KR102308228B1 - Manufcaturing method of eco-friendly inorganic solidifying agent, eco-friendly inorganic solidifying agent manufactured thereby and grout injection material including the same - Google Patents

Abstract

The present invention relates to a manufacturing method of an eco-friendly inorganic solidifying material, comprising: a mixing step of preparing a raw material mixture by mixing limestone, hectorite, allophane, ferronickel slag, and sodium nitrate; a primary sintering step of cooling the raw material mixture after heat treatment; a secondary sintering step of heat-treating the raw material mixture passing through the primary sintering step at a higher temperature than the primary sintering step and then cooling the raw material mixture; and a grinding step of pulverizing the raw material mixture passing through the secondary sintering step, an eco-friendly inorganic solidifying material manufactured thereby, and an eco-friendly grout injection material including the same. The eco-friendly inorganic solidifying material according to the present invention can promote the solidification of cement and is environmentally friendly.

Description

Manufacturing method of eco-friendly inorganic solidifying agent, eco-friendly inorganic solidifying agent manufactured thereby and grout injection material including the same

The present invention relates to a method for manufacturing an eco-friendly inorganic solidifying material, an eco-friendly inorganic solidifying material manufactured according to the method, and a grouting injection material comprising the same, and more particularly, to an environmentally friendly inorganic solidifying material that is environmentally friendly and can promote solidification of the grouting injection material it's about

In general, when constructing structures on soft ground such as coastal wetlands, rivers, lakes, harbors, reclamation or dredged landfills, tunnels and subways, the strength of the ground is weak, so problems such as ground subsidence may occur after constructing the structure. Therefore, before constructing the structure on the soft ground, the ground improvement work is performed.

For this ground improvement work, conventionally, a drainage method using a vertical drainage material has been widely used. However, the drainage method has disadvantages in that it is difficult to apply to soft ground with a deep depth if it is not easy to secure stability after a long construction period.

Accordingly, in recent years, a grouting injection method in which a suspension-type grouting injection material containing cement as a main component is injected into a soft ground to form a columnar or bulky shape has been mainly performed. This grouting injection method has the advantage that construction time can be shortened compared to the drainage method, there is little disturbance to adjacent structures, and low vibration and low noise construction are possible.

In the case of using the grouting injection method, in general, in order to sufficiently penetrate the grouting injection material into the soft ground, a grouting injection material in a suspension state with a large amount of water added is used.

Such a grouting injection material should be instantaneously solidified within 5 to 10 seconds after injection, but the conventional grouting injection material has a problem in that the instantaneous solidification performance of the grout and the compactness and strength of the hydration hardening body are insufficient. There was a problem in that it was difficult to maintain the water supply and the reinforcement of the soft ground due to severe leaching.

Accordingly, research and development for improving the performance of the grouting injection material is being actively performed. In particular, recent studies have been actively conducted to improve the performance of solidification materials to promote solidification of grouting injection materials, and development of eco-friendly solidification materials that minimize or exclude organic components is required to prevent contamination of the ground after construction. is becoming

Registered Patent No. 10-0681272 (registered on Feb. 5, 2007)

An object of the present invention is to provide an environmentally friendly inorganic solidifying material capable of efficiently accelerating the solidification of the grouting injection material.

An embodiment of the present invention for achieving the above object is a mixing step of preparing a raw material mixture by mixing limestone, hectorite, allophane, ferronickel slag and sodium nitrate; a first firing step of cooling the raw material mixture after heat treatment; a secondary sintering step of heat-treating the raw material mixture that has undergone the primary sintering step at a higher temperature than the primary sintering step and then cooling; and a pulverizing step of pulverizing the raw material mixture that has undergone the secondary calcination step.

