KR102650583B1 - Method for manufacturing of grout chemical using desulfurized gypsum, and grout construction method using the same - Google Patents

Abstract

The present invention relates to a method for producing a grout chemical solution (fast-setting silica sol, finished silica sol) used when performing grout construction to form a water barrier for the purpose of underground digging, and a grout construction method using the prepared grout chemical solution. The invention includes a process of forming a common chemical solution to produce a grout chemical solution, a step of forming a quick-setting chemical solution, and a step of forming a finished chemical solution, and mixing the common chemical solution and the quick-setting chemical solution to produce a quick-setting silica sol grout chemical solution and the above. A method of manufacturing a grout chemical solution using desulfurized gypsum, which has the effect of improving the early strength during grout construction and the initial reactive first-day strength by mixing the common chemical solution and the final chemical solution to form a finished silica sol grout chemical solution, and using the same It is about grout construction method.

Description

Method for manufacturing grout chemical using desulfurized gypsum, and grout construction method using the same {Method for manufacturing of grout chemical using desulfurized gypsum, and grout construction method using the same}

The present invention relates to a method for producing a grout chemical solution injected in construction such as ground reinforcement, water blocking, multi-stage steel pipe, pile filling, etc., and a grout construction method using the grout chemical solution formed by the above manufacturing method.

More specifically, through the reforming process and fine powder process of desulfurized gypsum, which is a recycled resource, the initial strength of the grout chemical solution is secured at more than 5 kg/cm2 during the grout construction process, and the permeability coefficient is secured at less than 10 ^-5 cm/sec. It relates to a method of manufacturing a grout chemical solution that can penetrate into the gravel layer, sand layer, and silt layer (clay layer), and a grout construction method using the grout chemical solution formed by the above manufacturing method.

In general, grout construction involves injecting and infiltrating injection material (or barrier material, filler material) into cracks in the ground or empty spaces in the ground to prevent water leaks or stabilize the soil in civil engineering or construction work to increase the strength (bearing capacity) of the ground. It is a construction method to stabilize the structure and prevent water leaks by improving compressibility (prevention of settlement), and reducing water permeability.

In other words, in grout construction, by injecting injection material (water barrier material or grout material) suitable for the construction site conditions, water accumulated in empty spaces in the ground or water flowing in the ground is blocked, and the strength of the soft ground is strengthened. Because it can be solidified, foundation construction can proceed smoothly.

In this case, the injection material (barrier material) used in grout construction is called grout material or filler, and the grout material is filled to fill gaps in the ground or empty spaces in the ground using gravity or a pump as an injection device. I order it.

Types of the above grout materials include cement-based grout materials (milk, mortar) using cement, water, clay, etc., iron-based grout materials used for filling steel foundations or for filling and reinforcing joints, and asphalt-based grout materials used for water retention and soil stability. Grout materials are being used, and recently, along with innovations in equipment used to solidify the ground, research on chemical grout materials as a variety of injection materials is being actively conducted.

The cement-based grout has a problem in that environmental contaminants contained in cement leach out and contaminate groundwater.

In addition, the chemical grout has a problem in that leaching of the grout progresses over time, causing the injected grout to lose its original function and contaminate groundwater. In order to improve these problems, research on chemical grout, which is a chemically modified (reforming) chemical grout, has recently been actively conducted.

When carrying out grout construction using the chemical grout, a mixture of the chemical solution and an aqueous cement solution (hereinafter referred to as 'cement sol') is used. However, the cement sol is also very toxic and has the problem of contaminating groundwater.

The chemical grout can be classified into polymer chemical injection materials, water glass-based chemical injection materials, and inorganic chemical injection materials.

The polymer chemical injection materials include Acryl-Amide type and Urethane type, but are currently not used except for special purposes due to serious environmental pollution.

The water glass-based chemical injection material is a suspension type injection material, mainly cement. Clay minerals. Sand and chemicals are used singly or mixed depending on the purpose of construction, and can be divided into alkaline suspension type and non-alkaline suspension type.

i) As a water glass-based chemical injection material, the alkaline suspension type uses water glass (soda silicate, or sodium silicate) as the main material. There are various types depending on the content of silicic acid, but when injecting on site, water glass No. 3 is usually used. (Disodium Trisilicate: Na2O. 3SiO2) is widely used, and water glass is not used alone, but is used together with various reactive agents (ordinary Portland cement (OPC), slag cement (S/C), lime, phosphoric acid, sodium chloride). There is a separate gel time regulator, which aims to control the gel time, improve permeability and water resistance, and maintain strength. Representative grout construction methods include the LW (Labiles Wasser Glass) method as a chemical injection method, The SGR (Space Grouting Rocket) method and the MSG (Micro Silica Grouting) method are known.

The LW method is a method of adding sodium silicate (water glass) to conventional cement milk while evolving from cement milk injection to chemical grout construction.

The LW method is a method of mixing soda silicate (water glass) and cement suspension and injecting it at low pressure using a 1.5 shot system (2 liquids, 1 process). It is more economical than the perforated method and allows re-injection when defects are found, but the injection depth is relatively shallow in the ground. This method is applied to sand layers with large gaps (not applicable to fine sand layers), so loss of injection material may occur in rock layers such as gravel with high flow velocity. It has the disadvantage of requiring careful management of injection pressure during construction, low vibration and impact resistance due to external forces, gel time control is not smooth, curing of seal material is required, and ground reinforcement and water blocking effects are not significant. Therefore, it is a method that does not currently have much applicability. The use of water glass has the disadvantage of low long-term durability, such as leaching, and contaminating groundwater.

The SGR method is a method of separately injecting quick-set material and finished material so that the gel time can be adjusted. After drilling to a predetermined depth with a double-pipe injection rod, quick-set material and finished material are cross-injected to fill voids in the ground. do.

In other words, it is a double pipe (exterior + inner pipe) type complex injection method using sodium silicate as the injection material. This is a method that uses a special tip device (rocket) to inject rapid and complete injection material at medium to low pressure through an induction space formed in the ground. Cross-inject.

By first filling the large pores in the ground with the rapid-setting injection material, the finished injection material is subsequently injected to prevent it from being lost outside the injection range. At this time, the completed injection material maintains a liquid state until it gels and penetrates into the micropores to fill the pores in the ground. Charge.

The SGR method can achieve a uniform work effect by forming an induction space, prevent ground uplift, and have the effect of reducing ground disturbance due to low injection pressure. In addition, since there is no rotation of the injection pipe, the packing of the rapid setting injection material can be achieved. Due to the effect, limited injection into the target ground can be expected and the gel time can be adjusted.

However, in the SGR method, leaching phenomenon caused by sodium silicate and volume reduction phenomenon after construction occur, and since cement is used, heavy metals in cement leach out and contaminate groundwater, grouting is uncertain in silty clay layers, and injection Not only does the injection effect deteriorate in the rock layer with a depth of 40 m or more, but it also takes a relatively long injection time due to low pressure and low speed injection, the equipment is relatively complex, it is difficult to expect strength as an earth wall, and the resistance to external forces is insufficient, so long-term damage is required. There is a problem that it is unsuitable for water blocking and ground reinforcement.

The MSG method is a method that improves both the injection material and the injection device, and is an eco-friendly low-pressure penetration injection method that improves permeability, strength, and durability by using a microcomposite silica-based injection material with a maximum particle size of 10㎛ or less.

The MSG method can be applied to sandy ground or multiple strata with various ground characteristics, and can be applied to various fields such as retaining back water, preventing piping, strengthening foundation ground, underpinning of building foundation, embankment foundation, etc. Since it is a low-pressure infiltration injection method, it is possible to maintain the original ground conditions without ground disturbance. It is easy to secure the working area by miniaturizing the equipment, the infiltration injection effect is good, and durability is excellent by suppressing leaching by groundwater. Although it is effective, there are problems in that there are few construction cases, the injection material is expensive, and because sodium silicate (water glass) is used, alkali leaching may occur, and long-term strength development is impossible.

As described above, chemical injection methods such as the LW method, SGR method, and MSG method, which use alkaline suspension type grout material injection material in the grout construction process, have a slight water flow rate when applied to a sand layer or sand gravel layer with large pores. Since the injection material is washed away, the loss of the injection material is very large, and in some cases, grout construction is impossible. Not only that, but sodium silicate (water glass) is used as a raw material for the grout agent, which causes alkali leaching phenomenon, which causes damage over time. There is a problem that the volume is greatly reduced as this is done.

ii) As a water glass-based chemical injection material, the non-alkaline suspension type is neutralized by adding sulfuric acid to water glass as the main material, and uses ordinary Portland cement (OPC) and slag cement (S/C) as reactants, and a representative grout construction method for this. This is the SMI (Space-Multi Injection Grouting) method, which is a low-pressure penetration injection method using non-alkaline silica sol. The injection pipe simultaneously injects rapid and finished materials from spray nozzles separated at the top and bottom, which deviates from the injection purpose and scope. It is effective in complex injection by preventing .

