolytic dialysis tank, a pair of anodes and cathodes respectively disposed on opposite end surfaces inside the tank, and An anion-exchange membrane on the anode side between the electrodes and a cation-exchange membrane on the cathode side, which are arranged so as to form three parallel and spaced compartments. An acidic silica sol aqueous solution obtained by mixing water glass and an acid in the center compartment, filling the compartments at both ends with water, and passing a current between the positive and negative electrodes. Thereby, Na ⁺ ions in the aqueous solution of acidic silica sol are permeated and released through the cation exchange membrane into the water filled in one of the adjacent compartments via the cation exchange membrane, and the acid radicals are adjacent via the anion exchange membrane The other side It is transmitted released through the membrane into the water which is stuffing the compartment, thereby characterized in that to obtain a less acidic water glass solution of the acidic aqueous silica sol solution is desalted acid radical content.

In order to achieve the above object, according to the method for injecting ground into the ground according to the present invention, the alkali glass obtained by subjecting water glass to electrolytic dialysis using an ion-exchange membrane as a membrane and subjecting to alkali removal treatment has a reduced alkali content. Electrodialysis of a water glass aqueous solution, an acidic water glass aqueous solution having a low acid content obtained by mixing this dealkalized water glass aqueous solution with an acid, and an acidic silica sol obtained by mixing water glass and an acid using an ion exchange membrane as a diaphragm. Then, an aqueous solution of acidic water glass having a low content of acid radicals obtained by desalting is injected directly into the ground, or a ground injection solution obtained by mixing a reactant with the aqueous solution of de-alkali or acidic water glass, respectively. It is characterized by being injected into the ground.

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the accompanying drawings.

The material for ground injection according to the present invention is an aqueous alkali-free water glass solution having a reduced alkali content and an acidic water glass aqueous solution having a small acid content as described above. The details are as follows.

(1) Aqueous alkali-free water glass solution This is a water glass aqueous solution with reduced alkali content obtained by subjecting water glass to electrolytic dialysis using an ion exchange membrane as a diaphragm and subjecting to alkali removal treatment. Water glass exhibits the following equilibrium reaction in an aqueous solution.

[0018]

Embedded image Na ₂ SiO ₃ + H ₂ O → NaOH + NaHSiO ₃ NaHSiO ₃ + H ₂ O → NaOH + H ₂ SiO ₃

Since the NaOH produced here is a strong electrolyte having a high degree of dissociation, it easily permeates through the ion exchange membrane.
On the other hand, since silica is a weak electrolyte and has large ionic molecules, it hardly permeates an ion exchange membrane. Therefore, the water glass is subjected to electrolytic dialysis using the ion exchange membrane as a diaphragm and dealkalized to form a water glass aqueous solution having a reduced alkali content.

However, if the dealkalization proceeds too much, p
Since H decreases to a neutral region and gelation easily occurs by itself, the dealkalization is stopped when the gelation time can be maintained to some extent, and the aqueous alkali-free water glass according to the present invention is obtained. This aqueous solution can be directly injected into the ground as a ground injection liquid.

Furthermore, in the present invention, water glass containing an additive as water glass can be subjected to electrolytic dialysis and dealkalization treatment. Examples of the additives include inorganic salts such as calcium chloride, aluminum chloride, sodium chloride, bicarbonate, sodium aluminate, sodium hexametaphosphate, and sodium phosphate, inorganic acids such as phosphoric acid, boric acid, and sulfuric acid, succinic acid, and citric acid. Acids, organic acids such as acetic acid, organic compounds such as glyoxal, diacetin, triacetin, ethylene carbonate, cement, lime, etc., ordinary water glass hardeners, buffers, pH adjusters, optional additives such as sequestering agents, etc. Used.

When such additive-containing water glass is subjected to electrolytic dialysis, an aqueous alkali-free water glass solution containing the additive is produced. This may be injected directly into the ground,
Further, by adding a reactant, an injection material having high strength and durability can be obtained. Of course, metal ions contained in the additive are also reduced by the above-described electrolytic treatment. In addition, anions other than silicate ions are also reduced. Therefore, if this aqueous solution of water glass is used as an injection material, it is possible to perform injection without changing the quality of groundwater.

In the above-mentioned electrodialysis, an ion exchange membrane used as a diaphragm selectively transmits cations but does not transmit anions, and a cation exchange membrane selectively transmits anions but does not transmit cations. It is an anion exchange membrane. The dealkalized water glass aqueous solution according to the present invention is produced as follows using such an ion exchange membrane as a diaphragm.

FIG. 1 is an explanatory view of one embodiment of an apparatus for producing an aqueous alkali-free water glass solution according to the present invention. The apparatus comprises an electrolytic dialysis tank 1, a pair of anodes and cathodes 2a and 2b, a cation exchange membrane 3, and a cathode. It is composed of an ion exchange membrane 4.

The electrolytic dialysis tank 1 is an ordinary box-shaped reaction tank made of synthetic resin or metal. A pair of anode and cathode 2
a and 2b are opposite end faces 5 inside the electrodialysis tank 1.
a, 5b or in the vicinity thereof.

Further, the cation exchange membrane 3 and the anion exchange membrane 4 are arranged alternately between the anode 2a and the cathode 2b in the electrodialysis tank 1 so as to form a plurality of sections 6a, 6b. At this time, the anion exchange membrane 3 is located closest to the anode 2a, and the cation exchange membrane 4 is located closest to the cathode 2b.