In the mixing step, based on 100 parts by weight of limestone, 18 to 32 parts by weight of hectorite, 12 to 29 parts by weight of allophane, 7 to 15 parts by weight of ferronickel slag, and 0.1 to 3 parts by weight of sodium nitrate are mixed to prepare a raw material mixture It may be a step to

The heat treatment temperature in the first firing step may be 600 ~ 1000 ℃.

The heat treatment temperature in the secondary firing step may be 1300 ~ 1600 ℃.

Between the first firing step and the second firing step, an electron beam irradiation step of irradiating an electron beam to the raw material mixture may be performed.

The first firing step may be performed in a nitrogen atmosphere.

The ferronickel slag may be quenched hydrolyzed ferronickel slag.

The ferronickel slag may be prepared through a pretreatment process of pulverizing and heating the ferronickel slag.

The pretreatment process includes a grinding step of pulverizing ferronickel slag, a by-product of the smelting process, to a particle size of 1 to 100 μm; and a rapid sintering step of heat-treating the pulverized ferronickel slag for 1 to 5 minutes.

Another embodiment of the present invention relates to an environmentally friendly inorganic solidifying material manufactured according to the above method.

Another embodiment of the present invention relates to an environmentally friendly grout injection material comprising an environmentally friendly inorganic solidifying material, cement, and water manufactured according to the above method.

The eco-friendly inorganic solidifying material according to the manufacturing method of the eco-friendly inorganic solidifying material of the present invention is eco-friendly and can effectively promote the solidification of the grouting injection material.

Hereinafter, before describing in detail through preferred embodiments of the present invention, terms or words used in the present specification and claims should not be construed as being limited to conventional or dictionary meanings, and meanings consistent with the technical spirit of the present invention and should be interpreted as a concept.

Throughout this specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

Throughout this specification, "%" used to indicate the concentration of a specific substance is (weight/weight)%, solid/liquid (weight/volume)%, and liquid, unless otherwise specified. /liquid means (volume/volume)%.

Throughout this specification, the particle size means the longest among the lengths from one end to the other end of the particle, and in the case of a sphere, it means the diameter.

Hereinafter, an embodiment of the present invention will be described. However, the scope of the present invention is not limited to the following preferred embodiments, and those skilled in the art can implement various modified forms of the contents described herein within the scope of the present invention.

The present invention relates to a method for manufacturing an environmentally friendly inorganic solidifying material, an environmentally friendly inorganic solidifying material manufactured thereby, and a grouting injection material comprising the same.

The eco-friendly inorganic solidifying material of the present invention can be used as a raw material for a grout injection material by promoting the hydration reaction of cement to quickly harden the cement, thereby enabling smooth process execution.

In addition, since it does not contain organic materials, it is environmentally friendly, and there is no concern about soil contamination because components that contaminate the existing ground are not released.

First, the method for producing an eco-friendly inorganic solidified material according to an embodiment of the present invention includes a mixing step of preparing a raw material mixture by mixing limestone, hectorite, allophane, ferronickel slag and sodium nitrate; a first firing step of cooling the raw material mixture after heat treatment; a secondary sintering step of heat-treating the raw material mixture that has undergone the primary sintering step at a higher temperature than the primary sintering step and then cooling; and a pulverizing step of pulverizing the raw material mixture that has undergone the secondary firing step.

The mixing step is a step of mixing the raw materials of the eco-friendly inorganic solidifying material. Specifically, based on 100 parts by weight of limestone, 18 to 32 parts by weight of hectorite, 12 to 29 parts by weight of allophane, 7 to 15 parts by weight of ferronickel slag and 0.1 to 3 parts by weight of sodium nitrate to prepare a raw material mixture.

When the limestone is combined with water, calcium hydroxide is produced, and the calcium hydroxide induces a water hardening reaction of the cement and contributes to the initial strength of the grout injection material. If limestone is not included, there is a problem in that the initiation of the hydrocuring reaction is delayed when cement, water, and inorganic solidifying material are mixed.

