KR101112742B1 - The composition for purification of contaminated soil and the manufacturing method for greener clay block which uses the composition - Google Patents

Abstract

PURPOSE: A manufacturing method of an environment-friendly clay block is provided to efficiently purify contaminated soil with high concentration which is difficult to be treated by existing biological method. CONSTITUTION: A manufacturing method of an environment-friendly clay block comprises: a composition manufacturing step(114) of manufacturing a composition for purification of contaminated soil by adding an oxidizer, a catalyst, a heavy metal anti-elution agent, a functional clay, OPC(Orkinary Portland Cement), blast-flake slag micro powders, a fly ash, natural CaSO4, and a soil binder; and an extrusion molding step(120) of molding products by using dry type oil hydraulic molding machine. The functional clay is artificial claymineral similar to clay bonded with silicon, aluminum and moisture, by mixing calcium silicate components to aluminosilicate industrial byproduct in which ferric oxide is contained.

Description

Composition for purification of polluted soil and manufacturing method of eco-friendly clay block using same {THE COMPOSITION FOR PURIFICATION OF CONTAMINATED SOIL AND THE MANUFACTURING METHOD FOR GREENER CLAY BLOCK WHICH USES THE COMPOSITION}

The present invention relates to a composition for the purification of contaminated soil and an environmentally friendly clay block manufacturing technology using the same, in particular, the soil contaminated with oil and hardly degradable organic pollutants at its original location, and the purified soil as a building and civil engineering material. The present invention relates to a composition for purification of contaminated soil for reuse as a main raw material of non-fired clay block, and an eco-friendly clay block manufacturing technology using the same.

In recent years, the pollution of soil which damages human health, property or environment is increasing due to rapid industrial development and human social activities. Soil pollution refers to soil being polluted as a substance that causes soil pollution, and soil pollutants are specified in the Enforcement Rules of the Soil Environment Conservation Act [Annex 1]. The soil environment has a very limited capacity that cannot be artificially multiplied and is the final result of all environmental pollutants that are heavier than air, and once contaminated is not only very difficult to restore to its original state, but also requires a lot of time and money to recover. You have to pay a high price.

 Soil purification means reducing or removing pollutants in the soil or mitigating risks caused by pollutants in the soil by biological, physical, chemical and thermal treatment methods. Soil purification is divided into in situ and ex situ methods. Contaminated soil purification techniques include land farming, which agitates contaminated soil to induce biodegradation of contaminants in aerobic conditions, and thermal desorption to separate contaminants from soil by applying heat, mechanical friction and cleaning Soil washing using water, Electrokinetic Separation to remove and remove pore water or pore water and ionic substances adsorbed on the surface of the soil by electric force from porous media, Polluted soil using plants And Phytoremediation, which purifies water quality, including groundwater, and Solidification / Stabilization, which fixes contaminants in solid solution, reduces fluidity, prevents elution, and detoxifies and removes toxicity. It is widely known.

The main targets for the cleanup of polluted soils in Korea were the first unsanitary landfills, but since the Soil Environment Conservation Act was enacted in 1995, soil pollution was investigated in factories, large industrial complexes, landfills, and abandoned mines. Soil pollution caused by organic compounds and heavy metals such as As, Zn, Pb, Cu, Cd, Ni, and organic matter causing leachate is reported to be serious, and soil pollutants are produced, transported, It is being expanded to facilities, devices, buildings, structures, and places that may contaminate soil by storage, handling, processing, or processing.

As a result, domestic cleanup projects included cleanup projects for 18 US military bases returned over three years from 2005 to 2007, in accordance with the 2002 Korea-US Land Partnership Plan (LPP) Agreement. And large-scale cleanup projects led by the nation, such as TKP closed pipelines due to the closure of the Trans Korea Pipeline (TKP) constructed by USFK for the purpose of oil transportation in 1970, and environmental pollution purification projects, and purification of waste mines and industrial complexes. And small-scale gas station cleanup projects at the private level. In addition, through the 'GAIA Project (Geo-Advanced Innovative Action Project)' in 2009, the Soil and Groundwater Pollution Prevention Technology Development Project established an advanced soil and groundwater integrated management base through on-site technology development and the soil and groundwater environmental market. There is a technology development support project to replace more than 90% of domestic technology with domestic technology.

While environmental pollution of soil and groundwater is difficult to recognize directly and progresses very slowly, the damage range is often widespread, and the cost of purification and the time required for purification are very long. In addition, various purification methods can be applied due to the variety and complexity of pollution characteristics, and there is a difficulty in that a uniform purification method cannot be applied uniformly. That's why it's a field that requires knowledgeable and experienced professionals. It is known that the environmental pollution of Korea has been widely spread to soil, rivers, groundwater and sea floor. Therefore, it is very urgent to implement the purification project. However, the domestic situation is still subject to trial and error by benchmarking the purification technology developed in advanced countries. At the same time, they are accumulating technology. However, with increasing social interest and large-scale cleanup projects such as US military return sites, the cleanup project is expected to become more active.

The technical problem to be solved by the present invention, the secondary pollution, including volatile air pollutants and treated wastewater generated by the physical and chemical treatment method to purify the high concentration of oil contaminated soil difficult to be treated by conventional biological treatment method The present invention provides a method for producing an environmentally friendly clay block that produces non-fired clay blocks by efficiently decomposing, binding, and fixing organic compounds and heavy metals in a short time without generating by-product pollutants.

Another technical problem to be solved by the present invention is to provide a composition for purification of contaminated soil used to manufacture the eco-friendly clay block.

