KR101293132B1 - The binder composition using the main stuff for soil - Google Patents

Abstract

The present invention relates to a soil permeable packaging composition, soil 10-30% by weight, magnesium oxide 15-50% by weight, blast furnace slag 15-40% by weight, phosphate fertilizer 5-10% by weight, volcanic soil 10-40% by weight, 30 to 70 parts by weight of raw material consisting of wollastonite 5 to 10% by weight, 10 to 60% by weight of magnesium chloride, 1 to 8% by weight of phosphate, 32 to 89% by weight of water (fresh water or seawater) Consists of parts by weight, binder composition mainly based on the soil according to the present invention can reduce the air pollution by suppressing the release of CO ₂ gas generated during cement production due to the use of cement, such as Cr ^{6 +} It is possible to block the occurrence of origin, to recycle industrial by-products such as blast furnace slag without causing environmental pollution, and to use it to filter out nonpoint pollutants (harmful heavy metals) in the initial rainwater, thus protecting the water environment. You can get the effect.

Description

Binder composition based on soil {The binder composition using the main stuff for soil}

The present invention relates to a soil pitcher packaging composition, and more particularly, to an environment-friendly soil pitcher packaging composition using industrial by-products such as blast furnace slag without using cement.

Eco-friendly packaging materials are attracting attention to packaging materials that look good around local governments by expanding awareness of eco-friendly well-being culture and improving quality of life. The current pavement material is based on flatness and permeability as well as road protection, and emphasizes aesthetics (visual characteristics, landscaping) while having permeability. In addition, as a part of the eco-environment creation project currently implemented by local governments, the soil pavement has a large budget, and is mainly installed in the main roads of bicycle paths, promenades, parks, and cultural property facilities.

Soil pavement material is mainly composed of soil and inorganic binder.Inorganic binder mainly includes cement, special cement, cement with inorganic salt, geopolymer cement, alkali activated cement, etc. Various soil pavement compositions have been developed.

For example: Patent No. 438138 describes a technique for limiting the range of natural soil, cement and solidified material composition, and inducing excellent physical properties by controlling the size of particles. Patent No. 625172 describes viscous or sandy soils with ocher. It describes the densification by adding a mixture of soil, cement and aggregate added with admixture, swelling agent, and water-retaining agent to the composition of paper sludge, constant sludge, and stone powder. However, such a technique is still a technique that depends on the adhesion of the cement, it is almost ineffective in improving the environmental problems.

In addition, Patent No. 504987 describes soil reinforcement improving materials composed of admixtures such as fly ash or paper sludge, cement, pigment, slaked lime and silica fume in soil pavement construction. Patent Nos. 789877, 570958, and 581227. Many soil packaging patents, such as Korean Patent No. 775360 and the like, are a packaging technology that improves functions through additives to cement as described above.

In addition, packaging technology has recently been advanced to the next generation packaging materials that have given structural characteristics such as water permeability and repair function. In particular, in the case of the permeation function, a recent immersion problem in some of the city of Seoul has emerged as a packaging material aimed at escaping the uniform cover-type packaging material, for the alternative of rainwater flooding, activation of the underground ecosystem, and promoting greening of surrounding plants.

Various methods of manufacturing a packaging material have been proposed. Patent No. 0692143 discloses, "Silicone: 15-20% by weight, 70 vol% or more of 4-5 mm silica sand: 75-80% by weight, pigment: 4% by weight or less, ocher: 2-5% by weight, charcoal: 0.01-0.1 Preparing the lower layer base material in the ratio of weight%, and mixing the base material, water and admixture into the mold to form the lower layer part: Back cement: 15-20% by weight, 70-vol% or more 1-2.5mm size Phosphorous sand: 74-80% by weight, pigment: 7% by weight or less, ocher: 1-5% by weight, charcoal: 0.01-0.1% by weight of the upper base material is prepared, and mixed with the base material, water and admixture Into the upper portion of the lower layer portion to form an upper layer portion; and covering the upper plate on the upper portion of the upper layer portion and pressurizing: characterized in that it includes.

As a result of emphasizing permeability only, after a certain period of time, cement, pigment, ocher, and charcoal, which are exposed to the permeable function and surface, adhere to dust and organic pollutants and adhere to the surface. There is a problem of shortening the replacement cycle of sex products.

Further, Patent No. 8983 describes "In a water-permeable concrete block bonded to aggregates with cement as a binder, a water-permeable concrete block characterized by polishing the surface of the block", but the amount of cement used is high. There is a problem that the pH is high.