The hectorite is a kind of clay mineral having a layered crystal structure, and when a weak layer charge occurs between two structurally adjacent layers and comes in contact with moisture, it expands and swells to increase the viscosity of the composition.

In particular, due to the characteristic that it expands and swells rapidly when it comes into contact with moisture and the viscosity is improved, it is possible to prevent the flow of the grout injection material during grout construction in which the grout injection material is injected in the upper direction such as tunnel construction, and the grout by absorbing excess moisture It has the advantage of being able to induce the hydration reaction of cement and water more effectively by preventing the dissolution of water during construction.

Other clay minerals such as bentonite and kaolinite may be used for this function, but when hectorite is used, it not only effectively combines with other raw materials in the process of calcining the raw material mixture, but also uses a solidifying material. Since the resulting crude steel properties are further improved, it is preferable to use hectorite rather than a general clay mineral.

Hectorite may have a particle size of 1 to 50 μm, and when the particle size is less than 1 μm, a problem occurs in that the hectorite particles are agglomerated with each other due to electrostatic attraction. Since there is a problem that uniform mixing is difficult due to the large size, it is preferable to use hectorite whose particle size is adjusted to the above-mentioned range.

Hectorite may be included in an amount of 18 to 32 parts by weight based on 100 parts by weight of limestone, and when it is included in less than 18 parts by weight, it is difficult to obtain the above-described effect, and when it is included in more than 32 parts by weight, the curing reaction promoting performance of cement This decreases, and rather absorbs moisture that should react with the cement, so there is a problem that unhardened cement is generated.

The allophane is an amorphous hydrous aluminum silicate containing aluminum oxide and silicon dioxide, and provides aluminum oxide and silicon dioxide that accelerates the curing rate according to the hydration reaction of cement. In addition, since the amorphous crystal structure facilitates bonding with other components during the firing process, there is an advantage of providing an eco-friendly inorganic solidifying material of uniform quality.

Allophane may be included in an amount of 12 to 29 parts by weight based on 100 parts by weight of limestone, and when included in an amount of less than 12 parts by weight, the effect of promoting hydration reaction is insignificant due to the lack of aluminum oxide content in the eco-friendly inorganic solidifying material, and 29 parts by weight When it exceeds, since the aluminum oxide content is excessive and may cause problems such as rapid hydration and an increase in the unreacted aluminum oxide content, an initial strength decrease, microcracks, etc., it is preferable to be included within the above-mentioned weight range.

The ferronickel slag is a by-product generated in the ferronickel manufacturing process and has silicon dioxide, magnesium oxide and iron oxide as main components. Conventionally, most have been disposed of by landfill, but in the present invention, it is eco-friendly because it is possible to reduce costs due to shortage of landfill or disposal by recycling it as a raw material for inorganic solidifying material.

As the ferronickel slag, quenched water chain ferronickel slag obtained by spraying water to the ferronickel slag in a molten state at a high temperature may be used. It significantly increases than the amount, and as the amount of the amorphous mineral increases, the chemical activity of the ferronickel slag increases, so that the performance as an eco-friendly inorganic solidifying material can be improved.

The ferronickel slag may be included in an amount of 7 to 15 parts by weight based on 100 parts by weight of limestone, and when it is included in an amount of less than 7 parts by weight, the performance improvement as a solidifying material is insignificant due to insufficient content of ferronickel slag, and 15 parts by weight If it exceeds, ferronickel slag is contained in excess, which may cause a decrease in the strength of the grouting injection material according to the use of an environmentally friendly inorganic solidifying material.

The ferronickel slag may be prepared through a pretreatment process.

The pretreatment process includes a grinding step of pulverizing ferronickel slag, a by-product of the smelting process, to a particle size of 1 to 100 μm; and a rapid sintering step of heat-treating the pulverized ferronickel slag at 900 to 1200° C. for 1 to 5 minutes.