Environmentally friendly clay block manufacturing method according to the present invention for achieving the above technical problem is oxidizing agent, catalyst, heavy metal leaching agent, functional clay, OPC (usually Portland cement), blast furnace slag powder, fly ash, natural anhydrous gypsum and soil Comprising a composition manufacturing step of producing a composition for cleaning soil contaminated by the addition of a binder and a compression molding step of manufacturing the product by molding the composition into a desired shape using a dry hydraulic molding machine.

Contaminated soil purification composition according to the present invention for achieving the above another technical problem, oxidizing agent, catalyst, heavy metal leaching inhibitor, functional clay, OPC (usually Portland cement), blast furnace slag powder, fly ash At least one of natural anhydrous gypsum and soil binder is added.

The contaminated soil purification composition according to the present invention and the eco-friendly clay block manufacturing technology using the same has the following effects.

First, it is possible to quickly purify high concentrations of oil contaminated soil that are difficult to treat by biological treatment.

Second, there is no secondary pollution because no treatment wastewater or air pollution by-products generated by soil washing or thermal desorption are generated.

Third, the treatment time of pollutants (organic compounds and heavy metals) is only about 1 to 3 days, so the removal rate is very fast compared to other treatment methods.

Fourth, there is no odor generated by rapidly decomposing odor causing substances when processing pollutants.

Fifth, it does not disturb or recontaminate the surrounding soil environment by removing and recycling the contaminated soil itself from its original location.

Sixth, verification of the cleanup process and completion is very simple and no subsequent management of the cleanup area is required.

Seventh, it is possible to drastically reduce energy and manufacturing costs by producing clay blocks in a non-plastic way, not plasticity.

Eighth, it is very environmentally friendly to prevent the destruction of the natural environment for collecting clay.

1 shows a method for producing an environmentally friendly clay block according to the present invention.
Figure 2 is a real picture of the clay mixture and clay block prepared according to the eco-friendly clay block manufacturing technology according to the present invention.

In order to fully understand the present invention and the operational advantages of the present invention and the objects achieved by the practice of the present invention, reference should be made to the accompanying drawings, which are provided for explaining exemplary embodiments of the present invention, and the contents of the accompanying drawings.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. Like reference numerals in the drawings denote like elements.

The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art, and are not construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.

Organic contaminants mentioned throughout this specification include hardly decomposable organic substances that are difficult to decompose by soil microorganisms, including organic compounds, chlorinated organic compounds, including pesticides, preservatives, petroleum and oils thereof.

Compositions for the purification of contaminated soil according to the present invention and compositions for eco-friendly clay block manufacturing technology using the same as catalyst containing oxidizing agent, heavy metal leaching inhibitor, functional clay, OPC, blast furnace slag powder, fly ash, natural anhydrous gypsum, and soil Binders are used.

Composition

Hereinafter, each composition will be described in more detail.

At this time, the content range of each composition described below is an optimum range for maximizing each effect obtained when using each composition and the synergy effect obtained by mixing with other compositions. Not get

The clay block composition according to the present invention is prepared based on the purified soil of the contaminated soil.

The contaminated soils are soil pollutants such as cadmium, copper, arsenic, mercury, lead, zinc nickel and their compounds, hexavalent chromium compounds, fluorine compounds, and organic substances that are harmful to human health and the environment due to human social activities. Phosphorus compounds, polychlorinated biphenyls, cyanide compounds, phenols, benzene, toluene, ethylbenzene, xylenes, petroleum-based hydrocarbons, trichloroethylene, tetrachloroethylene, benzo (a) pyrene, and other similar soil contaminants In order to prevent soil pollution, it is recognized that it needs to be specially managed, and it is contaminated with materials admitted by the Minister of Environment.

Here, the purified soil refers to a soil in which the polluted soil is reduced or removed from the soil by a biological, physical, chemical, or thermal treatment method, or the risk of the pollutant in the soil is alleviated.

Hydrogen peroxide (H ₂ O _2, molecular weight 34.016) is a colorless and transparent compound with strong oxidizing power. It has a weak acidity due to some dissociation of hydrogen ions in aqueous solution. It is a strong oxidant and at the same time has the function of a weak reducing agent. It is usually supplied in a slightly acidic state because decomposition occurs a lot above pH 6 and the decomposition rate increases rapidly as the pH rises. Hydrogen peroxide also has the property of generating free radicals in the presence of neutral or acidic low oxidizing metal ions. Oxidation process using hydrogen peroxide is a kind of AOP (Advanced Oxidation Process). When hydrogen peroxide is activated, OH and HO ₂ radicals are generated and their redox potential is very high to oxidize hardly decomposable organics. In general, hydrogen peroxide performs the following reaction in an aqueous solution.

H ₂ O ₂ → H ₂ O + ½O ₂ or 2H ₂ O ₂ → 2H ₂ O + O ₂

In order to generate a strong oxidizing power to oxidize hardly decomposable organic substances, a Fenton reaction that generates OH radical (? OH, Hydroxyl radical) using hydrogen peroxide (Fenton's reagent) and iron ions (Fe ²⁺ ) as a catalyst ( Fenton Reaction) is used, and the principle of fenton oxidation is as follows.