Patent No. 689183 discloses "A) (a-) cement, and the aggregate having a particle size of 5 to 13 mm in a mixer, and then mixing the permeable layer raw materials by adding the mixing water; (a-) cement, and the particle size 2.5 Mixing the finishing layer raw material by mixing the mixed material having a thickness of 5 mm in a mixer, and adding mixed water; and (a-) one of the permeable layer raw material or the finishing layer raw material to the molding machine to perform vibration molding. To prepare a block intermediate comprising the step of adding the remaining raw material to the molding machine and then vibrating to form a pattern of the embossed portion and the intaglio portion on the surface of the finishing layer (However, the particle size of the aggregate included in the permeable layer raw material) Is greater than the particle size of the aggregate included in the finishing layer raw material.) B) steam curing the molded block intermediate at a temperature of 40 to 80; and C) embossing of the cured block intermediate Method of manufacturing a water-permeable concrete block, including the step of polishing with, but it is very artificial because the color of the product depends on the pigment, the quality of the product is significantly degraded, the bending strength is less than the standard, and the surface polish is used. Natural texture is damaged, as well as the height difference between the intaglio and embossed, there is a problem such as causing ankle injury when wearing high heels.

Patent No. 770152 describes "70-90 parts by weight of natural aggregates of various colors, blast furnace slag 5-15 parts by weight, active fly ash 5-15 parts by weight, caustic lime 2.5-7.5 parts by weight, the upper and lower parts of the aggregate Is a multi-layered permeable block, characterized in that it consists of a slurry of 2-8 mm and 13-40 mm aggregate size, respectively. However, since zeolite is produced after curing at high temperature, energy consumption is high and another heat treatment is performed to obtain an active fly ash. Because of this, there is a problem in that the economical competitiveness is lowered.

Accordingly, an object of the present invention is to solve environmental problems such as air pollution caused by the use of cement and at the same time provide a durable earth permeable packaging composition that does not use cement and is environmentally friendly and does not adversely affect the human body. There is.

Another object of the present invention is to improve the utility of recycled materials by the soil pitcher packaging composition, and to provide a composition for soil pitcher packaging to minimize the destruction of the natural environment.

Another object of the present invention to provide an environmentally friendly soil pitcher packaging method using the composition of the above object.

Another object of the present invention is to impart the permeability performance to the packaging technology to prevent the flooding damage caused by the existing flood, environmentally friendly soil pitcher that has the effect of filtering the harmful substances in the process of passing the water permeation structure (porous structure) To provide a packaging method.

It is still another object of the present invention to adsorb non-point pollutants and heavy metals in the initial rainwater such as Cd by the adsorbent ceramic powders used and the calcium phosphate compounds synthesized during the manufacturing process. To provide an environment-friendly soil pitcher packaging composition.

The binder composition of the present invention is 10 to 30% by weight of soil, 15 to 50% by weight of magnesium oxide, 15 to 40% by weight of blast furnace slag, 5 to 10% by weight of phosphate fertilizer, 10 to 40% by weight of volcanic earth, 5 to 10 wollastonite It is composed of 100 parts by weight of powdered material composed of weight percent, liquid material composed of 10 to 60% by weight of magnesium chloride, 1 to 8% by weight of phosphate, and 32 to 89% by weight of water (fresh water or seawater). .

Hereinafter, the present invention will be described in detail.

Soil can be used mud clay such as red clay (red clay) and ocher, and sandy soil such as kaolin, white clay and masato, which are generally obtained from the surface of the soil. The type of soil is not particularly limited, but the grain composition is generally fine. It is preferable that 55% by weight or less (0.8 mm or less) and particles of granules are properly mixed at a ratio of about 45%. In particular, in the present invention, it is preferable to use the topsoil generated during various mining activities in which the properties of various static clay particles are evenly mixed. Topsoil contains small soil particles and aggregate fines.

The proper amount is 10 to 30% by weight. If the soil content is lower than this range, the efficiency of recycling the discarded soil decreases as the soil content decreases, and the adsorption capacity known as the soil's inherent performance decreases. There is a problem that the adsorption capacity is deteriorated. If this range is exceeded, the adsorption performance is excellent, but since the liquid phase is absorbed by the interlayer structure of the tetrahedron and octahedron with many silt components of the soil, the excess liquid is used. Its economical efficiency is low, and in particular, the compressive strength is remarkably lowered due to the use of excess liquid and plasticity of the soil. The lack of water resistance causes problems such as particle separation of the packaging material during rainfall.