The pulverizing step is a step of pulverizing the dried ferronickel slag to a particle size of 1 to 100 μm, and when the particle size of the ferronickel slag is in the above range, it can be uniformly mixed in an eco-friendly inorganic solidifying material, and at the same time ferronickel slag Since the reactivity of the nickel slag with water is increased, it is preferable to undergo the pulverization step to have the above-mentioned particle size range.

In particular, when the particle size exceeds 100㎛, the reactivity with water is low under general conditions, that is, at room temperature and atmospheric pressure, so that it does not contribute to promoting the hardening of cement and functions only as an aggregate. it is preferable

Next, the rapid sintering step is a step performed to remove various impurities contained in the ferronickel slag, and may be a step of heat-treating the pulverized ferronickel slag at 900 to 1200° C. for 1 to 5 minutes.

When the heat treatment temperature is lower than the above-mentioned minimum conditions, impurities are not sufficiently removed, and the physical properties of the grouting injection material containing the eco-friendly inorganic solidifying material may be reduced. Since the crystallization of the mineral occurs and the chemical activity of the ferronickel slag is lowered and does not react with water, the rapid calcination step is preferably performed under the above-described temperature conditions.

When the environment-friendly inorganic solidifying material is mixed with cement and water in the sodium nitrate, sodium ions of sodium nitrate function as a hydration reaction accelerator of the cement, thereby contributing to an increase in initial strength. Sodium nitrate may be included in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of limestone, and when it is included in an amount of less than 0.1 parts by weight, this effect is insignificant, and when it is included in more than 3 parts by weight, the physical properties of the grouting injection material may be reduced. Therefore, it is preferable to be included within the above-described weight range.

Meanwhile, impurities may be removed from the raw material mixture obtained through the above mixing step through the first firing step.

The first firing step is a step of heat-treating the raw material mixture in a temperature range of 600 to 1000 ° C. for 1 to 8 minutes and then cooling it. Through this step, moisture and various impurities contained in the raw material mixture are removed, and the final The purity and performance of the environmentally friendly inorganic solidified material can be improved. For this purpose, the heat treatment is preferably performed under a nitrogen atmosphere.

In the case where the heat treatment temperature in the first firing step is lower than the above temperature or the process is performed for a time shorter than the time, the above-described effect is not sufficiently achieved, so that the bonding between the raw material components in the second firing step is not sufficiently achieved. , thus, the functional improvement of the eco-friendly inorganic solidifying material may be insignificant. On the other hand, when the heat treatment temperature is higher than the above temperature or is performed for a longer time than the above time, the respective raw materials do not combine with each other to form crystals, but some crystallization of each raw material proceeds in a mixture state, rather than in the secondary firing step later Since the raw materials are not combined with each other or impurities are bound together in the finally obtained eco-friendly inorganic solidifying material, there is a problem that the performance is deteriorated, so that the primary firing is preferably performed under the above-described conditions.

At this time, in the first firing step, vibration is applied to the raw material mixture and heat treatment may be performed. In this case, the particles collide with each other by vibration. At this time, some particles are pulverized by the collision energy, and as the surface area is increased in this way, the effect of removing impurities can be improved.

For this effect, vibration is preferably applied with an amplitude of 1 to 10 mm and a frequency of 1 to 8 kHz. Since the effect of removing impurities is insignificant compared to the energy consumed for application, vibration is preferably applied under the above-described conditions.

The raw material mixture that has undergone such a heat treatment step may be naturally cooled and then added to the secondary firing step. Through natural cooling, the raw material mixture can be cooled to a temperature of 50° C. or lower.

The secondary firing step is a step of cooling after heat treatment at a higher temperature than the first firing.

As such, when the secondary firing proceeds after the primary firing, moisture and various impurities are removed in the first firing step heated to a relatively low temperature, thereby increasing the purity of the raw material mixture. The purity of the solidified material may be increased. In addition, in the secondary firing, the bonding of each raw material is made more efficiently, and clinker having a strong bonding force is formed.