^{_{? Fe 2+ + H 2 O 2}} → OH + OH - + Fe 3+

Fe ³⁺ + H ₂ O ₂ → HO ₂ ? + H ⁺ + Fe ²⁺

That is, to iron ions is circulated between Fe ²⁺ and Fe ³⁺ when the organic substance is oxidized and decomposed, Fe ²⁺ having a catalytic function is to catalyze the hydrogen peroxide generated from hydrogen peroxide and the OH radical is oxidized to Fe ³⁺ . The generated OH radicals decompose organic matter to form R? (Organic radicals), by which Fe ³⁺ is further reduced to Fe ²⁺ and R? Is oxidatively decomposed. This method has recently gained attention because it has the advantage of restoring soil contaminated oil within a short time, and has been applied to various oil contaminated soils. As the ferric ion catalyst, iron compounds such as iron, ferrous oxide, ferric oxide, ferrous chloride, ferric chloride, ferrous hydroxide, ferric hydroxide, ferrous sulfate, and ferric sulfate It can be used, hydrogen peroxide concentration 35% hydrogen peroxide is used. The metal catalyst and hydrogen peroxide may be mixed in an amount of 1: 1 to 0.5 parts by weight based on 100 parts by weight of contaminated soil.

SOREM contains 35-50% by weight of Potassium monopersulfate (KHSO ₅ ), 15-30% by weight of Potassium hydrogensulfate (KHSO ₄ ), 20-40% by weight of Potassium sulfate (K ₂ SO ₄ ), and 0.1-1% by weight. Refers to a mixture of acid catalysts. The components contained in the Sorem can generate SO ₄ ^- radicals with strong oxidizing power not only by heat but also by light, metals, etc., thus decomposing oil and hydrophobic substances which are pollutants of soil contaminated with oil or hydrophobic solvent by the oxidizing power of the Sorem can do. Sorem may be used alone, calcium peroxide (CaO ₂ ), potassium dioxide (KO ₂ ), potassium peroxide (K ₂ O ₂ ), magnesium peroxide (MgO ₂ ), ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), ozone (O ₃ ), hydrogen peroxide (H ₂ O ₂ ), sodium percarbonate (2Na ₂ CO ₃ ˜3H ₂ O ₂ ), nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), perchloric acid (HClO ₄ ), hypochlorous acid (HClO), permanganic acid (HMnO ₄ ), chromic acid (H ₂ CrO ₄ ), sodium hypochlorite (NaOCl), calcium hypochlorite (Ca (OCl) ₂ ), sodium persulfate (Na ₂ S ₂ O ₈ ) Or persulfates such as potassium persulfate (K ₂ S ₂ O ₈ ), salts of the aforementioned compounds, manganese oxide (Mn ₂ O ₇ ), lead dioxide (PbO ₂ ), manganese dioxide (MnO) ₂ ), at least one selected from the group consisting of cupric oxide (CuO), ferric chloride (FeCl ₃ ), fluorine (F), chlorine (Cl), bromine (Br), and iodine (I) as an oxidizing additive Can be. When the sorem composition further includes an oxidizing additive, the oxidizing additive may be mixed in an amount of 0.0001 to 90 parts by weight, preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the sorem.

Sorem restores contaminated soil by oxidizing power that generates SO4 ^- radicals by reacting with metals or metal salts naturally contained in soil. If necessary, metal catalysts can be added to restore the contaminated soil in areas with excessively low levels of soil heavy metals or metal salts. That is, the metal catalyst may be used as long as it is a metal compound capable of reacting with Sorem to generate SO 4 ^- radicals. In particular, the metal catalyst may be a metal or an iron compound, and the form of the metal catalyst is not particularly limited. However, it is preferable to use granular or powdered metal catalysts.

As the metal catalyst, iron oxides such as iron, ferrous oxide, ferric oxide, magnetite, and the like, iron hydroxides such as ferrous hydroxide and ferric hydroxide, iron sulfate (I) and iron sulfate (II) and Various iron compounds such as iron sulfides, iron chlorides such as iron (I), iron chlorides (II), transition metals such as copper, manganese, cobalt, nickel, salts, oxides of transition metals such as copper, manganese, cobalt or nickel Or one or more selected from the group consisting of hydroxides. When the sorem composition further comprises a metal catalyst, the metal catalyst may be mixed in an amount of 0.0001 to 50 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the sorem.

As described above, the Sorem containing 0.0001 to 90 parts by weight of the oxidizing additive and the 0.0001 to 50 parts by weight of the metal catalyst may be added to 0.01 to 1 part by weight per 100 parts by weight of the contaminated soil.

Sodium persulfate (Na ₂ S ₂ O ₈ ) is a white powder, soluble in water, aqueous solution is neutral or slightly acidic. Can generates a strong oxidizing power to decompose the pollutants ^- is easy solution in the oxidation potential sulfate radical (sulfate radical, SO _4?) Up to 2.01V. Sodium sulfate and the sulfate radical (SO ₄ ^- radical) is ozone and hydroxyl radicals of hydrogen peroxide ^- was found to also present a much more stable condition (OH radical) or a light metal catalyst or if high heat and contact of 2.6V by the catalytic action It is known to produce sulfate radicals with oxidation potentials.

Sodium persulfate is much less economical than hydrogen peroxide, so it can effectively decompose and remove oil pollutants in the soil, and it is very economical because it can decompose organic pollutants in a small amount. Sulfate radicals formed in sorem and sodium persulfate are considered to be very stable and have excellent field applicability due to the large amount of heat, water vapor and odor generated during the Fenton oxidation reaction of hydrogen peroxide and no soil hardening due to excessive injection. The radical reaction of sodium persulfate is shown below, and more powerful sulfate radicals are produced when metal catalysts (especially ferric ions) are used as oxidants.