The wollastonite used in the present invention is not particularly limited. Wollastonite was used as a reinforcing material to reinforce the bendability of the soil permeable pavement material proposed in the present invention as needle-shaped particles, and wollastonite, which is one of the mineral needle-like materials, was used in accordance with the prohibition of the use of representative asbestos of fibrous minerals. . Minerals that can be used as fibrous materials may be haemulite (sepiolite), ceramic fiber (spray method), glass fiber, and wollastonite and haemulite are most preferred.

The proper amount of use is 5 to 10% by weight, and if it is less than this range, strong compressive strength is expressed, but due to the lack of fiber, a problem of long cutting by the transverse or longitudinal axis of the pavement may occur due to the lack of fiber. In the case of exceeding the compressive strength is significantly lowered, the amount of binder and the amount of soil, including volcanic soil is relatively small, the problem of the expression of the target adsorption performance and water resistance occurs.

The volcanic soil used in the present invention is volcanic soil composed of boehmite (Al (OH) ₃ ), quartz and gypsum (calcium sulfate hydrate), which are well known for adsorption of heavy metals, and SiO ₂ and Al in chemical composition. ₂ O ₃ is composed of 40% by weight, 20.2% by weight, SO ₃ 12.9% by weight, CaO 11.9% by weight. Boehmite has excellent adsorption capacity of heavy metals, and gypsum acts to improve the water resistance of magnesium-based composites.

Appropriate amount of use is 10 to 40% by weight, and if it is less than this range, there is a problem of insufficient adsorption performance, and if it exceeds this range, the amount of other raw materials is reduced by excessive use, and the compressive strength is rapidly increased. There is a problem that can not be achieved to achieve the target compressive strength.

The magnesium oxide used in the present invention is not particularly limited, but magnesium oxide obtained from heat treatment of magnesium oxide extracted from dolomite, light magnesium, and magnesium hydroxide extracted from seawater can be used, and preferably, obtained by heat treating light magnesium and dolomite. It is to use magnesium oxide. The higher the purity of magnesium oxide is, the more preferable it is, but from an economical point of view, it is appropriate for 90% to have purity.

Magnesium oxide acts to form an inorganic complex by reacting with each other by the addition of chlorine inorganic mixed solution composed of blast furnace slag, phosphate fertilizer, and magnesium chloride and phosphate. The principle of the coupling reaction is based on the ionic reaction, and more specifically, the magnesium phosphate solidification principle. However, the biggest weakness of magnesium-based hardeners, which has been used previously, is water resistance, that is, the binder product reacts with water to change the product phase due to the problem of contact with water. It has been used indoors. Combined by the added raw materials to produce the product of 5Mg (OH) ₂ · MgCl ₂ 8H ₂ O and 3Mg (OH) ₂ · MgCl ₂ 8H ₂ O, and the blast furnace slag was added to the acidic liquid The gypsum component contained in CaO, SiO ₂ and volcanic earth by ion dissolving can produce ettringite gel, which can solve the problem of water resistance, which was a problem of the conventional magnesium-based binder. In addition, the ion-eluted Si ions act in combination, one acting as a generating factor of the etlingzite gel described above, and producing MSH (magnesium silicate hydrate).

The proper amount of use is 15 to 50% by weight, and if it is less than this range, there is a problem of showing a very low bonding strength that cannot act as a binder. If this range is exceeded, the bonding strength acts strongly to express compressive strength. Is very excellent, but water resistance has a problem such as cracks due to the contact of rain water, the problem of deterioration of the adsorption capacity of heavy metals aimed at the present invention due to the reduction of the amount of other raw materials used.

The phosphate fertilizer is generally one of phosphate fertilizers that are sold for agriculture, and is composed of phosphoric acid, goto (magnesium oxide), lime, silicic acid, and sulfur, and more specifically, phosphate fertilizer known as yongguarin. Goto phosphate fertilizer is a water-soluble phosphate group and contains magnesium oxide, lime, silicic acid, and sulfur, and includes elements suitable for the bonding principle of the present invention, and these various ions include 5Mg (OH) ₂ · MgCl ₂ · 8H _2. The product of O and 3Mg (OH) ₂ · MgCl ₂ · 8H ₂ O prevents the Mg (OH) ₂ phase transition by contact with water, thereby improving water resistance. In addition, because the use of fertilizers have a feature that can be utilized as a fertilizer of the soil by grinding even when discarded products developed and produced by the present application.