This secondary firing may be a step of cooling the raw material mixture after heat treatment for 20 minutes to 2 hours at a temperature condition of 1300 ~ 1600 ℃.

When the heat treatment is performed under these temperature and time conditions, crystal water in each raw material constituting the raw material mixture is removed, and bonding between each raw material component may be formed to form clinker, which is an inorganic mineral. The clinker thus formed has calcium carbonate, aluminum oxide, silicon dioxide and iron oxide as main components, and when it is mixed with cement and water, it can promote the hydrosetting reaction of cement and enable early high strength expression.

In the secondary firing step, when the heat treatment temperature is lower than the above temperature or the heat treatment time is shorter than the above time, there is a problem in that clinker is not formed because the bonding between the raw materials is not sufficiently achieved.

On the other hand, when the heat treatment temperature is higher than the above temperature or the heat treatment time is longer than the above time, the effect of improving the function of the eco-friendly inorganic solidifying material due to thermal energy consumption is insignificant, and the mineral crystals are formed in a more dense structure, which is mixed with moisture and cement. Since there is a problem that the reactivity is lowered and the function as a solidifying material is lowered, it is preferable that the heat treatment is performed under the above-described temperature and time conditions.

The secondary sintering step includes a step of cooling the heat treatment under the above-described conditions first and then cooling it. The cooling is preferably made in a natural cooling method, and it is preferable to cool the temperature of the clinker to 50° C. or less during cooling.

Meanwhile, an electron beam irradiation step of irradiating an electron beam to the raw material mixture may be performed between the first firing step and the second firing step. When an electron beam is irradiated to such a raw material mixture, the activity of the raw material surface is improved, and the bonding between each raw material occurs easily in the secondary firing step, which improves the clinker yield, which functions as a solidifying material. The effect of rapid growth and early strength development is more effective.

Specifically, the electron beam irradiation step may be a step of irradiating the raw material mixture with ^{an electron beam in the range of a density current of 200 to 400 A/cm 2} , and an acceleration voltage of 500 to 810 keV.

When the density current amount of the irradiated electron beam is within the above range, the entire raw material mixture is uniformly irradiated with the electron beam to obtain an environmentally friendly inorganic solidifying material of superior quality.

In addition, when the accelerating voltage is within the above range, the effect of improving the clinker yield is increased, and when it is less than 500 keV, this effect is insignificant, and when it exceeds 810 keV, unnecessary bonding with impurities increases due to excessive increase in surface activity. Since the function as a solidifying material is reduced, it is preferable to irradiate an electron beam in the voltage range described above.

Next, the pulverizing step is a step of pulverizing the raw material mixture that has undergone the secondary firing step. In this step, the raw material mixture that has undergone the secondary firing step, ie, clinker, may be pulverized to have a particle size of 50 to 200 μm.

When the particle size range of the clinker is within the above range, when mixed with water and cement, the clinker has excellent compatibility as well as excellent performance for accelerating initial water hardening, high initial strength can be expressed, and water leakage by absorbing excess moisture In the process of injecting grouting injection material into the upper part, such as in a tunnel, there is an advantage in that it can prevent construction defects due to moisture loss.

When the size of the particles obtained in the pulverization step exceeds 200 μm, the surface area of the particles is small and the above-mentioned effect is insignificant, so it is preferable to pulverize so that the maximum particle size becomes the above-mentioned size, and when the particle size deviation is large Since the quality of the grouting injection material according to the use of the eco-friendly inorganic solidifying material is different for each area, it is preferable to grind to have the above-mentioned particle size in this step for the production of the grouting injection material of uniform quality as a performance expression mill as a solidification material .

Another embodiment of the present invention relates to an environmentally friendly inorganic solidifying material manufactured according to an embodiment of the present invention.