Using the manufacturing apparatus described above, first, a plurality of sections, for example, sections 6a, 6a... 6a are filled with a water glass aqueous solution, and sections 6b, 6b. The compartments 6a and 6b are alternately filled with a water glass aqueous solution and water so as to be adjacent to each other. The section 6b where the anode is located and the section 6b where the cathode is located are both filled with water.

Next, when a direct current is applied between the anode 2a and the cathode 2b, Na in the aqueous solution of water glass in the section 6a is exposed.
⁺ Ions are introduced into the water filled in the adjacent one of the compartments 6b via the cation exchange membrane 3, and the cation exchange membrane 3
Is transmitted and emitted. Further, the OH ^- ions are permeated and released through the anion exchange membrane 4 into the water filled in the adjacent section 6b via the anion exchange membrane 4. As a result, the aqueous solution of water glass in the section 6a is subjected to a dealkalization treatment to obtain an aqueous solution of dealkalized water glass having a reduced alkali content.

FIG. 2 shows a modified production apparatus of FIG. 1, and as shown in FIG.
A pair of anodes 2a and cathodes 2b respectively disposed on opposite inner end surfaces 5a and 5b;
An anion exchange membrane 4 is provided on the anode 2a side between the electrodes 2a and 2b, and a cation exchange membrane 3 is provided on the cathode 2b side so as to form three parallel sections 6b, 6a and 6b. The three compartments 6b, 6a, 6b are provided with a water glass aqueous solution and the compartments 6b, 6 at both ends of the three compartments 6b, 6a, 6b.
b is filled with water and a DC current is applied between the positive and negative electrodes 2a and 2b, so that the Na ⁺ ions in the aqueous water glass solution are adjacent to each other via the cation exchange membrane 3. Through the membrane 3 into the water filled in the compartment 6b on the other side, and OH ^- ions pass through the membrane 4 into the water filled in the adjacent compartment 6b via the anion exchange membrane 4. It is transmitted and released, whereby the water glass aqueous solution in the central section is subjected to a dealkalization treatment to obtain a dealkalized water glass aqueous solution having a reduced alkali content.

In FIG. 1 and FIG. 2, the obtained aqueous solution of dealkalized water glass is recovered from each of the compartments 6a, 6a... 6a through a conduit 7, and at the same time, simultaneously with the compartments 6b, 6b.
The aqueous solution of NaOH in 6b is also recovered through the conduit 8.

[0031] Figure 3 is an improved manufacturing apparatus of FIG. 2, the electrolytic dialysis cell 1, the end face 5a, and a pair of electrodes 2a and cathode 2b respectively disposed 5b, the cation and anion exchange membranes 3, 4 2 in that it has three sections 6b, 6a, 6b.

FIG. 3 shows, in addition to the structure shown in FIG. 2, an aqueous alkali-free water glass tank X, and this tank X and the section 6a are connected via a pump P1, for example, through a conduit 7 at the bottom. , Tank X and section 6a are connected, for example, at the top through conduit 7a, forming a circulation system A between section 6a and tank X. Furthermore, each of the compartments 6b, 6b also passes through a conduit 8, for example from the bottom to the top, and is connected via a pump P2 to form a circulation system B.

In the apparatus shown in FIG. 3 having the above-described structure, the circulating system A is used to dispense the aqueous solution of dealkalized water glass into the electrodialysis tank 1.
The electrodialysis is repeated by circulating through the section 6a, and the circulation is stopped when the aqueous solution of de-alkali water glass becomes a desired state, and is transferred to a storage tank (not shown). Then, section 6
The untreated aqueous water glass solution is introduced into the section 6a, and circulated by the circulation system A in the same manner to repeat the electrodialysis.

By such a circulation, a large quantity of high-quality aqueous solution of dealkalized water glass can be continuously produced regardless of the size of the electrolytic dialysis tank 1 as shown in FIG.

Further, in FIG.
The H aqueous solution is circulated through the compartments 6b, 6b of the electrodialysis tank 1 to obtain a NaOH aqueous solution in a desired state.
In addition, in FIG. 3, installation of the circulation system B is arbitrary.
Further, the circulation systems A and B can be applied to the apparatus shown in FIG.

The alkali water glass aqueous solution thus obtained has a reduced alkali content, so that the alkali exerts less influence on the physical properties of the consolidated body and exhibits high compaction strength. In addition, even when a long period of time has passed after the consolidation, the release or deviation of the alkali from the consolidated body is small, and therefore, the compacted body does not shrink and the durability is improved.

In addition, since the ion exchange membrane used in the electrodialysis does not require regeneration unlike the ion exchange resin,
It can be used for a long time. Further, the ion exchange membrane is a leaving alkaline water glass solution readily manufactured that exhibits a high caking strength using obtained by dealkalization also high water glass with a SiO ₂ concentration, a high water glass having Accordingly SiO ₂ concentration obtain.

(2) Acidic water glass aqueous solution having a low content of acid radicals This is produced by using the alkali-free water glass aqueous solution produced by the above (1), or an acidic silica sol obtained by mixing water glass and an acid. It is manufactured by electrodialysis as described above. Hereinafter, these will be described in detail.