_{^{S 2 O 8 2- + 2e -}} → 2SO 4 2- oxidation potential 2.01V

When using a ferric ion (metal catalyst),

S ₂ O ₈ ^2- + Fe ²⁺ → Fe ³⁺ +? SO ₄ ^2- + SO ₄ ^2- Oxidation potential 2.60V

As the ferric ion catalyst, iron compounds such as iron, ferrous oxide, ferric oxide, ferrous chloride, ferric chloride, ferrous hydroxide, ferric hydroxide, ferrous sulfate, and ferric sulfate It can be used, the metal catalyst containing sodium persulfate containing 0.01 to 1 parts by weight of the metal catalyst (Fe ²⁺ ) in 100 parts by weight of sodium persulfate can be used by adding 0.01 to 1 parts by weight per 100 parts by weight of contaminated soil. In the present invention, each of the catalyst-containing oxidizing agents hydrogen peroxide, solem, sodium persulfate selected from any one selected from 0.01 to 1 parts by weight per 100 parts by weight of contaminated soil is used.

Heavy metal leaching inhibitor is a mixture of Na ₃ T and distilled water, the heavy metal is precipitated as a metal-Na ₃ T compound in the Na ₃ T aqueous solution through the following reaction. Analysis of the components of these compounds by the same method as elemental analysis showed that Na ₃ T molecules bound to 3 equivalents of heavy metals.

[Reaction Mechanism]

Monovalent ^{metal: 3Me + + Na3T 3 - →} Me 3 Na3T (Extremely low solubility)

Divalent ^{metal: 3Me 2 + + 2Na3T 3 -} → Me 3 (Na3T) 2 (Extremely low solubility)

Where Me ⁺ , Me ²⁺ = heavy metal

^{_{Na3T 3 - = C 3 N 3}} S3 3 -

Thiol group at the end of Trimercapto-S-Triazi stabilizes heavy metals by reacting with heavy metals to form chelates and polymerize high-molecular organometallic complexes. Dimethyldithiocarbamate (LC50 value of 20) and Sodium trithiocarbonate (LC50 value of 7.5) with other thiol groups are eco-friendly products with strong ecotoxicity, whereas Na3T-15 is almost nontoxic with aquatic toxicity above 4,000 ppm. Has features close to. In addition, it exists as a three-dimensional network structure with a macromolecular effect, so it does not cause any secondary pollution problems such as re-elution.It reacts with three equivalents of heavy metals, so the heavy metal removal efficiency is excellent and after reaction, Hydrogen Sulfide (H ₂ S) It is not separated and exists as metal-organic compounds rather than metallic sulfides.

In the present invention, it is used to add 0.01 to 0.1 parts by weight per 100 parts by weight of heavy metal contaminated soil.

The functional clay is an artificial clay mineral (粘土 鑛物, Clay mineral) similar to the clay combined with silicon, aluminum, and water after the weathering and decomposition of the rock by mixing calcium silicate components with aluminosilicate industrial by-products containing iron oxide As it is manufactured, the color and texture reminiscent of natural soils reduce the rejection of dark gray sludge and increase the value of the product.

In the present invention, by mixing the purified soil 65 ~ 85% by weight of purified soil and 15 ~ 35% by weight of functional clay to prepare a mixture for clay.

OPC (Ordinary Portland Cement) means one kind of ordinary portland cement. Class 1 ordinary portland cements can be used in either gray or white portland cement or in combination and are added for heavy metal fixation and strength enhancement. In the present invention, 5 to 15 parts by weight of OPC is added and used per 100 parts by weight of the mixture for clay.

Blast furnace slag powder is quenched with high-pressure water in which molten iron ore, coke and limestone, which are charged in iron-producing blast furnace (furnace), are quenched with high-pressure water and milled sand-like wood slag in mill. It refers to pulverized to a certain powder, and improves the long-term strength of the cured body and keeps the tissue tight, thereby improving durability. Powders of 7,000 cm ² / g or more are also used.

In the present invention, 5 to 15 parts by weight of blast furnace slag powder is added per 100 parts by weight of the mixture for clay.

Fly Ash refers to fly ash generated from by-products of less than 1% moisture content collected from an electric dust collector after combustion of pulverized coal, which is usually crushed into small particles of less than 0.7 mm in a coal-fired power plant. It is classified as fly ash and bottom ash according to the occurrence location, collectively called coal ash or coal ash. Fly ash accounts for 75% ~ 80% of the total ash production, and recycled large amounts of ready-mixed concrete, concrete admixtures, cement and clay bricks, but most of them depend on landfills in the off-season. Bottom ash, which accounts for 15 ~ 20% of the total coal ash production, is only used as a light aggregate substitute, and most of it is buried in its own landfill (ash treatment plant), so the recycling rate is very low. Although 6 million tonnes of coal ash is generated annually in Korea, the recycling rate has gradually decreased since 2003, and about 30% of the amount generated is simply landfilled in the ash processing plant.

In the present invention, 1 to 6 parts by weight of fly ash is further used per 100 parts by weight of the mixture for clay.

Natural anhydrous gypsum (CaSO ₄ ) is usually composed of blocks, fibers, and granules. It is tasteless, odorless, colorless, and nontoxic. It is a compound that exists all over the world as a compound. Natural gypsum ores include dihydrate gypsum (CaSO ₄ ㆍ 2H ₂ O) containing two molecules of crystalline water and anhydrous gypsum (CaSO ₄ ) containing no crystalline water. Originally gypsum minerals produced in nature, the use of chemical gypsum produced as a by-product of chemical industry is increasing. The role of gypsum in cement is to control the coagulation of cement (delay coagulation), promote hardening (improve initial strength), improve resistance to sulphate and reduce expansion and contraction after drying.

In the present invention, 0.1 to 1 parts by weight of natural anhydrous gypsum having a powder content of 425mesh (44 μm) or more is used per 100 parts by weight of the mixture for clay.