An appropriate amount is 5-10% by weight, in the case of less than the range, a _{5Mg (OH) 2 · MgCl 2} · 8H 2 O and _{3Mg (OH) 2 · MgCl 2} · Mg (OH) of the product _2, 8H ₂ O As the transition occurs, cracks and cracks are generated, and if it exceeds this range, problems of strength drop occur due to the lack of economical efficiency due to the use of expensive phosphate fertilizer and the action of preventing the reaction of the added raw materials.

The blast furnace slag is produced as a by-product when producing pig iron in the blast furnace, but is not particularly limited, but it is preferable to use a powder degree (Blaine) of 7,000 cm 2 / g.

In the examples below, 7,000 cm 2 / g produced and sold from the Basic Materials Research Institute Co., Ltd. was used, and the composition of the chemical phase is not particularly limited. Blast furnace slag, the chemical composition of the soil component is different from the composition SiO ₂ + Al ₂ O ₃ + The content of CaO is 88.6% by weight, other minor components account for 11.4% by weight, blast furnace slag was used for the purpose of improving the water resistance of the binder, and to increase the densification. Blast furnace slag is damaged by acidic group of chlorine inorganic solution, from which Si ions, Ca ions, Al ions, etc. are leached, and double Ca ions produce Ca (OH) ₂ , which are present in magnesium dioxide and phosphate fertilizer. MgO generates Mg (OH) ₂ to weakly alkalize the liquid of the product, and the eluted ions recombine to produce an ettringite and a CSH gel and to generate an MSH gel.

The suitable amount of use is 15 to 40% by weight, and if the amount is less than this range, there is a problem in that the water resistance is weakened due to the insufficient amount of the product of the CSH gel and ettringite, which are water-resistant substances for magnesium-based products. In this case, the use of magnesium-based materials decreases as the amount of use decreases, which causes a problem in that they cannot serve as packaging materials. In addition, there is also a problem that the liquid retention of pH 10 or less, which is the object of the present invention, cannot be achieved by excessive use of blast furnace slag.

Magnesium chloride and phosphate are used for the chlorine inorganic solution. Magnesium chloride is generally known as a brine, and the chemical formula is MgCl ₂ · 5H ₂ O, and magnesium chloride is an MSH gel, CSH gel and 5Mg (OH) ₂ · MgCl ₂ · 8H ₂ O and 3Mg (OH ) Plays a dominant role in the production of ₂ · MgCl ₂ · 8H ₂ O phases. Phosphate acts to acidify the liquidity of magnesium chloride and to produce phosphate compound which is one of the final products, and it is acidic in phosphate, H ₃ PO ₄ , KH ₂ PO ₄ , NaH ₂ PO ₄ , Na ₂ H ₂ P ₂ O ₇ , (NaPO ₃ ) _{5 ~ 9,} etc., Magnesium dioxide, wollastonite, blast furnace slag are stimulated by these phosphate groups, and are ion-eluted to Mg ^{2 +} , Ca ^{2 +} , Al ^{3 +} , Si ^{4 +} is ionized, such as by the reaction of a phosphate group added to this hydroxyl and the apatite-based phosphate compound produced, magnesium ions and the aluminum ions and the like are hydrotalcite _{(Mg 4 Al 2 (OH)} 12 CO 3 · 3H ₂ O) acts to produce.

The proper amount of magnesium chloride is 10 to 60% by weight, and if it is less than this range, the bonding strength is lowered, so it cannot act as a binder. As a result, a problem that cannot be produced in liquid form occurs.

The proper amount of phosphate is 1 to 8% by weight, and if it is less than this range, the liquid liquidity becomes the neutral zone, so that the blast furnace slag cannot be effectively stimulated, and the water resistance that is intended based on this cannot be expected. In the case of exceeding this range, the use of excessive phosphate is not as economical as the use of phosphate fertilizer. In recent years, the price of phosphate has risen sharply, raising the cost of products using it. Currently, the price of phosphate, especially acidic phosphate, has been set at over 4500 won per kg. It takes up more than 50% of the ratio is a problem that the competitiveness with other binders deteriorate.

Water can be either seawater or freshwater, and the appropriate amount is 32 to 89% by weight.