(A) Utilizing an aqueous alkali glass solution. It is obtained by mixing and reacting the aqueous alkali-free water glass solution produced as described above with an acid and shifting the pH to a strongly acidic region. Although the gelation time is greatly delayed, the gelation time may be directly injected into the ground as a ground injection liquid.

Since the amount of the acid is small as compared with the conventional acidic silica sol comprising water glass and acid, the content of the acid radical is reduced. In particular, the content of the acid radical is preferably 5000 ppm or less.

FIG. 4 is a process diagram for producing an aqueous acidic water glass solution using an aqueous alkali glass solution. In FIG. 4, L is a de-alkali water glass solution storage tank, A is an acid solution storage tank, W
Denotes a water supply tank, and M1 denotes a mixing tank.

An aqueous solution of electrolyzed dialyzed water glass from the storage tank L, an aqueous acid solution from the storage tank A, and water from the water supply tank W are supplied to the mixing tank M1 through conduits 9, 10, and 11, respectively. The reaction is carried out with stirring at 12 to obtain an acidic aqueous glass solution. In FIG. 4, 13, 14, 15, 16,
17 is a valve.

(B) Electrolytic dialysis of acidic water glass An acidic water silica sol obtained by mixing water glass and acid is subjected to electrolytic dialysis using an ion exchange membrane as a diaphragm and desalting treatment in the same manner as described above. The water glass may contain the same additives as described above. This manufacturing apparatus is shown in FIG.

FIG. 5 is an explanatory view of one embodiment of the apparatus for producing an aqueous acidic water glass solution according to the present invention.
Is the same as That is, this manufacturing apparatus is similar to FIG.
Electrolysis dialysis tank 1 and opposite end faces 5 inside this tank 1
a, a pair of anodes 2a and cathodes 2b respectively disposed on the anode 2a and the cathode 2b,
The anion exchange membrane 4 is located on the side, and the cation exchange membrane 3 is located closest to the cathode 2b.
6b, the cation exchange membrane 3 and the anion exchange membrane 4 are arranged.

Using the above-described manufacturing apparatus, first, an aqueous solution of acidic silica sol obtained by mixing water glass and an acid is added to a plurality of sections, for example, sections 6a, 6a,. .. 6b are each filled with water, whereby an aqueous solution of acidic silica sol and water are respectively filled in sections 6a,
6b are alternately filled so as to be adjacent to each other.

Next, when a direct current was applied between the anode 2a and the cathode 2b, Na ⁺ ions in the acidic silica sol aqueous solution in the section 6a were filled in the adjacent section 6b via the cation exchange membrane 3. The water is permeated and released through the cation exchange membrane 3. Further, the acid radicals are permeated and released through the anion exchange membrane 4 into the water filled in the adjacent compartment 6 b via the anion exchange membrane 4. The aqueous solution of acidic silica sol in this section 6a is subjected to a desalting treatment to obtain an aqueous solution of acidic water glass having a low acid content. The acid content in this aqueous solution is 5000 pp as above.
m or less.

FIG. 6 shows a modified manufacturing apparatus of FIG. 5, and as shown in FIG.
A pair of anodes 2a and cathodes 2b respectively disposed on opposite inner end surfaces 5a and 5b;
The anion exchange membrane 4 is located on the side of the anode 2a between the a and 2b, and the cation exchange membrane 3 is located on the side of the cathode 2b, forming three spaced-apart, parallel sections 6b, 6a, 6b. And the positive and negative ion exchange membranes 3 and 4 arranged so that the three compartments 6b, 6a and 6b
An acidic silica sol aqueous solution obtained by mixing water glass and an acid in the central section 6a, filling the sections 6b, 6b at both ends with water, and applying a direct current between the positive and negative electrodes 2a, 2b to form an acidic silica sol. Na ⁺ ions in the aqueous silica sol solution are permeated and released through the cation exchange membrane 3 into the water filled in the adjacent one-side compartment 2 b via the cation exchange membrane 3, and the acid radicals adjoin via the anion exchange membrane 4. Permeated and released through the membrane 4 into the water filled in the compartment 6b on the other side,
Thus, the acidic silica sol aqueous solution is subjected to a desalting treatment to obtain an acidic aqueous glass aqueous solution having a low acid content.

The obtained acidic water glass aqueous solution was applied to each section 6
a, 6a... It is recovered from 6a through the conduit 7, and can be directly injected into the ground. At the same time, section 6b,
6b ... The aqueous salt solution in 6b is also recovered through the conduit 8.

[0049] Figure 7 is an improvement manufacturing apparatus of FIG. 6, the electrolytic dialysis cell 1, the end face 5a, and a pair of electrodes 2a and cathode 2b respectively disposed 5b, the cation and anion exchange membranes 3, 4 And having three sections 6b, 6a, 6b as in FIG.

FIG. 7 shows that a desalted acidic water glass aqueous solution tank Y is provided in addition to the structure of FIG.
a, for example, through a conduit 7 at the bottom and connected via a pump P1, and the tank Y and the compartment 6a are connected, for example, via a conduit 7a at the top, and a circulation system between the compartment 6a and the tank Y Form A. Furthermore, each of the compartments 6b, 6b also passes through a conduit 8, for example from the bottom to the top, and is connected via a pump P2 to form a circulation system B.