As described above, the conventional grout construction method according to the prior art is a method of mixing a small amount of sodium silicate and cement, and the gel time required for the chemical solution in the sol state to change to a gel state is used. ) is very slow, and the scope of application is limited due to low water quality. To make up for this problem, a method of shortening the gel time by using sulfuric acid, sodium bicarbonate, etc. as an accelerator is sometimes used.

In the case of the grout construction method using water glass (sodium silicate) chemical grout material, there is a problem that alkali leaching phenomenon occurs and the volume is reduced after construction, and leaching is a disadvantage of the water glass ground injection material. In order to solve the durability problem, various construction methods were developed and constructed, such as using quick-set cement such as ordinary Portland cement (OPC), which hardens through hydration reaction and develops strength over time, as a ground injection material instead of water glass-based chemical grout material. It is currently being applied.

As a grout construction method for injecting the water glass chemical solution, the LW method, SGR method, and SMI method use the main material (sodium silicate - liquid A) and the reactive material (OPC, etc. - liquid B) to create a polymer network structure of sodium silicate and react. The material is covered and fixed, and strength is developed as the reactive material hardens. However, these construction methods are weak in strength because the hydration reaction of the coated reactive material is suppressed, and as time passes, the water retention effect rapidly decreases depending on the construction period due to leaching. There is a problem that it is reduced, and when regular Portland cement is used, there is a problem that environmental problems arise due to hexavalent chromium, a heavy metal.

In addition, recently, in the grout construction process, the general Portland cement is also excluded, and all raw materials for the chemical grout material are used as ground inorganic chemical injection materials made of non-cement based inorganic materials, which is evolving into an environmentally friendly method.

The injection material of the non-cementitious inorganic material is an ettringite-forming type, and calcium sulfoaluminate is used as the main material. Gypsum, ash, or general Portland cement (OPC) can be used as the binder, and the inorganic chemical solution A representative grout construction method using injection material is the EGM Eco-friendly Grouting Method.

The inorganic chemical injection material is used as a grout injection material with excellent initial strength and early strength as a hardened body is created through a pozzolanic reaction during grout construction and has excellent utility as a barrier material.

In general, pozzolanic materials cannot be hardened because they are not hydraulic in themselves, but they are a general term for materials that can slowly react at room temperature with metal salts, acids, or alkalis dissolved in water to form compounds that are insoluble in water.

Representative materials here are divided into natural materials such as tuff and diatomaceous earth and artificially created materials such as fly ash slag fine powder and silica fume.

The pozzolanic reaction mechanism by the inorganic chemical injection material is that soluble components such as silicon dioxide (SiO ₂ ) or aluminum oxide (Al ₂ O ₃ ) eluted from the pozzolanic material slowly react with slaked lime [Ca(OH) ₂ ] to form insoluble calcium silicate. A hard hardened body is created by forming a hydrate (CSH gel) or calcium aluminate hydrate (CAH gel) according to the following formula (1).

(Formula 1): [Ca(OH) ₂ + [SiO ₂ , Al ₂ O ₃ ] = 3CaO _{2.SiO 2} .3H ₂ O. or 3CaO.Al ₂ O ₃ .6H ₂ O]

Meanwhile, the CFBC (Circulating Fluidized Bed Combustion) ash or slag fine powder of supercritical fluidized bed boilers, which is used as a rapid setting agent, is not hydraulic in itself, but contains a large amount of silicon dioxide, which causes irritants (alkali agents) and desulfurization gypsum present in the gypsum. Slaked lime forms an insoluble C-S-H gel through a pozzolanic reaction, and when the insoluble gel thus formed penetrates into the ground, a dense hydrate is formed over time, forming a hard hardened body.

Calcium aluminate (3CaO.Al ₂ O ₃ .6H ₂ O) formed by the pozzolanic reaction of the above (Formula 1) reacts again with water to produce various calcium aluminate hydrates, and in the presence of SO ₃ , calcium sulfoaluminate-based hydrates. Phosphorus ettringite (3CaO·Al ₂ O ₃ ·3CaSO ₄ ·32H ₂ O) or monosulfate (3CaOAl ₂ O ₃ .CaSO ₄ .12H ₂ O) is produced by the following formula (2).

(Formula 2): (CaSO ₄ +CaO+nH ₂ O)+(CSA+nH ₂ O)→3CaO·Al ₂ O ₃ ·3CaSO ₄ ·32H ₂ O

The ettringite (3CaO · Al ₂ O ₃ · 3CaSO ₄ · 32H ₂ O) or monosulfate (3CaOAl ₂ O _{3.CaSO 4.12H 2} O) material is a gelling material that penetrates into the ground during grout construction. As time passes, dense hydrates are formed, so it is a hardened material with strong strength and is an important material that can demonstrate excellent performance as a barrier material during water barrier construction.

The inorganic material injection material is a grout construction method that uses materials that do not contain heavy metals by utilizing rapid setting of calcium aluminate or calcium sulfoaluminate, which are ground improvement materials, and ultrafine particles of by-products generated in thermal power plants or oil refining processes. In this case, semi-permanent water blocking and reinforcement solves the leaching phenomenon and strength reduction that occur when using existing water glass materials, has excellent durability and strength after construction, and solves the disadvantage of not being free from heavy metals when using cement. It is an environmentally friendly grout agent suitable for use in ground reinforcement, water blocking, multi-stage steel pipes in tunnels, and back filler for semi-shields.

Therefore, a study on a grout construction method using an inorganic injection material as a grout chemical solution that can not only block water flowing from ground layers with large pores such as sand or gravel layers, but can also be finely powdered and injected into the silt layer. Development is gradually expanding.

Patent registration number 10-1697964 (registered on January 13, 2017) Patent registration number 10-2255382 (registered on May 17, 2021) Patent registration number 10-2302868 (registered on September 11, 2021)

In order to solve the above problems, the purpose of the present invention is to provide a method for producing quick-set silica sol and finished silica sol as a grout chemical solution by modifying desulfurized gypsum.

In addition, according to the present invention, the rapid setting chemical and the finished chemical are finely powdered to ensure a permeability coefficient of 10 ^-5 cm/sec or less, so that the injection material can penetrate not only the gravel layer and sand layer but also the silt layer during grout construction. The purpose is to provide a method for manufacturing.

In addition, according to the present invention, the object is to provide a grout construction method using the grout chemical solution prepared as described above.

The method for producing a grout chemical solution according to an embodiment of the present invention is a method of producing a grout chemical solution used when performing grout construction to form a water barrier for the purpose of underground excavation, to improve early strength during grout construction. To this end, the first reforming process is performed to form the first intermediate material in which calcium sulfate accounts for more than 50% by weight of the total content of desulfurized gypsum, a recycled resource obtained as a by-product in the oil refining process, and to increase initial reactivity. In order to improve the strength on the first day, the proportion of calcium phosphate among the components included in the total content of desulfurized gypsum is 1 to 2% by weight of the calcium sulfate content, and the second reforming process is performed to form a second intermediate material. After performing the reforming step (S110) and the first intermediate material and the second intermediate material formed by the reforming process of desulfurized gypsum in the above (S110 step) using a grinder, the highly powdered A step (S120) of mixing the first intermediate material, the second intermediate material, and CFBC (Circulating Fluidized Bed Combustion) ash generated in a circulating fluidized bed boiler of a thermal power plant to form a powder-type common agent (S120), and forming in the step (S120) A step (S130) of forming a common chemical solution by mixing 30 to 35% by weight of a powdered common chemical and 60 to 75% by weight of water, and mixing finely powdered blast furnace slag, calcium sulfoaluminate and alkaline zein carbonate. A step of mixing to form a powdery quick-setting chemical (S140), and a step of mixing 30 to 35% by weight of the powdery quick-setting chemical formed from the step (S140) and 60 to 75% by weight of water to form a quick-setting chemical solution ( S150), and 40 to 60% by weight of the common chemical solution formed from the (S130) step, and 40 to 60% by weight of the quick setting chemical solution formed from the (S150) step are mixed immediately before ground injection to form a sol-type grout chemical solution. It is characterized by including a step (S160).

In addition, the method for producing a grout chemical solution according to another embodiment of the present invention is a method of producing a grout chemical solution used when performing grout construction to form a water barrier for the purpose of underground excavation, and the early strength is maintained during grout construction. In order to improve the first reforming process to form a first intermediate material in which calcium sulfate accounts for more than 50% by weight of the total content of desulfurized gypsum, a recycled resource obtained as a by-product in the oil refining process, and initial reactivity Desulfurization consisting of a secondary reforming process to form a second intermediate material in which the proportion of calcium phosphate among the components included in the total content of desulfurized gypsum is 1 to 2% by weight of the calcium sulfate content in order to improve the first-day strength by increasing the desulfurization. After performing the gypsum reforming step (S210) and the first intermediate material and the second intermediate material formed by the desulfurized gypsum reforming process in the above (S110 step) using a grinder, the high powder Mixing the converted first intermediate material, the second intermediate material, and CFBC (Circulating Fluidized Bed Combustion) ash generated in a circulating fluidized bed boiler of a thermal power plant to form a powdered common chemical (S220), and the step (S120) A step (S230) of forming a common chemical solution by mixing 30 to 35% by weight of the powdered common chemical formed in and 60 to 75% by weight of water, finely powdered blast furnace slag, calcium sulfoaluminate and alkaline zein. A step (S240) of mixing carbonates to form a powdery quick-setting chemical, 99.1 to 99.9% by weight of the powdery quick-setting chemical formed from the step (S240), and an organic acid as a reaction retardant (or carbon number prepared by fermenting sugarcane) A step (S250) of mixing 0.1 to 0.9% by weight of 6 organic acids to form a powdered drug, 30 to 35% by weight of the powdered drug formed from the step (S250), and 60 to 75% by weight of water. A step of mixing to form a complete chemical solution (S260), and 40 to 60% by weight of the common chemical solution formed from the step (S230), and 40 to 60% by weight of the complete chemical solution formed from the step (S260) immediately before injection into the ground. It is characterized in that it includes a step (S270) of mixing to form a grout chemical solution in the form of a sol.