This eco-friendly inorganic solidifying material is eco-friendly because it does not contain organic components, and has the advantage of inducing rapid hardening and early strength expression by accelerating the hydrocuring reaction between cement and water.

Another embodiment of the present invention relates to an eco-friendly grout injection material including the eco-friendly inorganic solidifying material.

The eco-friendly grout injection material according to this embodiment includes an eco-friendly inorganic solidifying material, cement, and water manufactured according to an embodiment of the present invention, and may be individually packaged and prepared before construction, and mixed immediately before grout construction.

The type of the cement is not particularly limited, and for example, Portland cement, medium heat cement, crude steel cement, etc. may be used.

The contents of the eco-friendly inorganic solidifying material, cement, and water constituting the eco-friendly grout injection material according to this embodiment are not particularly limited, and may be appropriately mixed according to the construction environment and conditions.

In addition, the eco-friendly grout injection material may further include a solidifying material, a hardening agent, an aggregate, etc. commonly used, and in addition to this, various commonly used additives may be included.

Hereinafter, specific actions and effects of the present invention will be described through an embodiment of the present invention. However, this is presented as a preferred example of the present invention, and the scope of the present invention is not limited according to the embodiments.

[ manufacturing example ]

First, 100 parts by weight of limestone, 24 parts by weight of hectorite, 15 parts by weight of allophane, 10 parts by weight of quenched water chain ferronickel slag and 1.2 parts by weight of sodium nitrate to prepare a uniform raw material mixture, and an amplitude of 5 to 8 mm and 4 After applying vibration having a frequency of ~6 kHz, heat treatment at 780° C. for 3 minutes, followed by natural cooling to 50° C. or less, the first firing step was completed. Next, it was heated again at 1420 ° C. for 40 minutes, cooled naturally to 50 ° C. or less to complete the secondary firing step, and pulverized and sieved so that the particle size was in the range of 80 to 150 μm to prepare an eco-friendly inorganic solidified material.

[ Experimental example One]

The environmental pollution harmful components of the environmentally friendly inorganic solidifying material prepared in Preparation Example were measured, and the results are shown in Table 1. If the measurement result was 0.01 ppm or less, it was indicated as non-detection. As shown in Table 1 below, the environmentally friendly inorganic solidifying material of the present invention did not detect environmental pollutants classified as environmental polluting harmful components, and thus it was confirmed that it was environmentally friendly.

Ingredient name ppm CD non-detection CN non-detection Pb non-detection Hg non-detection As non-detection Cr ^{6 +} non-detection PCBs non-detection

[ Experimental example 2]

An eco-friendly inorganic solidified material was prepared in the same manner as in the above preparation example, but an eco-friendly inorganic solidified material was prepared using quenched water chain ferronickel slag having different particle sizes through the following pretreatment.

Pretreatment, the quenched water crushed ferronickel slag was pulverized and sieved to have a particle size in the range of 1 to 200 μm, separated to have the particle size range shown in Table 2, and each pulverized product was heat-treated at 980° C. for 3 minutes. .

Then, a specimen was prepared by mixing 100 parts by weight of normal Portland cement, 280 parts by weight of water and 40 parts by weight of an eco-friendly inorganic solidifying material, and the gelation time and compressive strength for each hour according to KS F 2343 were measured, and the results are listed in Table 2 did.

quench water chain
ferronickel slag gelation time
(sec) Compressive strength by age
(kg/cm ³ ) Pretreatment Particle size (㎛) 1 hours 1 day 3 days 7 days 28 days Example 1 X 1 to 40 84 5.8 11.2 18.9 25.3 29.6 Example 2 O 0.01~1 72 6.3 12.2 20.0 24.9 31.5 Example 3 O 1 to 40 65 8.8 21.4 29.5 34.8 40.1 Example 4 O 40-60 66 8.4 19.9 28.5 34.0 39.8 Example 5 O 60-100 65 8.3 19.0 27.4 33.2 39.3 Example 6 O 100-140 120 2.9 8.4 12.6 22.6 30.4 Example 7 O 140-200 142 3.0 8.8 11.5 21.8 29.3