In the apparatus shown in FIG. 7 having the above-described structure, the desalted acidic aqueous glass solution is circulated through the section 6a of the electrolytic dialysis tank 1 by the circulation system A to repeat the electrolytic dialysis.
When the desalted acidic water glass solution becomes a desired state, the circulation is stopped and the solution is transferred to a storage tank (not shown). Subsequently, an untreated acidic silica sol is introduced into the section 6a, circulated by the circulation system A in the same manner, and electrodialysis is repeated.

By such circulation, a large quantity of high-quality aqueous solution of desalted acidic water glass can be continuously produced irrespective of the size of the electrodialysis tank 1 as shown in FIG.

Further, in FIG. 7, the saline solution is circulated through the sections 6b and 6b of the electrolytic dialysis tank 1 by the circulation system B,
An aqueous salt solution in a desired state can be obtained. In FIG. 7, installation of the circulation system B is optional. further,
The circulation systems A and B can be applied to the apparatus shown in FIG.

FIG. 8 is a block diagram showing the production of the above acidic water glass aqueous solution. In FIG. 8, S is a water glass aqueous solution storage tank, W is a water supply tank, A is an acid aqueous solution storage tank, M2
Denotes a mixing tank and E2 denotes an electrodialysis treatment device.

A water glass aqueous solution is supplied from the water glass aqueous solution storage tank S, water is supplied from the water supply tank W, and an acid aqueous solution is supplied from the acid aqueous solution storage tank A to the mixing tank M2 through conduits 18, 19, and 20, respectively. While mixing and reacting, an acidic silica sol is obtained. This water glass aqueous solution may contain additives as described above.

The obtained acidic silica sol is supplied to the apparatus shown in FIG. 5, that is, the electrolytic dialysis apparatus E2 shown in FIG. 8, and is subjected to desalting treatment to obtain an aqueous solution of acid water having a low content of desalted acid radicals. Also in this case, the content of the acid radical is preferably 5000 ppm or less.

The obtained aqueous acidic water glass solution has a reduced salt content, that is, an acid radical content, and therefore has less effect of the salt on the physical properties of the consolidated body, and exhibits high compaction strength. In addition, even if a long period of time has passed after the consolidation, the release or deviation of the salt from the consolidated body is small, so that the compacted body does not shrink and the durability is improved.

Further, since the ion exchange membrane used in the electrodialysis does not require regeneration unlike the ion exchange resin,
It can be used for a long time. Further, this ion exchange membrane can desalinate even water glass having a high SiO ₂ concentration, so that an aqueous solution of an acidic water glass exhibiting high consolidation strength can be easily produced using water glass having a high SiO ₂ concentration. .

In the manufacturing apparatus shown in FIGS. 1, 2, 3, 5, 6, and 7, the raw material is shown flowing in from the upper part of the electrolytic dialysis tank, and the treated solution is drawn out from the lower part. However, the raw material may flow in from the lower part and the treated solution may flow out from the upper part.

The water glass used in the present invention is not particularly limited, and any molar ratio can be used. However, practically, use of JIS No. 3 water glass is preferred. Also, water glass concentration SiO ₂ content of 2-15%, preferably 2 to 12% SiO ₂ in the case of the ion exchange resin method
Content 2-10%, preferably considerably wider range than 2-6%.

Further, the acid used in the present invention is an organic acid,
Although not particularly limited, such as inorganic acids, sulfuric acid, hydrochloric acid, phosphoric acid,
Inorganic acids such as nitric acid are common, and among them, sulfuric acid is particularly preferred.

The ion exchange membrane is preferably made of a material having a high permselectivity for ions, a low electric resistance, a high mechanical strength, and a chemically stable material.

Further, the current density at the time of the electrodialysis is appropriately selected depending on the concentration of the aqueous solution of water glass, the concentration of the acidic water glass, the kind of the membrane, etc., but is approximately 3 amps / dm ^2.
The degree is preferred.

In the material for ground injection according to the present invention obtained as described above, the aqueous alkali glass solution maintains a certain gelation time, and the acidic aqueous glass solution maintains a long gelation time. In any case, it can be injected into the ground to be injected through the liquid feed pipe by operating the injection pump as it is.

Further, the material for ground injection according to the present invention may be mixed with a reactant or mixed and mixed with a reactant and injected into the ground, if necessary, in order to shorten the gel time and use.

As the reactant, when the suspension grout is used, a suspension type reactant such as cement or slag is used. When the suspension grout is used, when the solution grout is used, bicarbonate, phosphoric acid, phosphoric acid, or the like is used.
A solution-type reactant for water glass such as a phosphate or an alkaline earth metal salt is used, and a curing agent such as water glass, an alkali, or various salts is used for an acidic aqueous glass solution.

According to the present invention, the above-described various types of ground injection materials can be injected alone or in an appropriate combination so as to be adapted to any ground conditions, and the ground can be efficiently consolidated. This ground injection method will be described in detail with reference to FIG.

FIG. 9 is an explanatory view of a specific example of the injection method according to the present invention, which comprises a material supply system, an injection material production system, and an injection system.

The material supply system comprises a water glass aqueous solution storage tank S, an acid aqueous solution storage tank A, a water supply tank W, and a reactant storage tank R.