The soil binder is a high performance water reducing agent per 100 parts by weight of pure water, and is a mixture of 1 to 1 polycarboxylic acid-based water soluble polymer (CP-WB) and 2 to 1 polycarboxylic acid-based water soluble polymer (CP-WRM). 5 parts by weight of any one selected from aluminum sulphate (Al ₂ (SO ₄ ) ₃ ) and ferrous sulfate monohydrochloride (FeSO ₄ ㆍ H ₂ O) or hexate (FeSO ₄ · 7H ₂ O) And 0.1 to 2 parts by weight of methyl cellulose The CP-WB is a high-performance slump-retaining polycarboxylic acid-based water-soluble polymer that improves the fluidity of the composition even in the region of high susceptibility and increases workability by maintaining fluidity for a long time. CP-WRM is a high-performance polycarboxylic acid-based water-soluble polymer that improves the curing time.The aluminum sulfate and ferrous sulfate (monohydrate and hexahydrate) are used to aggregate particulate soil particles. It serves to stabilize.

Methyl Cellulose is a Hydroxyalkyl Methyl Cellulose based on Cellulose obtained from wood and cotton. Cellulose is an insoluble natural polymer having 30-65% crystallinity due to intermolecular hydrogen bonding. Cellulose that is insoluble in water is made of water-soluble polymer called cellulose ether (Cellulose ether) through etherification. Methyl cellulose is a nonionic water-soluble polymer, and is used as a thickener, humectant, lubricant, stabilizer, etc. in various fields such as construction, cement extrusion, ceramic extrusion, polymer polymerization, paint, detergent and medicine, and household goods.

In the present invention, 5 to 15 parts by weight of the soil binder is added and used per 100 parts by weight of the mixture for clay.

Manufacturing technology

Hereinafter, an eco-friendly clay block manufacturing method of the present invention will be described with reference to the accompanying drawings.

1 shows a method for producing an environmentally friendly clay block according to the present invention.

Figure 2 is a real picture of the clay mixture and clay block prepared according to the eco-friendly clay block manufacturing technology according to the present invention.

Referring to FIG. 1, the method 100 for producing an environmentally friendly clay block includes a mixture manufacturing step 110, a compression molding step 120, and a curing step 130.

The mixture production step 110 includes a first mixture production step 111, a second mixture production step 112, a third mixture production step 113, and a composition production step 114.

The first mixture production step 111 is hydrogen peroxide (H ₂ O ₂ ), including the metal catalyst, Sorem, sodium and sulfur persulfate (Na ₂ S ₂ O ₈ ) containing the metal catalyst and the oxidation additive and the metal catalyst Any one is added to 100 parts by weight of contaminated soil at 0.01 to 1 part by weight to prepare a first mixture.

In the second mixture production step 112, 0.01 to 0.1 parts by weight of the heavy metal elution inhibitor is further added to 100 parts by weight of the primary mixture to prepare a second mixture. At this time, the heavy metal leaching inhibitor is diluted 2 to 5 times in ultrapure water purified using reverse osmosis membrane, ultrafiltration membrane, and ion exchange resin to increase reactivity.

In the third mixture manufacturing step 113, a mixture of 15 to 35% by weight of functional clay is further mixed with 65 to 85% by weight of the first or second mixture to prepare a third mixture, which is a mixture for clay. In this case, the dotted line may be selectively applied when the second mixture manufacturing step 112 is mixed with organic contaminants and heavy metals, and thus, when the second mixture manufacturing step 112 is not performed, the first mixture manufacturing step is performed. (111) After the progress means that the third mixture production step 113 is performed.

Composition manufacturing step 114 is 5 to 15 parts by weight of OPC (usually Portland cement) per 100 parts by weight of the third mixture, 5 to 15 parts by weight of blast furnace slag powder, 1 to 6 parts by weight of fly ash, 0.1 to 1 weight of natural anhydrite gypsum Part, 5 to 15 parts by weight of the soil binder is further mixed to prepare a composition for soil purification. Here, OPC, blast furnace slag powder, fly ash, and natural anhydrite are stored in a dry cylindrical sealed container that does not penetrate moisture, and the soil binder is stored in a liquid tank and quantitatively supplied using a rotary feeder and a pump.

In the compression molding step 120, the contaminated soil purification composition is manufactured into a desired shape by using a dry hydraulic molding machine to manufacture a product.

Curing step 130 is curing the product undergoing compression molding step 120 in the room temperature curing room for 1-2 days.

Usage

The clay block manufactured through the above-described steps is preferably used as a non-plastic eco-friendly clay block replacing plastic clay blocks because the clay blocks have no durability and strength standards and do not re-dissolve contaminants.

[Table 1] below shows the results of heavy metal dissolution test according to the Waste Process Test Criteria: 2008 of non-plastic clay block prepared by purifying soil contaminated with waste oil in automobile repair station. It can be seen that they are all within the standard and harmless.

Test Items unit Sample classification Results Test Methods Pb mg / L 0.06 Waste Process Test Standard: 2008 Cu mg / L Not detected Waste Process Test Standard: 2008 As mg / L Not detected Waste Process Test Standard: 2008 Hg mg / L Not detected Waste Process Test Standard: 2008 CN ^- mg / L Not detected Waste Process Test Standard: 2008 Cr (Ⅵ) mg / L Not detected Waste Process Test Standard: 2008 CD mg / L 0.002 Waste Process Test Standard: 2008 Organic phosphorus mg / L Not detected Waste Process Test Standard: 2008 Oil % 1.028 Waste Process Test Standard: 2008 Tetrachloroethylene mg / L Not detected Waste Process Test Standard: 2008 Trichlorethylene mg / L Not detected Waste Process Test Standard: 2008

Relevant standards; Pb 3, Cu 3, As 1.5, Hg 0.005, Cd 0.3, Cr (VI) 1.5, cyan 1, organophosphorus 1, TCE 0.3, PCE 0.1mg / L, oil content 5% or more.