Referring to the results in Table 2, it was found that when the particle size of ferronickel slag was pulverized to 100 μm or less and pre-treated, the effect of shortening the gelation time and improving the compressive strength of the specimen appeared. It is judged to be the result because the impurities of the ferronickel slag were removed through the heat treatment step during the process. In particular, when it exceeds 100 μm, the surface area is low, so the effect of accelerating the initial hardening does not appear sufficiently, and it is judged that it merely functions as an aggregate.

In particular, when the particle size of the ferronickel slag is 1 to 100㎛, the water hardening effect by the ferronickel slag is increased, and it is judged that the density of the specimen is increased. appeared to be

Therefore, from the results of this experiment, it was confirmed that it is preferable to pretreat the quenched water chain ferronickel slag to promote initial hardening, secure initial strength, and improve final strength, but grind the particle size to 1 ~ 100㎛ before heat treatment.

[ Experimental example 3]

The same eco-friendly inorganic solidifying material as in Example 3 was prepared, but the content of ferronickel slag added to the eco-friendly inorganic solidifying material was changed as shown in Table 3 below, and usually 100 parts by weight of Portland cement, 280 parts by weight of water and After preparing each specimen by mixing 40 parts by weight of an environmentally friendly inorganic solidifying material, the compressive strength for each age was measured in the same manner as in Experimental Example 2, and the results are shown in Table 3.

In Table 3, the content of the quenched water chain ferronickel slag means the content ratio with respect to 100 parts by weight of limestone.

Quenched water chain ferronickel
Slag (parts by weight) Compressive strength by age (kg/cm ³ ) 1 hours 1 day 3 days 7 days 28 days Example 3 10 8.8 21.4 29.5 34.8 40.1 Example 8 7 8.3 20.9 28.8 33.5 39.6 Example 9 15 8.5 22.1 30.2 35.1 40.8 Comparative Example 1 5 4.2 13.1 19.9 29.6 34.3 Comparative Example 2 18 9.0 18.5 23.4 27.3 31.5

Referring to the results of Table 3, in the case of Examples 3, 8 and 9, the compressive strength according to the initial age was significantly higher than that of Comparative Examples 1 and 2, and the compressive strength after the age of 28 days It can be seen that the higher the It is considered that this is because the initial hardening is promoted and the final strength is enhanced by the ferronickel slag. However, in the case of Comparative Example 1, the content of ferronickel slag was low and it was judged that the above-described effect was insignificant, and in the case of Comparative Example 2, the content of ferronickel slag was rather excessive and unreacted ferronickel slag was used as an impurity. It is judged that the effect of promoting hardening and enhancing strength does not appear.

Therefore, from the results of this experiment, it was confirmed that the quenching water chain ferronickel slag contained in the environmentally friendly inorganic solidifying material of the present invention is preferably included in an amount of 7 to 15 parts by weight based on 100 parts by weight of limestone.

[ Experimental example 4]

An eco-friendly inorganic solidifying material was prepared in the same manner as in Example 3, but an electron beam irradiation step of irradiating an electron beam between the first and second firing steps in the manufacturing step was further performed to prepare an eco-friendly inorganic solidified material.

For each example, the electron beam was ^{irradiated with a density current of 320 A/cm 2} for 5 minutes, and the acceleration voltage was changed as shown in Table 4.