In order to inject the dealkalized water glass aqueous solution produced according to FIG. 1, 2 or 3 into the ground, water glass is supplied from the water glass aqueous solution storage tank S and the water supply tank W
From the production apparatus of FIG. 1, FIG. 2 or FIG.
The mixture is supplied to an electrolytic dialysis treatment apparatus E1 of an injection material production system, subjected to electrolytic dialysis, and subjected to a dealkalization treatment. The obtained alkali-free water glass aqueous solution is stored in an alkali-free water glass aqueous solution storage tank L,
From here, it is transferred to the injection system and injected into the ground through the injection pump P1 and the liquid feed pipe I1.

In order to inject the acidic aqueous glass aqueous solution produced according to FIG. 4 into the ground, an acidic aqueous solution is supplied from the acidic aqueous solution storage tank A of the material supply system to the mixing tank M1 of the injection material producing system, and from the storage tank L. The dealkalized water glass aqueous solution is supplied to the mixing tank M1 to be mixed and reacted. The obtained acidic water glass aqueous solution is transferred to an injection system, and injected into the ground through an injection pump P2 and a liquid sending pipe I2.

In order to inject the acidic water glass aqueous solution produced according to FIG. 5, FIG. 6 or FIG. 7 into the ground, a water glass is supplied from the storage tank S of the material supply system, an acid aqueous solution is supplied from the storage tank A, and a water supply tank W is provided. From the mixing tank M2 of the injection material production system, respectively.
To produce an acidic silica sol. This is supplied to the manufacturing apparatus of FIG. 5, FIG. 6, or FIG. 7, that is, the electrolytic dialysis treatment apparatus E2 to perform electrolytic dialysis and desalting treatment.

The obtained acidic water glass aqueous solution is transferred from the acidic water glass aqueous solution storage tank D to the injection system, and injected into the ground through the injection pump P3 and the liquid feeding pipe I3.

Further, the dealkalized water glass aqueous solution is transferred from the storage tank L to the injection pump P4 of the injection system, and the reactant is transferred from the reaction agent storage tank R to the injection pump P4. The obtained ground injection chemical solution is obtained and injected into the ground through the injection pump P4 and the liquid feed pipe I4.

Further, an aqueous solution of acidic water glass is stored in a storage tank D.
To the injection pump P5 of the injection system, and the reaction agent from the reaction agent storage tank R to the injection pump P5. The two are mixed to obtain a ground injection liquid mixed with the reaction agent. And it injects into the ground through the liquid sending pipe I5.

Each of these injection materials or ground injection chemicals is injected into the ground singly or in any combination of two or more kinds from arbitrary plural places through separate liquid feed pipes. With such an injection method, the ground injection adapted to the ground condition can be efficiently performed.

[0077]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

(Materials Used) Water glass JIS No. 3 water glass having the following composition is used. Specific gravity (20 ° C.): 1.39, SiO ₂ : 29.0% Na ₂ O: 9.6%, molar ratio: 3.12

2. Acid 75% industrial sulfuric acid is used.

3. Reactant (1) Suspension type reactant Portland cement is used.

(2) Solution-type reagent Sodium hydrogencarbonate (NaHCO ₃ : primary reagent) was used.

Example 1 [Production of De-alkali Water Glass Aqueous Solution] Using the apparatus shown in FIG. 1, a 40% aqueous glass solution (SiO ₂ : 11.6%, N
a ₂ O: 3.84%, pH: 11.7) into compartments 6a, 6a
6a is filled with water in each of the sections 6b, 6b,... 6b, and a DC current of 3 A / dm ² is applied between the anode 2a and the cathode 2b until the pH of the water glass aqueous solution becomes about 10.0. Dialysis was continued. The obtained aqueous solution of dealkalized water glass showed SiO ₂ : 11.1% and pH: 10.0, and the gelation time was less than about 2 hours at 20 ° C. This was injected into the ground through an injection pump P1 and a liquid feed pipe I1, as shown in FIG.

Example 2 [Production of Acidic Water Glass Aqueous Solution (I)] Using the apparatus shown in FIG.
Was supplied to the mixing tank M1, then stirrer de alkali water glass solution 800g from the reservoir L to the mixing tank M1 1
2 and slowly added with vigorous stirring.

The obtained aqueous acidic water glass solution had the following composition and physical properties. SiO ₂ : 8.9%, SO ₄ : 0.73% (7300 ppm) pH: 2.1, Gel time (20 ° C.): about several tens of hours

As shown in FIG. 9, the acidic aqueous glass solution was injected into the ground through an injection pump P2 and a liquid feed pipe I2.

Example 3 [Production of Acidic Water Glass Aqueous Solution (II)] Acidic water glass was prepared in the same manner as in Example 2 except that a 3% aqueous solution of sulfuric acid was used instead of the 5% aqueous solution of sulfuric acid in Example 2. An aqueous solution was obtained.

The composition and physical properties of the obtained acidic aqueous glass solution were as follows. SiO ₂ : 8.8%, SO ₄ : 0.44% (4400 ppm) pH: 2.7 Gelation time (20 ° C.): about several tens of hours

Example 4 [Production of an aqueous solution of acidic water glass (III)] An acidic aqueous solution was prepared in the same manner as in Example 2 except that a 1.6% aqueous sulfuric acid solution was used in place of the 5% aqueous sulfuric acid solution in Example 2. A glass solution was prepared.