According to the present invention, in the first reforming process of the (S110) step, in order to improve the early strength during the grout construction process, water and sulfuric acid are mixed with the desulfurized gypsum so that the proportion of calcium sulfate is determined by the total content of the desulfurized gypsum. In order to improve the first-day strength by increasing the initial reactivity during the grout construction process, the second reforming process in the step (S110) is performed by adding water and phosphoric acid to the desulfurized gypsum. It is characterized by mixing to form a second intermediate material in which calcium phosphate is 1 to 2% by weight of the calcium sulfate content contained in the desulfurized gypsum.

According to the present invention, in the first reforming process of the (S110) step, in order to improve early strength during the grout construction process, calcium oxide contained in the desulfurized gypsum reacts with water to form calcium hydroxide, and the calcium hydroxide and This is a process in which sulfuric acid reacts to produce calcium sulfate and two molecules of water. The second reforming process in the (S110) step is to increase the initial reactivity during the grout construction process and improve the first-day strength by adding the desulfurized gypsum to the desulfurized gypsum. The process is characterized in that the contained calcium oxide and water react to form calcium hydroxide, and the calcium hydroxide and phosphoric acid react to produce calcium phosphate and two molecules of water.

According to the present invention, the first intermediate material is produced by the formula {CaO + H ₂ O → Ca(OH) ₂ } and {Ca(OH) ₂ + H ₂ SO ₄ → CaSO ₄ + 2H ₂ O} , the second intermediate material is characterized in that it is produced by the chemical formula {CaO + H ₂ O → Ca(OH) ₂ } and {Ca(OH) ₂ + H ₃ PO ₄ → CaHPO ₄ + 2H ₂ O} .

According to the present invention, when the grout chemical solution formed by the first intermediate material is injected into the ground during grout construction, the early strength is cured to a strength of 10 kg/cm2 or more within 3 to 7 days.

According to the present invention, when the grout chemical solution formed by the first intermediate material is injected into the ground during grout construction, the initial reactivity (1st day strength) is characterized by hardening to a strength of 5 kg/cm2 or more.

According to the present invention, the reaction retardant is an organic acid or an organic acid having 6 carbon atoms produced by fermenting sugarcane.

In addition, the grout construction method according to the present invention is characterized by using a grout chemical solution prepared according to claim 1 or claim 2.

Since sodium silicate (water glass) is not used during grout construction using the grout chemical solution formed according to the present invention, there is little reduction in the volume of the grout due to leaching phenomenon.

In addition, the present invention does not use general Portland cement but uses desulfurized gypsum, an industrial by-product without heavy metals, so it has the effect of recycling resources and preventing heavy metal contamination of the soil.

In addition, the present invention uses calcium phosphate to increase the initial hardening speed and prevent musking, so that when finished silica sol, a grout chemical solution, is injected, the permeability coefficient can be lowered to 10 ^-5 cm/sec or less by consolidating the soft ground. , the injection material can penetrate not only the gravel layer and sand layer, but also the finely powdered silt layer.

Figure 1 is a schematic diagram for explaining the mechanism for producing quick-setting silica sol and finished silica sol as a grout chemical solution according to the present invention.
Figure 2 is a flow chart showing the process of producing quick-setting silica sol as a grout chemical solution according to the present invention.
Figure 3 is a flow chart showing the process of producing finished silica sol as a grout chemical solution according to the present invention.
Figure 4 is a diagram comparing common medicines manufactured using the modified desulfurized gypsum of the present invention and common medicines manufactured using the desulfurized gypsum before modification according to the prior art.
Figure 5 compares the leaching phenomenon of a mold specimen of a grout chemical solution manufactured using the modified desulfurized gypsum of the present invention with that of a mold specimen of a grout chemical solution manufactured using the desulfurized gypsum before modification according to the prior art. It is a drawing.
Figure 6a is a diagram showing the results of a test on the homogel permeability coefficient for a quick-set grout chemical solution mixed with a common chemical solution and a quick-setting chemical solution prepared according to the present invention.
Figure 6b is a diagram showing the test results for the homogel permeability coefficient for the finished grout chemical solution mixed with the common chemical solution and the finished chemical solution prepared according to the present invention.

Since the description of the present invention is only an example for structural or functional explanation, the scope of the present invention should not be construed as limited by the examples described in the text. In other words, since the embodiments can be modified in various ways and can have various forms, the scope of rights of the present invention should be understood to include equivalents that can realize the technical idea.

In all the drawings below, components having the same function are given the same reference numerals, so repeated descriptions are omitted, and the terms described below are defined in consideration of the functions in the present invention, which is consistent with the technical idea of the present invention. It is specified that the concept should be interpreted according to its own common meaning.

Meanwhile, the meaning of the terms described in the present invention should be understood as follows.

Terms such as “first” and “second” are used to distinguish one component from another component, and the scope of rights should not be limited by these terms. For example, a first component may be named a second component, and similarly, the second component may also be named a first component.

When a component is referred to as being “connected” to another component, it should be understood that it may be directly connected to the other component, but that other components may exist in between. On the other hand, when a component is referred to as being “directly connected” to another component, it should be understood that there are no other components in between. Meanwhile, other expressions that describe the relationship between components, such as "between" and "immediately between" or "neighboring" and "directly neighboring" should be interpreted similarly.

Singular expressions should be understood to include plural expressions, unless the context clearly indicates otherwise, and terms such as “comprise” or “have” refer to the specified features, numbers, steps, operations, components, parts, or them. It is intended to specify the existence of a combination, and should be understood as not excluding in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

For each step, identification codes (e.g., a, b, c, etc.) are used for convenience of explanation. The identification codes do not explain the order of each step, and each step clearly follows a specific order in context. Unless specified, events may occur differently from the specified order. That is, each step may occur in the same order as specified, may be performed substantially simultaneously, or may be performed in the opposite order.

All terms used herein, unless otherwise defined, have the same meaning as commonly understood by a person of ordinary skill in the field to which the present invention pertains. Terms defined in commonly used dictionaries should be interpreted as consistent with the meaning they have in the context of the related technology, and cannot be interpreted as having an ideal or excessively formal meaning unless clearly defined in the present invention.

Additionally, in describing the present invention, if it is determined that a detailed description of a related known function or configuration may obscure the gist of the present invention, the detailed description will be omitted.

Hereinafter, the method for producing a grout chemical solution using desulfurized gypsum according to the present invention and the grout construction method using the same will be described in detail.

The present invention was developed to improve the disadvantages of water glass-based grout injection material during the grout construction process. Since calcium silicate or ettringite is generated by the grout injection material made of non-cementitious inorganic material, not only does it not cause leaching or heavy metals, but it is also a grout material for ground blocking that can be used in seawater, and is currently manufacturing the highest level grout chemical solution. Method and grout construction method using the same.

According to the present invention, in order to ensure workability in the grout construction process as a chemical solution for ground grout for waterproofing purposes, two types of quick-set silica sol grout chemical solution are manufactured by combining a common chemical solution and a quick-setting chemical solution, or a common chemical solution and a complete chemical solution are prepared. A finished silica sol grout chemical solution combining is manufactured, and is characterized in that it is a grout construction method using the rapid setting/complete silica sol grout chemical solution prepared as described above.

According to the present invention, during the grout construction process, after drilling the ground, the common chemical solution and the quick setting chemical solution or the complete chemical solution are injected and transported at low pressure through a double pipe, and are mixed at the point where they meet the ground to form a quick setting/complete silica sol grout chemical solution. GEL formation and loss of fluidity occur within a few seconds, and in this case, the gel formation time is approximately 10 seconds (rapid setting) or hardening occurs in approximately 1 minute (complete setting).

The role of the quick-set silica sol grout chemical is to strengthen the initial strength during the drilling process and prevent the chemical solution injected around the drilling rod, which has changed to the weakest ground state, from being ejected through the injection pipe to the ground surface, and the completed silica The sol grout chemical solution flows into weak areas of the original perforated ground, consolidates (increases the density of the ground), and then hardens, ultimately lowering the permeability coefficient. Through a series of repetitive processes as above, ground water protection work is performed. You can proceed.