Although specific embodiments of the present invention have been described and illustrated above, it is obvious that the present invention may be variously modified and implemented by those skilled in the art. Such modified embodiments should not be individually understood from the technical spirit or the prospect of the present invention, and such modified embodiments should fall within the scope of the appended claims.

<Examples>

First, waste diesel engine oil was mixed with waste field sand containing a part of general field soil and heavy metals to artificially prepare soil contaminated with organic pollutants and heavy metals. After the addition of the solem containing the metal catalyst was oxidized and then chelated with heavy metal leaching agent, 80% by weight of the purified purified soil and 20% by weight of functional clay was mixed to prepare a clay mixture. In addition, 6 parts by weight of a first mixture of polycarboxylic acid-based water-soluble polymer (CP-WB) and second polycarboxylic acid-based water-soluble polymer (CP-WRM) 1: 1 mixture, 100 parts by weight of pure water prepared in advance, aluminum sulfate 6 parts by weight of (aluminum sulphate, (Al ₂ (SO ₄ ) ₃ )) and 1.5 parts by weight of methyl cellulose were added and mixed to prepare a soil binder.

The clay block was mixed with 100 parts by weight of OPC (usually Portland cement), 10 parts by weight of blast furnace slag powder, 4 parts by weight of fly ash, 0.5 parts by weight of natural anhydrite, and 5 parts by weight of soil binder. The clay block was prepared by putting it in a mold and pressing, and then cured for 2 days to prepare a desired non-plastic clay block.

Each composition used at this time is as shown in the following [Table 2].

Sample name (% by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Clay Mixture Soil 34.5 37 39.5 42 44.5 Waste Foundry Sand 20 22.5 25 27.5 30 Waste Diesel Engine Oil 25 20 15 10 5 Metal catalyst 0.01 0.01 0.01 0.01 0.01 Sorem 0.465 0.465 0.455 0.455 0.445 Heavy Metal Elution Agent 0.025 0.025 0.035 0.035 0.045 Functional clay 20 20 20 20 20 Total (mixture for clay) 100 100 100 100 100
Solidifying aids
OPC 10 10 10 10 10 Blast Furnace Slag Powder 10 10 10 10 10 Fly ash 4 4 4 4 4 Natural Anhydrous Gypsum 0.5 0.5 0.5 0.5 0.5 Soil binder 5 5 5 5 5

&Lt; Example 1 >

Artificial soil was prepared by mixing 34.5% by weight of soil soil, 20% by weight of waste foundry sand, and 25% by weight of waste diesel engine oil, and oxidized with 0.01% by weight of metal catalyst and 0.465% by weight of Sorem, and then added 0.025% by weight of heavy metal leaching inhibitor. 20 wt% of functional clay was further added to the purified and chelated purified soil to prepare a mixture for clay at 100 wt% in total. Subsequently, 10 parts by weight of OPC, 10 parts by weight of blast furnace slag powder, 4 parts by weight of fly ash, 0.5 parts by weight of natural anhydrous gypsum, and 5 parts by weight of soil binder were added to the clay block mold. Pressurized clay blocks were prepared and then cured for 2 days to produce the desired non-plastic clay blocks.

<Example 2>

Artificial soil was prepared by mixing 37% by weight of soil soil, 22.5% by weight of waste foundry sand, and 20% by weight of waste diesel engine oil, and oxidized with 0.01% by weight of metal catalyst and 0.465% by weight of Sorem, and then added 0.025% by weight of heavy metal leaching inhibitor. 20 wt% of functional clay was further added to the purified and chelated purified soil to prepare a mixture for clay at 100 wt% in total. Subsequently, 10 parts by weight of OPC, 10 parts by weight of blast furnace slag powder, 4 parts by weight of fly ash, 0.5 parts by weight of natural anhydrous gypsum and 5 parts by weight of soil binder were added to the clay block mold. Pressurized clay blocks were prepared and then cured for 2 days to produce the desired non-plastic clay blocks.

<Example 3>

An artificially contaminated soil was prepared by mixing 39.5% by weight of soil soil, 25% by weight of waste foundry sand, and 15% by weight of waste diesel engine oil, and then oxidized with 0.01% by weight of metal catalyst and 0.455% by weight of Sorem. The mixture was further prepared by adding 20% by weight of functional clay to the chelated purified soil and adding 100% by weight. Subsequently, 10 parts by weight of OPC, 10 parts by weight of blast furnace slag powder, 4 parts by weight of fly ash, 0.5 parts by weight of natural anhydrous gypsum and 5 parts by weight of soil binder were added to the clay block mold. Pressurized clay blocks were prepared and then cured for 2 days to produce the desired non-plastic clay blocks.

<Example 4>

Artificial soil was prepared by mixing 42% by weight of soil soil, 27.5% by weight of waste foundry sand, and 10% by weight of waste diesel engine oil, and then oxidized with 0.01% by weight of metal catalyst and 0.455% by weight of Sorem, and then added 0.035% by weight of heavy metal leaching inhibitor. 20 wt% of functional clay was further added to the purified and chelated purified soil to prepare a mixture for clay at 100 wt% in total. Subsequently, 10 parts by weight of OPC, 10 parts by weight of blast furnace slag powder, 4 parts by weight of fly ash, 0.5 parts by weight of natural anhydrous gypsum and 5 parts by weight of soil binder were added to the clay block mold. Pressurized clay blocks were prepared and then cured for 2 days to produce the desired non-plastic clay blocks.