The composition and physical properties of the obtained aqueous acidic water glass solution were as follows. _{SiO 2: 8.8%, SO 4} : 0.23% (2300ppm) pH: 3.2, gelation time: about 5-6 hours

Example 5 [Production of Acidic Water Glass Aqueous Solution (IV)] Referring to FIG.
An appropriate amount of a 10% sulfuric acid aqueous solution is supplied from the storage tank A to the mixing tank M2 through the conduit 20, and then, while continuing to vigorously stir by the stirrer 21, the 50% by volume aqueous glass solution is mixed from the storage tank S with the same amount as the sulfuric acid aqueous solution through the conduit 18. The mixture was gradually added to and mixed with the tank M2 to obtain an acidic silica sol having a pH of 1.8.

This acidic silica sol was supplied together with the water from the water supply tank W to the electrolytic dialysis treatment apparatus E2, that is, the production apparatus shown in FIG.

In FIG. 5, the acidic silica sol aqueous solution is supplied to the sections 6a, 6a... 6a, and the water is supplied to the sections 6b, 6b.
.. 6b, respectively, anode 2a and cathode 2b
During that time, a DC current of 3 A / dm ² was supplied to perform the electrodialysis treatment. As a result, Na ⁺ ions in the acidic silica sol in the sections 6a, 6a,... 6a pass through the cation exchange membrane 3, and acid radicals such as SO ₄ ²⁻ and HSO ₄ ⁻ pass through the anion exchange membrane 4. 6b, 6b ... 6 respectively
b.

This electrolytic dialysis treatment is performed in sections 6a, 6a,.
An aqueous acidic water glass solution was obtained continuously until the pH of 6a reached 2.3. The composition and physical properties of this aqueous solution are shown in Table 1 in comparison with the acidic silica sol as a raw material.

[0094]

[Table 1]

The obtained acidic water glass aqueous solution was stored in a storage tank D as shown in FIG. 9, and injected into the ground through an injection pump P3 and a liquid sending pipe I3.

Example 6 [Production of Acidic Water Glass Aqueous Solution (V)] The acidic silica sol obtained in Example 5 was subjected to electrolytic dialysis treatment in the same manner as in Example 5, and the pH of sections 6a, 6a,. The treatment was continued until 2.8 was reached to obtain an acidic water glass aqueous solution.

The composition and physical properties of this aqueous solution are as follows. Gel time (20 ° C.): about 20 hours, pH: 2.8 SiO ₂ : 8.4%, SO ₄ : 0.41% (4100 ppm)

Example 7 [Production of Acidic Water Glass Aqueous Solution (VI)] The acidic silica sol obtained in Example 5 was subjected to electrolytic dialysis in the same manner as in Example 5, and the pH of the compartments 6a, 6a,. The treatment was continued until 3.4, to obtain an acidic water glass aqueous solution.

The composition and physical properties of this aqueous solution are as follows. Gelation time (20 ° C.): about 10 hours, pH: 3.4 SiO ₂ : 8.4%, SO ₄ : 0.19% (1900 ppm)

Example 8 [Production of Suspended Ground Injection Chemical Solution] The aqueous solution of dealkalized water glass produced in Example 1, that is, the aqueous solution of dealkalized water glass stored in storage tank L of FIG. And,
The reactant in the reactant storage tank R shown in FIG.
These AB liquids were combined by an injection pump P4, and injected into the ground as a suspension type ground injection liquid through a liquid feed pipe I4.

For comparison, S was replaced with S
Using a water glass aqueous solution having substantially the same iO ₂ concentration and not being subjected to a desalination treatment, this was combined with the solution B to obtain a suspension-type ground injection chemical solution. The composition and physical properties of these are shown in Table 2.

[0102]

[Table 2]

As is apparent from Table 2, the aqueous alkali glass solution according to the present invention has a significantly higher consolidation strength than the comparative example using water glass that has not been subjected to alkali removal treatment. Also, the gel time is reduced.

Example 9 [Production of solution type ground pouring solution] The acidic water glass aqueous solution (pH 2.8) of Example 6, that is, the aqueous solution of acidic water glass in storage tank D in FIG. The reactant in the reactant storage tank R was an aqueous sodium hydrogencarbonate solution (solution B), and these AB solutions were merged by an injection pump P5 and injected into the ground as a solution type ground injection chemical through a liquid sending pipe I5.

For comparison, SiO 2 was replaced with SiO 2
_The solution B was combined with an acidic silica sol composed of water glass and sulfuric acid having substantially the same concentration but not subjected to desalination treatment, and the solution B was combined therewith to obtain a solution type ground injection chemical solution. Table 3 shows the blending and physical properties.

[0106]

[Table 3]

From Table 3, it can be seen that the desalted acidic water glass aqueous solution according to the present invention has a higher consolidation strength and a longer gelation time than the comparative example using water glass not subjected to desalination treatment. It can be seen that despite the small amount of the reactant, the amount was significantly shortened.

In the examples described above, the gel time was measured by the cup inversion method, and the uniaxial compressive strength was measured by the Japanese Society of Geotechnical Engineers, “Uniaxial compressive test method for soil”.

Example 10 The shrinkage of the compact was measured for each of the samples Nos. 1 to 6 shown in Table 4, and the results are shown in Table 4. The shrinkage rate was calculated from the amount of synergic water released after the homogel of each sample was cured in a closed container made of polypropylene resin, and was expressed in%.