On the other hand, when the phenomenon of silica sol occurs due to the rapid setting silica sol as a grout chemical solution, no matter how much finished silica sol grout chemical solution is injected, it penetrates into weak areas of the ground and its role in consolidating the ground is weakened, so the finished silica sol grout chemical solution is used. Since the water blocking effect caused by the chemical solution cannot be exerted, the effect of strength development can be obtained due to the rapid curing of the quick-setting silica sol grout chemical solution according to the present invention, that is, due to the injection of the quick-setting silica sol grout chemical solution according to the present invention. It has excellent initial strength (1st day strength) and early strength (3 to 7 days), and because it is manufactured from fine powder, it has the ability to penetrate into the silt layer, making it a valuable material for barrier materials that can exhibit excellent barrier effects. It works.

Hereinafter, specific examples of a method for producing quick-set silica sol and finished silica sol as a grout chemical solution according to the present invention will be described.

Figure 1 is a schematic diagram for explaining the mechanism for producing quick-setting silica sol and finished silica sol as a grout chemical solution according to the present invention.

That is, the present invention relates to a method for producing a grout chemical solution (fast-setting silica sol, finished silica sol) used when grouting is performed to form a water barrier for the purpose of underground digging, and a grout solution using the grout chemical solution prepared in this way. We will explain the construction method.

First, a process of forming a common chemical solution to manufacture a grout chemical solution, secondly, a process of forming a quick-setting chemical solution, thirdly, a process of forming a finished chemical solution, and finally, a quick setting process by mixing the common chemical solution and the quick-setting chemical solution. The process of forming the silica sol grout chemical solution and the finished silica sol grout chemical solution will be explained step by step.

I. [Common chemical solution formation process]

(I - Step 1): This is a process for reforming desulfurized gypsum, which is the raw material according to the present invention. The reforming process (I-S10 step) of desulfurized gypsum, a recycled resource obtained as a by-product in the oil refining process, is carried out.

More specifically, according to the present invention, in the step (I-S10), in order to use the desulfurized gypsum, which is a recycled resource obtained as a by-product in the petroleum refining process, as a raw material for a barrier material with excellent performance, it is used as a barrier material for the purpose of digging underground. In order to form a ground penetration, it is important to i) secure the development of early strength (strength on the 3rd to 7th day) and ii) improve the initial reactivity (strength on the 1st day).

Therefore, according to the present invention, in order to secure the early strength (3 to 7 days), the first plaster is formed so that the proportion of calcium sulfate (CaSO ₄ ) in the total content of desulfurized gypsum is 50% by weight or more. In order to proceed with the secondary reforming process (I-S11) and improve the strength on the first day, which is the initial reactivity, the proportion of calcium phosphate (CaHPO ₄ ) in the total content of desulfurized gypsum is calcium sulfate (CaSO ₄ ). ) The second reforming process (I-S12) is performed to form a content of 1 to 2% by weight, that is, two reforming processes are performed.

The first and second reforming processes progressing through the (I-S11) and (I-S12) steps are specifically as follows.

First, the [(I-S11) step] (first reforming process) is as follows.

The first reforming process, which is the (I-S11) step, is a reforming process of forming a first intermediate material so that the content of calcium sulfate (CaSO ₄ ) is 50% by weight or more among the components included in the total content of desulfurized gypsum. The tea reforming process is as follows.

The main components of desulfurized gypsum, a recycled resource obtained during the oil refining process, consist of calcium sulfate (40 to 45% by weight) and calcium oxide (55 to 60% by weight).

Therefore, when grouting is performed to form a barrier wall for the purpose of underground digging according to the present invention, the grout chemical solution using the desulfurized gypsum is injected and penetrates into the ground and hardens within a few days, that is, within 3 to 7 days. In order to develop strength, a first reforming process of forming a first intermediate material such that the proportion of calcium sulfate (CaSO ₄ ) in the total content of the desulfurized gypsum is 50% by weight or more,

The reforming process is performed according to the following (Formula 3) and (Formula 4).

(Formula 3) CaO + H ₂ O → Ca(OH) ₂

That is, according to the present invention, the first intermediate material is formed so that the proportion of calcium sulfate (CaSO ₄ ) in the total content of the desulfurized gypsum is 50% by weight or more, so that the early strength (strength on the 3rd to 7th day) can be improved. , Calcium oxide (CaO) contained in the desulfurized gypsum reacts with water (H ₂ O) as shown in (Formula 3) above to form calcium hydroxide (Ca(OH) ₂ ).

(Formula 4) Ca(OH) ₂ + H ₂ SO ₄ → CaSO ₄ + 2H ₂ O

Calcium hydroxide (Ca(OH) ₂ ) formed by the above (Formula 3), as in the above (Formula 4), calcium hydroxide (Ca(OH) ₂ ) and sulfuric acid (H ₂ SO ₄ ) react to form calcium sulfate (CaSO ₄ ) and two molecules of water (2H ₂ O) are generated, and the two molecules of water (2H ₂ O) generated by the above (Formula 4) react with calcium oxide (CaO) again as shown in (Formula 3) Calcium hydroxide (Ca(OH) ₂ ) is produced and a cyclic reaction occurs.

As a result, the first intermediate material produced through the above-mentioned series of reforming processes is formed so that the proportion of calcium sulfate (CaSO ₄ ) accounts for more than 50% by weight of the total content of desulfurized gypsum, and therefore, the inorganic grout chemical injection material Ettlingite, a gelling material produced by a pozzolanic reaction mechanism, is generated and penetrates into the ground during grout construction, forming dense hydrates over time, thereby developing early strength that hardens within 3 to 7 days, making the material strong. As a hardened material, it can demonstrate excellent performance as a barrier material during water barrier construction.

Lot
No Before reformation
Desulfurized gypsum (g) Dilute sulfuric acid input amount (g)
(150g) Calcium sulfate production amount (g) note _H2O (g) H ₂ SO ₄ (g) CaSO ₄ (g) Increase rate (%) 1-1 1,000 135 15 20.8 1.81 1-2 1,000 120 30 41.6 3.62 1-3 1,000 105 45 62.5 5.43 1-4 1,000 90 60 83.3 7.24 1-5 1,000 75 75 104.1 9.05 1-6 1,000 60 90 124.9 10.86 1-7 1,000 45 105 145.7 12.67 1-8 1,000 30 120 166.5 14.48 1-9 1,000 15 135 187.4 16.30 1-10 1,000 0 150 208.2 18.10

[Table 1] above is a table of the reaction results between desulfurized gypsum and dilute sulfuric acid, from which the first intermediate material formed in the first reforming process is formed. In other words, as a circular resource obtained during the petroleum refining process, desulfurized gypsum in the stage before the reforming process, consisting of 40 to 45% by weight of calcium sulfate (CaSO ₄ ) and 55 to 60% by weight of calcium oxide (CaO), accounts for 50% by weight of the total content. This table shows the reaction results of desulfurized gypsum and dilute sulfuric acid during the reforming process in which the first intermediate material containing more than calcium sulfate (CaSO ₄ ) and less than 50% by weight of calcium hydroxide (Ca(OH) ₂ ) is formed.

In [Table 1], the amount of calcium sulfate produced and the increase rate (%) of calcium sulfate can be expressed by the following (Equation 1) and (Equation 2).

(Equation 1) [Sulfuric acid input amount (g) / 98 (sulfuric acid molecular weight)] * 136 (calcium sulfate molecular weight) = Calcium sulfate production amount

(Equation 2) (Calcium sulfate production / 1,150 (desulfurized gypsum + dilute sulfuric acid) * 100 = Calcium sulfate increase rate (%)

When the grout chemical solution formed by the first intermediate material, which is included so that the proportion of calcium sulfate (CaSO ₄ ) in the total content of the desulfurized gypsum as described above is 50% by weight or more, is injected into the ground during grout construction, 3 to 7 It is a hard hardened body that is formed with an early strength of 10 kg/cm2 or more within a day, and has the effect of demonstrating excellent performance as a water barrier material during water barrier construction.

Next, the [(I-S12) step] (second reforming process) is as follows.

The second reforming process, which is the step (I-S12), is performed so that the proportion of calcium phosphate (CaHPO ₄ ) among the components included in the total content of desulfurized gypsum is 1 to 2% by weight of the calcium sulfate (CaSO ₄ ) content. As a reforming process for forming the second intermediate material, the secondary reforming process is specifically as follows.

When performing grout construction to form a water barrier for the purpose of digging underground according to the present invention, the grout chemical solution using the desulfurized gypsum is injected and penetrated into the ground, and in order to improve the initial reactive primary strength, the total content of the desulfurized gypsum must be adjusted. A secondary reforming process to form a second intermediate material such that the proportion of calcium phosphate (CaHPO ₄ ) among the included components is 1 to 2% by weight of the calcium sulfate (CaSO ₄ ) content,

The reforming process is performed according to the following (Formula 5) and (Formula 6).