Example 5

Artificial soil was prepared by mixing 44.5% by weight of soil soil, 30% by weight of waste foundry sand, and 5% by weight of waste diesel engine oil, and oxidized with 0.01% by weight of metal catalyst and 0.445% by weight of Sorem, and then added 0.045% by weight of heavy metal leaching inhibitor. 20 wt% of functional clay was further added to the purified and chelated purified soil to prepare a mixture for clay at 100 wt% in total. Subsequently, 10 parts by weight of OPC, 10 parts by weight of blast furnace slag powder, 4 parts by weight of fly ash, 0.5 parts by weight of natural anhydrous gypsum and 5 parts by weight of soil binder were added to the clay block mold. Pressurized to prepare a clay block, and then cured for 2 days to produce the desired non-plastic clay.

The clay block samples prepared by the method of Examples 1 to 5 were respectively taken to measure compressive strength and water absorption, and are shown in the following [Table 3]. As a comparative example 1, KS standard (KS F 4004: 2008) A type brick , KS standard as Comparative Example 2 (KS F 4004: 2008) B type brick, KS standard as Comparative Example 3 (KS F 4004: 2008) Class C brick as Class 1, KS standard as Comparative Example 4 (KS F 4004: 2008) Concrete brick quality standards of Class C bricks are shown. In addition, A and B bricks are lightweight bricks using light aggregates, and bricks using only plain aggregates should be suitable for C bricks.

Strength and Absorption Rate of Clay Blocks (Bricks) According to the Present Invention division Compressive strength
(N / mm ² ) Absorption rate (%) Test Methods Remarks Example 1 38.00 6 KS F 2405 Example 2 31.00 5 KS F 2405 Example 3 32.00 5 KS F 2405 Example 4 30.00 5 KS F 2405 Example 5 37.00 6 KS F 2405 Comparative Example 1 A Type Brick 8 or more - KS F 2405 KS F 4004 Comparative Example 2 B Brick 12 or more - KS F 2405 KS F 4004 Comparative Example 3 (Class C Brick) 16 or more 7 or less KS F 2405 KS F 4004 Comparative Example 4 (Class C Brick 2nd Grade) 8 or more below 10 KS F 2405 KS F 4004

As can be seen from Table 3, clay blocks prepared by the method of Examples 1, 2, 3, 4, and 5 using soil hardeners are shown in KS F 4004 of Comparative Examples 1, 2, 3, and 4. It can be seen that the compressive strength and absorption rate of the A, B, C vertical bricks are superior to the standard values. Therefore, the non-plastic clay block manufactured by the composition for the contaminated soil purification of the present invention and the eco-friendly clay block manufacturing technology using the same can replace ordinary plastic clay bricks used as flooring materials, which can dramatically reduce energy generation and air pollutant generation. have. In-situ method can be adopted to handle the contaminated soil on-site without moving it to the outside, thereby dramatically reducing the cost of purification and reusing the contaminated soil into recycled clay blocks for efficient use of resources. It is possible and does not generate any pollutants affecting the atmosphere, soil and water system, which has the advantage of contributing to environmental protection.

Claims (10)