[0110]

[Table 4]

As is clear from Table 4, Sample Nos. 1, 2,
Samples Nos. 3 and 5 (both samples according to the present invention) all have shrinkage ratios in the range of 2 to 8%, showing very slight shrinkage ratios. On the other hand, sample Nos. 4 and 6
(Control samples) all have considerably high shrinkage. In addition, the shrinkage rate of each of the samples of the present invention hardly changes even when the number of days for curing increases. On the other hand, in the control sample, the shrinkage ratio increases as the curing days increase.

From the above examples, it can be seen that the material for ground injection according to the present invention has a high consolidation strength and a small shrinkage, so that it has excellent durability.

[0113]

【The invention's effect】

(1) The material for injecting ground from the aqueous alkali glass solution of the present invention is obtained by subjecting water glass to a dealkalization treatment by electrolytic dialysis using an ion-exchange membrane, so that the alkali content is reduced. The effect on the physical properties of the body is reduced, and high compaction strength is exhibited. In addition, even when a long period of time has passed after the consolidation, the release or deviation of the alkali from the consolidated body is small, and therefore, the compacted body does not shrink and the durability is improved.

(2) The soil injection material comprising the aqueous acidic water glass solution of the present invention has a reduced content of acid radicals or other salts, and therefore has less influence on the physical properties of the consolidated body due to the salt, resulting in a higher consolidation. Present strength. In addition, even if a long period of time has passed after the consolidation, the release or deviation of the salt from the consolidated body is small, so that the compacted body does not shrink and the durability is improved. In addition, the influence on the water quality of the injection ground is extremely small, and therefore, it can be said that it is excellent also from the viewpoint of environmental conservation.

(3) Moreover, the ion exchange membrane used for the electrodialysis does not require regeneration unlike the ion exchange resin, and can be used for a long period of time. Furthermore, this ion exchange membrane can also remove alkali or demineralize water glass having a high SiO ₂ concentration. Therefore, an aqueous alkali solution or an acid solution which exhibits high consolidation strength by using a water glass having a high SiO ₂ concentration. A water glass aqueous solution can be easily produced.

(4) The aqueous alkali-free water solution, the acidic water glass aqueous solution, and the ground pouring solution obtained by mixing each of the aqueous glass solution with a reactant according to the present invention are used alone or in combination of two or more. By injecting into the ground from a plurality of arbitrary locations through separate liquid feed pipes, the ground injection adapted to the ground condition can be efficiently performed.

(5) The discharged caustic soda solution and salt solution are relatively pure and can be reused.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a specific example of an electrodialysis apparatus according to the present invention.

FIG. 2 is an explanatory view of one specific example of a modified device of FIG. 1;

FIG. 3 is an explanatory diagram of a specific example of the improvement device of FIG. 2;

FIG. 4 is a production block diagram of an aqueous acidic water glass solution according to the present invention.

FIG. 5 is an explanatory view of a specific example of the electrodialysis apparatus according to the present invention.

FIG. 6 is an explanatory diagram of one specific example of the modified device of FIG. 5;

FIG. 7 is an explanatory diagram of a specific example of the improvement device of FIG. 6;

FIG. 8 is a production block diagram of an aqueous acidic water glass solution according to the present invention.

FIG. 9 is a block diagram of a specific example of the injection method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Electrodialysis tank 2a Anode 2b Cathode 3 Cation exchange membrane 4 Anion exchange membrane 5a End face 5b End face 6a Section 6b Section A Acid aqueous solution storage tank M1 Mixing tank L De-alkali water glass aqueous solution tank W Water supply tank X De-alkali water glass aqueous solution Tank Y Desalted acidic water glass solution tank

──────────────────────────────────────────────────続 き Continued on the front page (72) Nobuyuki Fujisawa, Inventor 4-2-35, Kudankita, Chiyoda-ku, Tokyo Light Industry Co., Ltd. (72) Kenji Kayahara 2-15-10, Hongo, Bungo-ku, Tokyo Engineering Co., Ltd. (56) References JP-A-60-144382 (JP, A) JP-A-60-106985 (JP, A) JP-A-5-306112 (JP, A) JP-A-60-106986 ( JP, A) JP-A-60-108318 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09K 17/12 C01B 33/20

Claims (16)