(Formula 5) CaO + H ₂ O → Ca(OH) ₂

That is, according to the present invention, the initial strength (first-day strength) can be improved by forming a second intermediate material containing calcium phosphate (CaHPO ₄ ) equivalent to 1 to 2% by weight of the calcium sulfate (CaSO ₄ ) content. , Calcium oxide (CaO) contained in desulfurized gypsum reacts with water (H ₂ O) to form calcium hydroxide (Ca(OH) ₂ ) as shown in (Formula 5) above.

(Formula 6) Ca(OH) ₂ + H ₃ PO ₄ → CaHPO ₄ + 2H ₂ O

Calcium hydroxide (Ca(OH) ₂ ) formed by the above (Formula 5) is formed by reacting calcium hydroxide (Ca(OH) ₂ ) and phosphoric acid (H ₃ PO ₄ ) as shown in the above (Formula 6) to form calcium phosphate (CaHPO ₄ ) and two molecules of water (2H ₂ O) are generated, and the water (2H ₂ O) produced by (Formula 6) reacts with calcium oxide (CaO) again as (Formula 5) to produce calcium hydroxide (Ca( A repetitive cyclic reaction occurs to produce OH) ₂ ).

As a result, the second intermediate material produced through the above series of reforming processes is formed so that calcium phosphate (CaHPO ₄ ) is 1 to 2% by weight of the calcium sulfate (CaSO ₄ ) content contained in the desulfurized gypsum. When the second intermediate material is used during grout construction, ettringite, a gelled material produced by the pozzolanic reaction mechanism by the inorganic grout chemical injection material, is generated and penetrates into the ground during grout construction to form a dense hydrate, resulting in initial reactivity. By increasing the first-day strength, it can demonstrate excellent performance as a water barrier material during water barrier construction.

Lot
No Before reformation
Desulfurized gypsum (g) Dilute phosphoric acid input amount (g)
(150g) Phosphate gypsum production amount (g) note _H2O (g) H ₃ P O ₄ (g) CaHPO ₄ (g) Calcium phosphate (% by weight) 2-1 1,000 148.5 1.5 2.1 0.18 2-2 1,000 147.0 3.0 4.2 0.36 2-3 1,000 145.5 4.5 6.3 0.54 2-4 1,000 144.0 6.0 8.3 0.72 2-5 1,000 142.5 7.5 10.4 0.91 2-6 1,000 141.0 9.0 12.5 1.09 2-7 1,000 139.5 10.5 14.6 1.27 2-8 1,000 138.0 12.0 16.7 1.45 2-9 1,000 136.5 13.5 18.7 1.63 2-10 1,000 135.0 15.0 20.8 1.81

[Table 2] above is a table of the reaction results between desulfurized gypsum and dilute phosphoric acid, from which the second intermediate material formed in the secondary reforming process is formed. That is, as a circular resource obtained during the oil refining process, desulfurized gypsum yarn consisting of 40 to 45% by weight of calcium sulfate (CaSO ₄ ) and 55 to 60% by weight of calcium oxide (CaO) has the calcium sulfate (CaSO ₄ ) content. This table shows the reaction results of desulfurized gypsum and dilute phosphoric acid during the reforming process of the second intermediate material containing 2 to 3% by weight of calcium phosphate (CaHPO ₄ ).

In [Table 2], the amount of calcium phosphate produced and the increase rate (%) of calcium phosphate can be expressed by the following (Equation 3) and (Equation 4).

(Equation 3) [Phosphoric acid input amount (g) / 98 (phosphoric acid molecular weight)] * 136 (calcium phosphate molecular weight) = Calcium phosphate production amount

(Equation 4) (Calcium phosphate production / 1,150 (desulfurized gypsum + diluted phosphoric acid) * 100 = Calcium phosphate increase rate (%)

Grouting with a grout chemical solution formed by a second intermediate material containing calcium phosphate (CaHPO ₄ ) equivalent to 1 to 2% by weight of the calcium sulfate (CaSO ₄ ) content in the total content of the desulfurized gypsum modified as described above. When injected into the ground, it is a hard hardened body with an initial reactivity (1st day strength) of 5 kg/cm2 or more, and has the effect of demonstrating excellent performance as a barrier material during water barrier construction.

(I - 2nd step): A process of forming a common medicinal material according to the present invention, including the first and second steps such as the (I-S11) and (I-S12) steps of the (I-S10) step. The first intermediate material is formed through a reforming process so that the content of calcium sulfate (CaSO ₄ ) is more than 50% by weight of the components of the desulfurized gypsum, and the calcium sulfate (CaSO ₄ ) content of the calcium phosphate (CaHPO ₄ ) contained in the desulfurized gypsum is ) The second intermediate material, which is formed at 1 to 2% by weight of the content, is made into a high powder (e.g., a powder level of 3,000 to 5,000 brains (g/cm ² ) or more) using a grinder such as a lemon mill or ball mill. After proceeding, mixing the highly powdered first intermediate material, the second intermediate material, and CFBC (Circulating Fluidized Bed Combustion) ash generated in a circulating fluidized bed boiler of a thermal power plant to form a powdered common medicine. Proceed with (I-S20).

(I - Step 3): A process of forming a common drug solution according to the present invention, by mixing 30 to 35% by weight of the powdered common drug formed in the above (Step I-S20) and 60 to 75% by weight of water. Proceed with the step of forming a common chemical solution (I-S30).

II. [Quick-setting chemical solution formation process]

(II - Step 1): A process of forming a quick setting agent according to the present invention, using finely powdered blast furnace slag produced in the iron making process, calcium sulfoaluminate [C.S.A. (Calcium Sulfoaluminate)], and alkaline carbonate. Proceed with the step (II-S10) of mixing to form a powder-type quick-setting chemical.

(II - Step 2): A process of forming a quick-setting chemical solution according to the present invention, by mixing 30 to 35% by weight of the powdery quick-setting chemical formed from the step (II-S10) and 60 to 75% by weight of water. Proceed with the step of forming a quick-setting chemical solution (II-S20).

III. [Complete chemical solution formation process]

(III - Step 1): The process of forming the finished drug according to the present invention. The powder form is completed by mixing 99.1 to 99.9% by weight of the powdered quick-setting chemical formed from the step (II-S10) and 0.1 to 0.9% by weight of the organic acid as a reaction retardant (or an organic acid with 6 carbon atoms produced by fermenting sugarcane). Proceed with the step of forming the medicine (III-S10).

(III - Step 2): A process of forming a finished drug solution according to the present invention, mixing 30 to 35% by weight of the powdered finished drug formed from the step (III-S10) and 60 to 75% by weight of water. Proceed with the step of forming the complete chemical solution (III-S20).

IV. [Fast setting silica sol grout chemical solution formation process]

(IV - Step 1): A process of forming a quick-setting silica sol grout chemical solution according to the present invention, comprising 40 to 60% by weight of the common chemical solution formed from the (I-S30) step and from the (II-S20) step A step (IV-S10) of forming quick-setting silica sol is performed by mixing 40 to 60% by weight of the formed quick-setting chemical solution immediately before injection into the ground.

V. [Completed silica sol grout chemical solution formation process]

(V - Step 1): A process of forming a finished silica sol grout chemical solution according to the present invention, comprising 40 to 60% by weight of the common chemical solution formed from the (I-S30) step and from the (III-S20) step A step (V-S10) of forming a finished silica sol is performed by mixing 40 to 60% by weight of the completed chemical solution just before injection into the ground.

When the rapid setting/complete silica sol grout chemical solution formed from (IV - first step) and (V - first step) is used in grout construction to form a water barrier for the purpose of underground digging, the modified desulfurized gypsum When the grout chemical solution formed by the first intermediate material, which contains calcium sulfate (CaSO ₄ ) in a proportion of more than 50% by weight of the total content, is injected into the ground during grout construction, the early strength is reduced within 3 to 7 days. It is a hard cured body that is formed to develop a strength of more than 10 kg/cm2 and an initial reactivity (1st day strength) of more than 5 kg/cm2, and has the effect of demonstrating excellent performance as a barrier material during water barrier construction.

In addition, the first intermediate material and agent formed from the first and second reforming processes progressing to the (I-S11) and (I-S12) stages of the reforming process (I-S10 stage) of desulfurized gypsum, a recycled resource. 2 The rapid setting/complete silica sol grout chemical solution formed by processing the intermediate material into a high powder (e.g., 3,000 to 5,000 grains (g/cm ² ) or higher) using a grinder such as a lemonade mill or ball mill is finely powdered. When it is powdered and injected into the ground during grout construction, the permeability coefficient is secured to 10 ^-5 cm/sec or less, making it possible to penetrate into the gravel layer, sand layer, and silt layer (clay layer) .

Hereinafter, the method for producing quick-set silica sol and finished silica sol as a grout chemical solution according to the present invention will be discussed in more detail.

Figure 2 is a flow chart showing the process of manufacturing quick-setting silica sol, a grout chemical solution according to the present invention.

As shown, the method for producing quick-setting silica sol as a grout chemical solution according to the present invention is as follows.

In the method for producing a quick-setting silica sol grout chemical solution used when performing grout construction to form a water barrier for the purpose of underground digging,

A step (S110) is performed to reform desulfurized gypsum, a recycled resource obtained as a by-product in the oil refining process.