Thereafter, a specimen was prepared in the same manner as in Experimental Example 2 using the eco-friendly inorganic solidifying material of each Example, and the compressive strength for each age was measured, and the results are shown in Table 4.

electron beam irradiation step Compressive strength by age (kg/cm ³ ) processing or not Acceleration voltage (keV) 1 hours 1 day 3 days 7 days 28 days Example 3 X - 8.8 21.4 29.5 34.8 40.1 Example 10 O 450 9.0 21.8 30.0 35.2 40.9 Example 11 O 500 10.6 30.8 34.5 42.0 47.3 Example 12 O 580 10.9 31.0 35.6 43.1 48.2 Example 13 O 720 11.2 31.2 36.8 42.5 48.0 Example 14 O 810 10.7 30.5 36.0 42.2 47.5 Example 15 O 850 5.3 20.2 31.5 35.9 42.1

Referring to the results of Table 4, it was confirmed that the effect of improving the final compressive strength was confirmed when the electron beam treatment was performed on the raw material mixture on which the primary firing step was performed. However, when the acceleration voltage was low as in Example 10, results similar to those of Example 3 without the electron beam treatment were shown, and when the acceleration voltage was low, it was confirmed that the effect of improving the solidification performance by the electron beam treatment was insignificant. When the acceleration voltage is high as shown in Fig. 15, it was found that the securing of the ultra-initial strength was insignificant.

Therefore, from the results of this experiment, it was confirmed that the raw material mixture was first fired and then subjected to electron beam treatment to improve the strength of the grout injection material. It was confirmed that it is desirable to treat.

The present invention is not limited to the specific embodiments and descriptions described above, and without departing from the gist of the present invention claimed in the claims, anyone with ordinary skill in the art to which the invention pertains can implement various modifications and such modifications shall fall within the protection scope of the present invention.

Claims (11)

a mixing step of preparing a raw material mixture by mixing limestone, hectorite, allophane, ferronickel slag and sodium nitrate;
a first firing step of cooling the raw material mixture after heat treatment;
a secondary sintering step of heat-treating the raw material mixture that has undergone the primary sintering step at a higher temperature than the primary sintering step and then cooling; and
a grinding step of pulverizing the raw material mixture that has undergone the secondary firing step;
Between the first firing step and the second firing step, an electron beam irradiation step of irradiating an electron beam to the raw material mixture is performed, the method for producing an environmentally friendly inorganic solidifying material.
According to claim 1,
In the mixing step, based on 100 parts by weight of limestone, 18 to 32 parts by weight of hectorite, 12 to 29 parts by weight of allopein, 7 to 15 parts by weight of ferronickel slag, and 0.1 to 3 parts by weight of sodium nitrate are mixed to prepare a raw material mixture A method of manufacturing an eco-friendly inorganic solidifying material, characterized in that the step of
According to claim 1,
The method of manufacturing an environmentally friendly inorganic solidified material, characterized in that the heat treatment temperature in the first firing step is 600 ~ 1000 ℃.
According to claim 1,
The heat treatment temperature in the secondary firing step is 1300 ~ 1600 ℃, characterized in that the environment-friendly inorganic solidified material manufacturing method.
delete According to claim 1,
The first firing step is a method of manufacturing an environmentally friendly inorganic solidifying material, characterized in that performed in a nitrogen atmosphere.
According to claim 1,
The ferronickel slag is, characterized in that the quenching water chain ferronickel slag, an environmentally friendly inorganic solidification method.
According to claim 1,
The ferronickel slag is a method of manufacturing an environmentally friendly inorganic solidification material, characterized in that prepared through a pretreatment process of grinding and heating the ferronickel slag.
9. The method of claim 8,
The pretreatment process is
a pulverization step of pulverizing ferronickel slag, a by-product of the smelting process, to a particle size of 1 to 100 μm; and
A method for producing an environmentally friendly inorganic solidified material, comprising: a rapid sintering step of heat-treating the pulverized ferronickel slag for 1 to 5 minutes.
An eco-friendly inorganic solidifying material manufactured according to any one of claims 1 to 4 and 6 to 9.
An eco-friendly grout injection material comprising an eco-friendly inorganic solidifying material, cement, and water manufactured according to any one of claims 1 to 4 and 6 to 9.