(57) [Claims] 1. A material for ground injection comprising an aqueous alkali-free water glass solution having reduced alkali content and obtained by subjecting water glass to electrolytic dialysis using an ion exchange membrane as a diaphragm and de-alkali treatment. 2. An acid radical content obtained by mixing an aqueous solution of alkali glass with reduced alkali content obtained by subjecting water glass to electrolytic dialysis using an ion-exchange membrane as a diaphragm and de-alkali treatment, and an acid. Ground injection material consisting of acidic water glass aqueous solution with low water content. 3. An injection material for soil comprising an aqueous solution of acidic water glass having a low content of acid radicals, obtained by subjecting an acidic silica sol obtained by mixing water glass and an acid to electrolytic dialysis using an ion exchange membrane as a diaphragm and desalting. 4. The additive according to claim 1, wherein the aqueous alkali solution contains an additive.
The material for ground injection according to claim 1, which comprises: 5. An aqueous solution of acidic water glass according to claim 2 or 3.
The material for ground injection according to claim 2 or 3, which comprises an additive. 6. The cation exchange membrane according to claim 1, 2 or 3, which selectively permeates cations but does not transmit anions, and selectively permeates anions but not cations. An anion exchange membrane that does not permeate, 1,
The material for ground injection described in 2 or 3 . 7. An electrolytic dialysis tank, a pair of anodes and cathodes respectively disposed on both opposite end surfaces inside the tank, an anion exchange membrane on the most anode side between the positive and negative electrodes, and the most cathode side Consists of cation and anion exchange membranes, each of which has a cation exchange membrane, and is arranged alternately and to form a plurality of compartments, of which the anode and cathode are located By filling the compartments with water and alternately filling the other compartments with a water glass solution and water, respectively, and passing an electric current between the positive and negative electrodes, the Na ⁺ ions in the water glass solution exchange cations. The OH ^- ions are permeated and released through the membrane into the water filled in one adjacent compartment through the membrane, and the OH ^- ions are introduced into the water filled in the other adjacent compartment through the anion exchange membrane. Through the membrane Transmission is released, thereby manufacturing apparatus of the ground infusion timber, characterized in that to obtain a reduced de-alkaline water glass solution of water glass solution is dealkalization alkali content. 8. An electrolytic dialysis tank, a pair of anodes and cathodes respectively arranged at opposite ends inside the tank, an anion exchange membrane on the anode side between the positive and negative electrodes, and a positive electrode on the cathode side. Ion exchange membranes are located and spaced from each other, and are composed of positive and anion exchange membranes arranged so as to form three parallel juxtaposed compartments. By filling the compartments at both ends with water and passing a current between the positive and negative electrodes, Na ⁺ ions in the aqueous solution of water glass were filled in the adjacent compartment on the one side via the cation exchange membrane. The OH ^- ions are permeated and released through the membrane into the water and the OH ^- ions are permeated and released through the membrane through the anion exchange membrane into the water filled in the other side compartment, whereby the aqueous solution of water glass in the central compartment Is al al Li treated with apparatus for manufacturing a ground injection timber, characterized in that to obtain a de-alkali water glass solution having a reduced alkali content. 9. An electrolytic dialysis tank, a pair of anodes and cathodes respectively disposed at opposite ends inside the tank, an anion exchange membrane at the most anode side between the positive and negative electrodes, and a cathode at the most cathode side. Is composed of cation and anion exchange membranes in which cation exchange membranes are respectively located and arranged alternately and so as to form a plurality of compartments, of which compartments where the anode and cathode are located While filling water, the other compartments are alternately filled with an aqueous solution of acidic silica sol obtained by mixing water glass and acid, and water, and by passing a current between the positive and negative electrodes,
Na ⁺ ions in the acidic silica sol aqueous solution are permeated and released through the cation exchange membrane into the water filled in one adjacent compartment via the cation exchange membrane, and the acid radicals are adsorbed on the other side via the anion exchange membrane. An apparatus for permeating and discharging the aqueous solution of acidic silica sol through the membrane into water filled in the side compartment, whereby the aqueous solution of acidic silica sol is desalted to obtain an aqueous solution of acidic water glass having a low content of acid radicals. . 10. An electrolytic dialysis tank, a pair of anodes and cathodes respectively disposed at opposite ends inside the tank, an anion exchange membrane on the most anode side between the positive and negative electrodes, and a cathode on the cathode side. Cation exchange membranes consist of cation and anion exchange membranes, which are located at a distance from each other and are arranged to form three parallel juxtaposed compartments. Aqueous silica sol aqueous solution obtained by mixing water and acid, filling the compartments at both ends with water, and passing a current between positive and negative electrodes, Na ⁺ ions in the acidic silica sol aqueous solution pass through the cation exchange membrane. And the acid radicals are permeated and released through the membrane into the water filled in one adjacent compartment and the acid radicals are passed through the membrane through the anion exchange membrane into the water filled in the other adjacent compartment. ,to this Ri said ground infusion timber manufacturing apparatus acidic silica sol aqueous solution and wherein the obtaining a less acidic water glass solution of desalination has been acid radical content. 11. The glass of dealkalized water according to claim 7 or 8.
9. The aqueous solution according to claim 7, wherein the aqueous solution contains an additive.
Production equipment for ground injection materials. 12. The acidic water glass water according to claim 9 or 10.
The solution according to claim 9 or 10, wherein the solution comprises an additive.
Production equipment for ground injection material. 13. An aqueous alkali glass solution having a reduced alkali content obtained by subjecting water glass to electrolytic dialysis using an ion exchange membrane as a diaphragm and a dealkalization treatment, and mixing the aqueous alkali glass solution with an acid. An acidic water glass aqueous solution having a low acid radical content obtained, and an acidic silica sol obtained by mixing water glass and an acid are subjected to electrolytic dialysis using an ion exchange membrane as a diaphragm, and an acidic water having a low acid radical content obtained by desalting treatment. A method for injecting a ground into a ground, wherein each of the glass aqueous solutions is directly injected into the ground, or a ground injection chemical solution obtained by mixing a reactant with the aqueous alkali or acidic water glass solution is injected into the ground. 14. The method according to claim 13, wherein the acid of claim 13 is an inorganic acid. 15. The method according to claim 13, wherein the reactant according to claim 13 is a gelling agent for water glass. 16. The method according to claim 13, wherein the reactant according to claim 13 is a curing agent for an acidic aqueous glass solution comprising water glass, an alkali or a salt.