More specifically, the step (S110) is,

In order to improve early strength (3 to 7 days) during the grout construction process, the first intermediate material in which calcium sulfate (CaSO ₄ ) accounts for more than 50% by weight of the total content of desulfurized gypsum is used to form the first intermediate material. Proceed with the tea reforming process (S111).

The first reforming process (S110) is to mix desulfurized gypsum with water (H ₂ O) and sulfuric acid (H ₂ SO 4 ), as shown in (Formula 3) and (Formula ₄ ), to produce calcium sulfate (CaSO ₄ ). This forms the first intermediate material whose proportion is more than 50% by weight of the total content of desulfurized gypsum.

In addition, in order to increase the initial reactivity during the grout construction process and improve the first-day strength, the proportion of calcium phosphate (CaHPO ₄ ) in the total content of desulfurized gypsum is 1 to 2% by weight of the calcium sulfate (CaSO ₄ ) content. The second reforming process (S112) to form the second intermediate material is performed.

In the second reforming process (S112), as shown in (Formula 5) and (Formula 6), water (H ₂ O) and phosphoric acid (H ₃ PO ₄ ) are mixed with desulfurized gypsum to produce calcium phosphate (CaHPO ₄ ). A second intermediate material is formed that is 1 to 2% by weight of the calcium sulfate (CaSO ₄ ) content contained in the desulfurized gypsum.

An agent in which the content of calcium sulfate (CaSO ₄ ) is formed by more than 50% by weight of the components of desulfurized gypsum by the first and second reforming processes such as the steps (S111) and (S112) of the (S110 step). 1. The intermediate material and the second intermediate material, which has a calcium phosphate (CaHPO ₄ ) content of 1 to 2% by weight of the calcium sulfate (CaSO ₄ ) content contained in the desulfurized gypsum, are ground into high powder using a grinder such as a lemonade mill or ball mill. After the process is performed (e.g., a fineness of 3,000 to 5,000 branes or more), the highly powdered first intermediate material, the second intermediate material, and CFBC (Circulating Fluidized Bed Combustion) generated in the circulating fluidized bed boiler of the thermal power plant ) A step (S120) of mixing ash to form a powdered common herb is performed.

A step (S130) of forming a common drug solution is performed by mixing 30 to 35% by weight of the powdered common drug formed in the step (S120) and 60 to 75% by weight of water.

A step (S140) of mixing finely powdered blast furnace slag, calcium sulfoaluminate (C.S.A), and carbonate, an alkaline agent, is performed to form a powder-type quick-setting chemical.

A step (S150) of forming a quick-setting chemical solution is performed by mixing 30 to 35% by weight of the powdered quick-setting chemical formed from the step (S140) and 60 to 75% by weight of water.

40 to 60% by weight of the common chemical solution formed from the (S130) step and 40 to 60% by weight of the quick setting chemical solution formed from the (S150) step are mixed immediately before ground injection to form a sol-like quick setting silica sol grout chemical solution. Proceed to step S160.

The grout construction method using quick-setting silica sol, a grout chemical solution manufactured according to the present invention, transports the common chemical solution and the quick-setting chemical solution at low pressure through a double pipe after drilling the ground, and transfers the common chemical solution and the quick-setting chemical liquid at a tip device where the double pipe meets the ground where the double pipe is combined. The quick-setting chemical solution is mixed to form a quick-setting silica sol grout chemical solution, and the quick-setting silica sol grout chemical solution formed as described above is injected into a ground layer with large pores, such as a sand layer or a gravel layer, using grouting equipment.

Figure 3 is a flow chart showing the process of manufacturing finished silica sol, a grout chemical solution according to the present invention.

As shown, the method for producing the finished silica sol, which is a grout chemical solution according to the present invention, is as follows.

In the method for producing a finished silica sol grout chemical solution used when performing grout construction to form a water barrier for the purpose of underground digging,

A step (S210) is performed to reform desulfurized gypsum, a recycled resource obtained as a by-product in the oil refining process.

A step (S210) of reforming desulfurized gypsum, a recycled resource obtained as a by-product in the oil refining process, is performed.

More specifically, the step (S210) is,

In order to improve early strength (3 to 7 days) during the grout construction process, the first intermediate material in which calcium sulfate (CaSO ₄ ) accounts for more than 50% by weight of the total content of desulfurized gypsum is used to form the first intermediate material. Carry out the tea reforming process (S211).

The first reforming process (S211) is to mix desulfurized gypsum with water (H ₂ O) and sulfuric acid (H ₂ SO 4 ), as shown in (Formula 3) and (Formula ₄ ), to produce calcium sulfate (CaSO ₄ ). This forms the first intermediate material whose proportion is more than 50% by weight of the total content of desulfurized gypsum.

In addition, in order to improve the first-day strength, which is initially reactive during the grout construction process, the proportion of calcium phosphate (CaHPO ₄ ) in the total content of desulfurized gypsum is 1 to 2% by weight of the calcium sulfate (CaSO ₄ ) content. The second reforming process (S212) to form the second intermediate material is performed.

In the second reforming process (S212), as shown in (Formula 5) and (Formula 6), water (H ₂ O) and phosphoric acid (H ₃ PO ₄ ) are mixed with desulfurized gypsum to produce calcium phosphate (CaHPO ₄ ). A second intermediate material is formed that is 1 to 2% by weight of the calcium sulfate (CaSO ₄ ) content contained in the desulfurized gypsum.

An agent in which the content of calcium sulfate (CaSO ₄ ) is formed to be more than 50% by weight of the components of desulfurized gypsum by the first and second reforming processes such as the steps (S211) and (S212) of the (S210 step). 1 The intermediate material and the second intermediate material, which has a content of calcium phosphate (CaHPO ₄ ) of 1 to 2% by weight of the calcium sulfate (CaSO ₄ ) content contained in the desulfurized gypsum, are made into high powder using a grinder such as a lemonade mill or ball mill. (For example, a fineness of 3,000 to 5,000 branes or more) After the process, the highly powdered first intermediate material, the second intermediate material, and CFBC (Circulating Fluidized Bed Combustion) generated in the circulating fluidized bed boiler of the thermal power plant. A step (S220) of mixing ash to form a powdered common herb is performed.

A step (S230) of forming a common drug solution is performed by mixing 30 to 35% by weight of the powdered common drug formed in the step (S220) and 60 to 75% by weight of water.

A step (S240) of mixing finely powdered blast furnace slag, calcium sulfoaluminate (C.S.A.), and carbonate, an alkaline agent, is performed to form a powder-type quick-setting chemical.

99.1 to 99.9% by weight of the powdered quick-setting agent formed from the step (S240) and 0.1 to 0.9% by weight of an organic acid as a reaction retardant (or an organic acid with 6 carbon atoms produced by fermenting sugarcane) are mixed to make a powdered finished agent. Proceed with the forming step (S250).

A step (S260) of mixing 30 to 35% by weight of the powdered finished drug formed from the step (S250) and 60 to 75% by weight of water to form a finished drug solution is performed (S260).

40 to 60% by weight of the common chemical solution formed from the step (S230) and 40 to 60% by weight of the complete chemical solution formed from the step (S260) are mixed immediately before injection into the ground to form a finished silica sol grout chemical solution in a sol state. Proceed to step (S270).

The grout construction method using finished silica sol, which is a grout chemical solution manufactured according to the present invention, transports the common chemical solution and the complete chemical solution at low pressure through a double pipe after drilling the ground, and transfers the common chemical solution and the finished chemical liquid at a tip device where the double pipe meets the ground where the double pipe is combined. The finished chemical solution is mixed to form a finished silica sol, and the finished silica sol formed as described above is injected into a ground layer with large pores such as a sand layer or gravel layer using grouting equipment.

In the following, specific examples of the manufacturing method of quick-set silica sol and finished silica sol, which are grout chemicals used when performing grout construction to form a barrier wall for the purpose of underground digging of the present invention, will be described. .

Lot No. Common herbal medicine Quick payment medicine Check physical properties note reformed
desulfurization
I reformed
desulfurization
II CFBC
ash Slag sulfuric acid
salt C.
S.
A alkaline agent Gel time
(candle) 1 day
robbery
(kg/㎠) 7 days
robbery
(kg/㎠) 28th
robbery
(kg/㎠) Homogel permeability coefficient (cm/sec) 3-1 25 25 50 58 2 20 20 11 5 15 20 3-2 30 20 50 58 2 20 20 11 3 16 19 3-3 20 30 50 58 2 20 20 10 5 17 18 3-4 50 50 58 2 20 20 12 One 15 18 3-5 50 50 58 2 20 20 10 5 11 18 3-6 60 40 58 2 20 20 10 2 16 18 3-7 60 40 52 3 25 20 10 5 10 16 3-8 40 60 57 3 20 20 11 One 16 19 3-9 40 60 57 3 20 20 10 5 11 16 3-10 30 30 40 67 3 10 20 formation
(X) - - - 3-11 30 30 40 57 3 20 20 11 4 16 20 3-12 30 30 40 57 3 23 17 10 4 18 21 10 ^-5 3-13 30 30 40 57 3 25 15 11 5 17 21 10 ^-5 3-14 30 30 40 57 3 25 15 60 - 19 23 10 ^-5 retardant
0.25% by weight
use

Here, [Table 3] is a table of mixing experiments and results of ground barrier materials. In [Table 3], Lot No. 3-1 ~ No. The mixing test and results of ground barrier materials according to 3-14 are Lot No. 1 in [Table 1]. Modified desulfurized gypsum of 1-6 and Lot No. of [Table 2]. This is the result of applying 2-6, and the test method was conducted according to KS L 5105-2007, a uniaxial compressive strength test method, and ASTM D 5084-2003, a homogel water permeability test method.