The use ratio of the above powdery raw material and the liquid raw material is preferably 100: 30 to 70% by weight. More preferably, 100: 40-60 weight ratio is good. If the amount of the liquid raw material is less than the above range, there is a problem that can not be molded, if it exceeds the above range, the flowability is high and flows through the gap when the raw material is placed in the mold or mold, or solid and liquid phase during filling molding This separation problem occurs and finally leads to a decrease in compressive strength, which is undesirable.

The binder composition mainly based on soil according to the present invention can reduce air pollution by suppressing the release of CO ₂ gas generated during cement production due to unused cement, and block the generation of Cr ^{6 +} , which is toxic to cement. It is possible to recycle industrial by-products such as blast furnace slag without causing environmental pollution, and it is possible to filter out nonpoint pollutants (harmful heavy metals) in the initial rainwater, thereby protecting the water environment. have.

1 is a microstructure photograph of the soil permeable packaging specimen prepared by Example 3 in the present invention,
2 is a microstructure photograph of a specimen prepared by Comparative Example 2,
3 is a microstructure photograph of the cement specimen prepared by Comparative Example 6,
Figure 4 is a graph showing the difference between the XRD diffraction pattern generated by Example 3 and Comparative Example 6.

(Examples 1-6 and Comparative Examples 1-6)

To prepare a binder composition mainly composed of soil by the prescription as shown in Table 1 below, the compressive strength measurement results of each specimen obtained using this composition was as shown in Table 2 below. Heavy metal adsorption capacity test results were as shown in Table 3, and the data in Table 3 is the concentration of Cd remaining.

(Example 7)

The same procedure as in Example 2, except that the weight binder of magnesium oxide, wollastonite, blast furnace slag, phosphate fertilizer and volcanic soil was reduced from 90% to 70% by weight, and 30% of the surface soil of the dolomite mine was replaced. Increased to%. As a result, 7, 14, and 28-day compressive strengths of 35.9 MPa, 42.2 MPa, and 57.4 MPa were expressed, and 28 days of natural curing specimens were impregnated with water for 28 days and the compressive strength was measured. The pH value was measured and found to be 7.78. As the amount of soil increased to 30% by weight, the compressive strength decreased, and the pH value moved to the neutral region. Cd adsorption capacity was not detected as 0, 0, 0 as a result of 5 minutes of adsorption on standard solution 2ppm, 10ppm, 50ppm.

(Comparative Example 7)

The same procedure as in Example 7, except that the weight percent of magnesium oxide, wollastonite, blast furnace slag, phosphate fertilizer, and volcanic soil were reduced from 90% to 50% by weight, and 50% by weight of the surface soil of the dolomite mine was used instead. Increased to. As a result, the compressive strengths of 1,7, 14, and 28 days were 11.4 MPa, 14.7 MPa, and 16.9 MPa. The compressive strength could not be measured due to cracking after 28 days of natural curing specimens were immersed in water for 28 days. , pH value was 6.54 and neutral.

Claims (7)

Powder raw material consisting of 10 to 30% by weight of soil, 15 to 50% by weight of magnesium oxide, 15 to 40% by weight of blast furnace slag, 5 to 10% by weight of phosphate fertilizer, 10 to 40% by weight of volcanic soil, and 5 to 10% by weight of wollastonite Binder composition mainly composed of 100 parts by weight of soil consisting of 10 to 60 parts by weight of magnesium chloride, 1 to 8% by weight of phosphate, and 32 to 89 parts by weight of liquid raw material consisting of 32 to 89% by weight of water (fresh water or seawater). .
The binder composition according to claim 1, wherein the soil comprises clay soil such as mud (red clay) and loess, and sandy soil such as kaolin, white clay, and masato.
The soil-based binder composition according to claim 2, wherein the soil is suitably mixed in a proportion of 55% by weight or less of fine particles (0.8 mm or less) and particles of granules in a proportion of 45% by weight.
The binder composition according to claim 1, wherein the volcanic soil is volcanic soil composed of boehmite (Al (OH) ₃ ), crystallites of quartz and gypsum (calcium sulfate hydrate).
2. The binder composition according to claim 1, wherein the magnesium oxide comprises magnesium oxide obtained by heat-treating magnesium oxide extracted from dolomite, light magnesium, and magnesium hydroxide extracted from seawater.
The binder composition based on soil according to claim 1, wherein the blast furnace slag has a powder degree of 7,000 cm 2 / g.
[Claim 2] The binder composition according to claim 1, wherein the use ratio of the powder raw material and the liquid raw material is 100: 40 to 60 weight ratio.

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