[Table 3] shows common chemicals formed using the first intermediate material formed in the first reforming process of [Table 1], the second intermediate material formed in the second reforming process of [Table 2], and rapid crystallization. It shows the results of tests on medicinal ingredients and finished medicinal ingredients in mixing ratios.

<Example 1>

As shown in Lot No. 3-1 in [Table 3],

i) Common agent: Formed by mixing reformed desulfurization I (25% by weight), reformed desulfurization II (25% by weight), and CFBC ash (50% by weight).

ii) Quick-setting chemical: It is formed by mixing slag fine powder (58% by weight), sulfate (2% by weight), C.S.A. (20% by weight), and carbonate (20% by weight), which is an alkaline agent.

iii) Mix each of the common medicine and quick-fixing medicine formed above in a ratio of water: (common medicine or quick-setting medicine) = 200: 100 to form a common medicine solution and a quick-setting medicine solution.

iv) The quick-setting silica sol grout chemical solution can be formed by mixing the formed common chemical solution and the quick-setting chemical solution.

When the quick-set silica sol grout chemical solution formed in Example 1 was used during grout construction, the gel time was 11 seconds, the early strength per day was 5 kg/cm2, and the compressive strength at 7 days was good, such as 15 kg/cm2. It can be seen that the characteristics appear.

[Table 4] is a comparative mixing experiment and result table of ground barrier materials using desulfurized gypsum before modification and is as follows.

Lot No. Common herbal medicine Quick payment medicine Check physical properties note Desulfurized gypsum CFBC
ash Slag sulfuric acid
salt C.S.A. alkaline agent Gel time
(candle) 1 day
robbery
(kg/㎠) 7 days
robbery
(kg/㎠) 28th
robbery
(kg/㎠) Homogel permeability coefficient (cm/sec) Comparison 1 50 50 58 2 20 20 10 formationx 7 15 Comparison 2 60 40 57 3 25 15 12 One 8 15 Comparison 3 60 40 57 3 25 15 58 One 8 16 Retardant 0.25% by weight

<Comparative Example 1>

In Example 1, 50% by weight of desulfurized gypsum fine powder before reforming was used instead of the first intermediate material by reforming desulfurization 1 and the second intermediate material by reforming desulfurization 2, and the remainder was compared with Example 1 under the same conditions. .

As a result of comparison according to [Table 3] and [Table 4], when the quick-setting silica sol from the first and second intermediate materials after modification of desulfurized gypsum was used during grout construction, the gel time was 11 seconds, whereas the gel time was 11 seconds when using desulfurized gypsum before modification. The gel time during construction is 10 seconds, and the early strength per day is 5 kg/cm2 when the quick-setting silica sol grout chemical solution made of the first and second intermediate materials after desulfurized gypsum modification according to the present invention is used during grout construction. On the other hand, when desulfurized gypsum before modification was used, the 1-day strength was not developed, and when the quick-setting silica sol grout chemical solution according to the present invention was used, the 7-day compressive strength showed good characteristics such as 15 kg/cm2. On the other hand, when desulfurized gypsum was used before modification, the 7-day compressive strength was found to be 7 kg/cm2.

<Example 2>

As shown in Lot No. 3-13 in [Table 3],

i) Common agent: Formed by mixing reformed desulfurization I (30 wt%), reformed desulfurization II (30 wt%), and CFBC ash (40 wt%).

ii) Quick-setting chemical: It is formed by mixing slag fine powder (57% by weight), sulfate (3% by weight), C.S.A. (25% by weight), and carbonate (15% by weight), which is an alkaline agent.

iii) Mix each of the common medicine and quick-fixing medicine formed above in a ratio of water: (common medicine or quick-setting medicine) = 200: 100 to form a common medicine solution and a quick-setting medicine solution.

iv) The quick-setting silica sol grout chemical solution can be formed by mixing the formed common chemical solution and the quick-setting chemical solution.

When the quick-set silica sol grout chemical solution formed in Example 2 was used during grout construction, the gel time was 11 seconds, the early strength per day was 5 kg/cm2, and the compressive strength at 7 days was good, such as 17 kg/cm2. It can be seen that the characteristics appear.

<Comparative Example 2>

In Example 2, 60% by weight of desulfurized gypsum fine powder before reforming was used instead of the first intermediate material by reforming desulfurization 1 and the second intermediate material by reforming desulfurization 2, and the remainder was compared with Example 2 under the same conditions.

As a result of comparison according to [Table 3] and [Table 4], when the quick-setting silica sol grout chemical solution of the first and second intermediate materials after desulfurized gypsum modification was used during grout construction, the gel time was 11 seconds, whereas before modification, the gel time was 11 seconds. The gel time during grout construction using desulfurized gypsum is 12 seconds, and when the quick-setting silica sol grout chemical solution made by the first and second intermediate materials after modification of desulfurized gypsum according to the present invention is used during grout construction, the early strength per day is 5. On the other hand, when desulfurized gypsum before modification is used, the 1-day strength is 1 kg/cm2, and when the quick-setting silica sol grout chemical solution according to the present invention is used, the 7-day compressive strength is equal to 17 kg/cm2. While good properties are shown, when desulfurized gypsum is used before modification, the 7-day compressive strength is 8 kg/cm2.

<Example 3>

In Lot No. 3-14, a common medicine is made by mixing 30% by weight of reforming desulfurization 1, 30% by weight of reforming desulfurization 2, and 40% by weight of CFBC ash, and the final medicine is slag fine powder by weight. After mixing 57% by weight and 3% by weight of sulfate, 25% by weight of C.S.A., 15% by weight of alkaline carbonate, and 0.25% by weight of organic acid. Each chemical solution was prepared with W (water) : B (medication) = 200 : 100, and then mixed with the common chemical solution and the complete chemical solution to prepare a finished silica sol, and the gel time, uniaxial compressive strength, and homogel permeability coefficient were evaluated.

As No. 3-14 in [Table 3],

i) Common agent: Formed by mixing reformed desulfurization I (30 wt%), reformed desulfurization II (30 wt%), and CFBC ash (40 wt%).

ii) Finishing agent: Mix slag fine powder (57% by weight), sulfate (3% by weight), C.S.A. (25% by weight) and alkaline carbonate (15% by weight) and then mix with organic acid (0.25% by weight). form

iii) Form the common drug solution and the complete drug solution with the above-formed common drug solution and complete drug solution at a ratio of W (water) : B (medicinal material) = 200 : 100.

The gel time, uniaxial compressive strength, and homogel permeability coefficient of the completed silica sol formed in this way were evaluated.

iv) The finished silica sol grout chemical solution can be formed by mixing the formed common chemical solution and the finished chemical solution.

When the finished silica sol grout chemical solution formed in Example 2 was used during grout construction, it can be seen that good properties such as a gel time of 60 seconds and a 7-day compressive strength of 19 kg/cm2 were exhibited.

<Comparative Example 3>

In Example 3, 60% by weight of desulfurized gypsum fine powder before reforming was used instead of the first intermediate material by reforming desulfurization 1 and the second intermediate material by reforming desulfurization 2, and the remainder was compared with Example 3 under the same conditions. .

As a result of comparison according to [Table 3] and [Table 4], when the finished silica sol grout chemical solution of the first and second intermediate materials after desulfurized gypsum modification was used during grout construction, the gel time was 60 seconds, whereas the gel time was 60 seconds after desulfurization gypsum modification. The gel time during construction using gypsum is 58 seconds, and when the finished silica sol grout chemical solution made of the first and second intermediate materials after modification of desulfurized gypsum according to the present invention is used during grout construction, the 7-day compressive strength is 19 kg/ While good properties such as ㎠ are shown, when desulfurized gypsum is used before modification, the 7-day compressive strength is 8 kg/㎠.

The grout construction method using quick-set silica sol and finished silica sol, which are grout chemicals prepared according to the present invention, is to transport the common chemical solution and the quick-setting chemical solution or the common chemical solution and the finished chemical solution at low pressure through a double pipe after drilling the ground, and the double pipes are combined. At the tip device that meets the ground, the common chemical solution and the quick-setting chemical solution are mixed to form quick-set silica sol or the common chemical solution and the finished chemical solution to form finished silica sol, and the quick-set silica sol or finished silica sol is applied to a sand layer or gravel layer by grouting equipment. It is characterized in that it is supplied to a ground layer with large pores as shown.

Figure 4 is a diagram comparing common medicines manufactured using the modified desulfurized gypsum of the present invention and common medicines manufactured using the desulfurized gypsum before modification according to the prior art.

As shown, the left view is a photograph of a common medicinal material manufactured using desulfurized gypsum before modification according to the prior art, and is relatively dark brown in color, while the right view is a photograph of a common medicinal material manufactured using the modified desulfurized gypsum according to the present invention. You can see from the photo of the common medicinal product that it has a relatively light brown color.

Figure 5 compares the leaching phenomenon of a mold specimen of a grout chemical solution manufactured using the modified desulfurized gypsum of the present invention with that of a mold specimen of a grout chemical solution manufactured using the desulfurized gypsum before modification according to the prior art. It is a drawing.

As shown, the left figure is a photograph observing the leaching phenomenon caused by seawater of a mold specimen formed into a cubic structure manufactured using desulfurized gypsum before modification according to the prior art, and some white precipitate crystals are slightly generated. On the other hand, the right view is a photograph observing the leaching phenomenon by seawater of a mold specimen formed into a cubic structure manufactured using the modified desulfurized gypsum according to the present invention. No leached sediment was observed, indicating the material stability in seawater. You can tell it’s excellent.

Figure 6a is a diagram showing the test results for the homogel permeability coefficient for the quick-set grout chemical solution mixed with the common chemical solution and the quick-setting chemical solution prepared according to the present invention, and Figure 6b is a diagram showing the test results for the homogel permeability coefficient of the common chemical solution prepared according to the present invention and the finished chemical solution mixed. This diagram shows the test results for homogel permeability coefficient for a finished grout chemical solution.

As shown, as shown in Figure 6a, the quick-set grout chemical solution is formed in a cubic structure manufactured by mixing the common chemical powder (5,761 cm ² /g) and the quick-setting chemical powder (5,244 cm ² /g) according to the present invention. As a result of the homogel water permeability test on the mold, it can ^be seen that the homogel water permeability coefficient is ^5.7 As a result of the homogel water permeability test on the mold of the finished grout chemical solution formed into a cubic structure manufactured by mixing the chemical powder (5,205 cm ² /g), the homogel water permeability coefficient was found to be 1.4 × 10 ^-7 cm/sec. You can. As a result, if the fineness is 5,000 branes or more, the permeability coefficient can be secured to 10 ^-5 cm/sec or less, so the grout chemical solution according to the present invention has the effect of penetrating into the silt layer during grout construction.

Claims (9)

In the method of manufacturing a grout chemical solution used when performing grout construction to form a water barrier for the purpose of underground digging,
In order to improve early strength during grout construction, the first intermediate material in which calcium sulfate accounts for more than 50% by weight of the total content of desulfurized gypsum, a recycled resource obtained as a by-product in the petroleum refining process, is used. In order to improve the first-day strength by increasing the initial reactivity in the secondary reforming process, an agent that forms a second intermediate material in which the proportion of calcium phosphate among the components included in the total content of desulfurized gypsum is 1 to 2% by weight of the calcium sulfate content. A reforming step (S110) of desulfurized gypsum consisting of a secondary reforming process,
After performing a high powder process on the first intermediate material and the second intermediate material formed by the desulfurized gypsum reforming process in the above (step S110) using a grinder, the highly powdered first intermediate material and the second intermediate material are A step (S120) of mixing intermediate materials and CFBC (Circulating Fluidized Bed Combustion) ash generated from a circulating fluidized bed boiler of a thermal power plant to form a powdered common chemical,
A step (S130) of mixing 30 to 35% by weight of the powdered common drug formed in the step (S120) and 60 to 75% by weight of water to form a common drug solution;
A step (S140) of mixing finely powdered blast furnace slag, calcium sulfoaluminate, and alkaline carbonate to form a powdered quick-setting chemical,
A step (S150) of mixing 30 to 35% by weight of the powdered quick-setting chemical formed from the step (S140) and 60 to 75% by weight of water to form a quick-setting chemical solution, and
Forming a sol-type grout chemical solution by mixing 40 to 60% by weight of the common chemical solution formed from the step (S130) and 40 to 60% by weight of the quick setting chemical solution formed from the step (S150) immediately before ground injection (S160) ) A method for producing a grout chemical solution using desulfurized gypsum, characterized in that it contains. In the method of manufacturing a grout chemical solution used when performing grout construction to form a water barrier for the purpose of underground digging,
In order to improve early strength during grout construction, the first intermediate material in which calcium sulfate accounts for more than 50% by weight of the total content of desulfurized gypsum, a recycled resource obtained as a by-product in the petroleum refining process, is used. In order to improve the first-day strength by increasing the initial reactivity in the secondary reforming process, an agent that forms a second intermediate material in which the proportion of calcium phosphate among the components included in the total content of desulfurized gypsum is 1 to 2% by weight of the calcium sulfate content. A reforming step (S210) of desulfurized gypsum consisting of a secondary reforming process,
After performing a high powder process on the first intermediate material and the second intermediate material formed by the desulfurized gypsum reforming process in the above (step S110) using a grinder, the highly powdered first intermediate material and the second intermediate material are A step (S220) of mixing intermediate materials and CFBC (Circulating Fluidized Bed Combustion) ash generated from a circulating fluidized bed boiler of a thermal power plant to form a powdered common chemical,
A step (S230) of mixing 30 to 35% by weight of the powdered common drug formed in the step (S120) and 60 to 75% by weight of water to form a common drug solution;
A step (S240) of mixing finely powdered blast furnace slag, calcium sulfoaluminate, and alkaline carbonate to form a powder-type quick setting chemical,
A step (S250) of mixing 99.1 to 99.9% by weight of the powdery quick-setting agent formed from the step (S240) and 0.1 to 0.9% by weight of the reaction retardant to form a powdery final agent,
A step (S260) of mixing 30 to 35% by weight of the powdered finished drug formed from the step (S250) and 60 to 75% by weight of water to form a finished drug solution, and
Forming a sol-type grout chemical solution by mixing 40 to 60% by weight of the common chemical solution formed from the step (S230) and 40 to 60% by weight of the complete chemical solution formed from the step (S260) immediately before ground injection (S270) ) A method for producing a grout chemical solution using desulfurized gypsum, characterized in that it contains. In claim 1 or claim 2,
In the first reforming process of the (S110) step, in order to improve early strength during the grout construction process, water and sulfuric acid are mixed with the desulfurized gypsum so that the proportion of calcium sulfate is 50% by weight or more in the total content of the desulfurized gypsum. It forms the first intermediate good that becomes,
In the second reforming process of the (S110) step, in order to improve the first-day strength by increasing the initial reactivity during the grout construction process, water and phosphoric acid are mixed with the desulfurized gypsum to change the calcium sulfate content in the desulfurized gypsum. A method for producing a grout chemical solution using desulfurized gypsum, characterized in that the second intermediate material is formed in an amount of 1 to 2% by weight. In claim 1 or claim 2,
In the first reforming process of the (S110) step, in order to improve early strength during the grout construction process, calcium oxide contained in the desulfurized gypsum reacts with water to form calcium hydroxide, and the calcium hydroxide reacts with sulfuric acid to form sulfuric acid. This is a process in which calcium and two molecules of water are created.
In the second reforming process of the (S110) step, in order to improve the first-day strength by increasing the initial reactivity during the grout construction process, calcium oxide contained in the desulfurized gypsum reacts with water to form calcium hydroxide, and the calcium hydroxide and A method for producing a grout chemical solution using desulfurized gypsum, characterized in that it is a process in which phosphoric acid reacts to produce calcium phosphate and two molecules of water. In claim 1 or claim 2,
The first intermediate material is produced by the chemical formulas {CaO + H ₂ O → Ca(OH) ₂ } and {Ca(OH) ₂ + H ₂ SO ₄ → CaSO ₄ + 2H ₂ O},
The second intermediate material is a desulfurization product characterized in that produced by the chemical formula {CaO + H ₂ O → Ca(OH) ₂ } and {Ca(OH) ₂ + H ₃ PO ₄ → CaHPO ₄ + 2H ₂ O} Grout chemical manufacturing method using gypsum. In claim 1 or claim 2,
Manufacturing of grout chemical solution using desulfurized gypsum, characterized in that when the grout chemical solution formed by the first intermediate material is injected into the ground during grout construction, the early strength is cured to a strength of 10 kg/cm2 or more within 3 to 7 days. method. In claim 1 or claim 2,
When the grout chemical solution formed by the first intermediate material is injected into the ground during grout construction, the initial reactivity (1st day strength) is cured to a strength of 5 kg/cm2 or more. A method of producing a grout chemical solution using desulfurized gypsum. . The method of claim 2, wherein the reaction retardant is
A method of producing a grout chemical solution using desulfurized gypsum, characterized in that it is an organic acid or an organic acid with 6 carbon atoms produced by fermenting sugar cane. A grout construction method using a grout chemical solution, characterized in that using a grout chemical solution prepared according to claim 1 or claim 2.