Preparation of the contaminated soil purification composition by adding oxidizing agent, catalyst, heavy metal leaching agent such as Na ₃ T aqueous solution, functional clay, OPC (usually Portland cement), blast furnace slag powder, fly ash, natural anhydrous gypsum and soil binder Composition manufacturing step; And
It comprises a compression molding step of manufacturing the product by molding the composition into a desired shape using a dry hydraulic molding machine,
The functional clay is a method for producing an environmentally friendly clay block, which is an artificial clay mineral similar to silicon, aluminum, and water combined with clay after weathering and decomposing rock by mixing calcium silicate components with aluminosilicate industrial by-products containing iron oxide. . According to claim 1, The composition manufacturing step,
A first mixture manufacturing step of preparing a first mixture by adding the oxidant and the catalyst to the contaminated soil;
A third mixture manufacturing step of preparing a third mixture, which is a mixture for clay, by mixing the first mixture with the functional clay; And
Method for producing an environmentally friendly clay block comprising the step of preparing the composition by adding OPC (usually Portland cement), blast furnace slag powder, fly ash, natural anhydrous gypsum and soil binder to the third mixture. The method of claim 2,
Further comprising a second mixture manufacturing step of preparing a second mixture by adding the heavy metal elution inhibitor to the first mixture,
The third mixture manufacturing step of producing an environmentally friendly clay block for mixing the first mixture or the second mixture with the functional clay to produce the third mixture. The method of claim 3,
The first mixture production step, any one of hydrogen peroxide (H ₂ O ₂ ), a metal catalyst containing a metal catalyst, Sorem, an oxide additive and a sodium catalyst containing a metal catalyst and sodium persulfate (Na ₂ S ₂ O ₈ ) containing a metal catalyst 0.01 to 1 part by weight is added to 100 parts by weight of contaminated soil to prepare a first mixture,
In the preparing of the second mixture, the second mixture is prepared by adding 0.01 to 0.1 parts by weight of the heavy metal elution inhibitor to 100 parts by weight of the first mixture.
In the third mixture manufacturing step, by mixing 15 to 35% by weight of the functional clay to 65 to 85% by weight of the first mixture or the second mixture to prepare the third mixture,
The composition manufacturing step, 5 to 15 parts by weight of the OPC (usually Portland cement), 5 to 15 parts by weight of the blast furnace slag powder, 1 to 6 parts by weight of the fly ash, the natural anhydrous gypsum per 100 parts by weight of the third mixture 0.1 to 1 part by weight and 5 to 15 parts by weight of the soil binder by mixing the environmentally friendly clay block manufacturing method for producing the composition. The method of claim 4, wherein
The heavy metal leaching inhibitor is a method for producing an environmentally friendly clay block which is diluted 2 to 5 times in ultrapure water purified from raw water using a reverse osmosis membrane, an ultrafiltration membrane and an ion exchange resin. The method of claim 4, wherein
The OPC, the blast furnace slag powder, the fly ash, and the natural anhydrous gypsum are stored in a dry cylindrical sealed container that does not penetrate moisture,
The soil binder is stored in a liquid tank to produce an eco-friendly clay block for quantitative supply using a rotary feeder and a pump. The method of claim 1,
Eco-friendly clay block manufacturing method further comprises a curing step of curing the product undergoing the compression molding step at room temperature curing room for 1-2 days. In the composition for cleaning soil contaminated by the method of claim 1,
On contaminated soil containing contaminants,
At least one of an oxidizing agent, a catalyst, a heavy metal leaching inhibitor such as an aqueous solution of Na ₃ T, functional clay, OPC (usually Portland cement), blast furnace slag powder, fly ash, natural anhydrous gypsum and soil binder is added.
The functional clay is an artificial clay mineral composition similar to clay, which is silicon, aluminum, and moisture-bonded clay after weathering and decomposition of rocks by mixing calcium silicate components with aluminosilicate industrial by-products containing iron oxide. The method of claim 8, wherein the soil cleaning composition,
Hydrogen peroxide (H ₂ O ₂ ) with metal catalyst, Sore (SOREM), Sorem with oxidizing agent and metal catalyst and Sodium persulfate (Na ₂ S) with metal catalyst in 100 parts by weight of contaminated soil Oxidation treatment by mixing any one of ₂ O ₈ ) to 0.01 to 1 part by weight,
To clean contaminated soil by adding 0.01 ~ 0.1 parts by weight of heavy metal leaching inhibitor to 100 parts by weight of oxidized soil,
65 to 85% by weight of purified soil and 15 to 35% by weight of functional clay were mixed to prepare a mixture for clay,
5 to 15 parts by weight of OPC (usually Portland cement), blast furnace slag powder 5 to 15 parts by weight, fly ash 1 to 6 parts by weight, natural anhydrous gypsum 0.1 to 1 parts by weight, soil binder 5 ~ Polluted soil purification composition further comprises 15 parts by weight. 10. The method of claim 9,
The contaminated soil is cadmium, copper, arsenic, mercury, lead, zinc nickel and compounds thereof, hexavalent chromium compounds, fluorine compounds, organophosphorus compounds, polychlorinated biphenyls, cyanide compounds, phenols, benzene, Soil contaminated with toluene, ethylbenzene, xylene, petroleum-based hydrocarbons, trichloroethylene, tetrachloroethylene, benzo (a) pyrene, and other similar soil contaminants,
The purified earth may be hydrogen peroxide (H ₂ O ₂ ) containing a metal catalyst, or Sorem (SOREM) or Sorem containing an oxidation additive and a metal catalyst, or sodium persulfate (Na ₂ S ₂ O ₈ ) containing a metal catalyst. Any one is mixed 0.01 to 1 parts by weight to oxidize the contaminated soil, and 0.01 to 0.1 parts by weight of heavy metal elution inhibitor is added to 100 parts by weight of the contaminated soil, and the soil is purified.
The hydrogen peroxide is a substance having a concentration of 35% causing a Fenton Reaction that generates hydroxy radicals by using ferric ions (Fe ²⁺ ) as a catalyst.
The sorem (SOREM) is 35 to 50% by weight of Potassium monopersulfate (KHSO ₅ ), 15 to 30% by weight of Potassium hydrogensulfate (KHSO ₄ ), Potassium sulfate (K ₂ SO ₄ ) 20 to 40 to generate sulfate radicals It is a powdery substance mixed with an acid catalyst in an amount of 0.1% to 1% by weight, and used alone or as a calcium peroxide (CaO ₂ ), potassium dioxide (KO ₂ ), or potassium peroxide (K). ₂ O ₂ ), magnesium peroxide (MgO ₂ ), ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ), ozone (O ₃ ), hydrogen peroxide (H ₂ O ₂ ), sodium percarbonate (2Na ₂ CO ₃ ㅇ 3H ₂ O ₂ ), nitric acid (HNO ₃ ), sulfuric acid (H ₂ SO ₄ ), perchloric acid (HClO ₄ ), hypochlorous acid (HClO), permanganic acid (HMnO ₄ ), chromic acid (H ₂ CrO ₄ ), sodium hypochlorite ( Persulfates such as NaOCl), calcium hypochlorite (Ca (OCl) ₂ ), sodium persulfate (Na ₂ S ₂ O ₈ ) or potassium persulfate (K ₂ S ₂ O ₈ ), salts of the aforementioned compounds , Manganese oxide (Mn ₂ O ₇ ), lead dioxide (PbO ₂ ), manganese dioxide Oxidize one or more selected from the group consisting of liver (MnO ₂ ), cupric oxide (CuO), ferric chloride (FeCl ₃ ), fluorine (F), chlorine (Cl), bromine (Br) and iodine (I) Additives and iron oxides such as iron, ferrous oxide, ferric oxide, magnetite, ferrous hydroxides such as ferrous hydroxide, ferric hydroxide, iron sulfides such as iron (I) and iron (II) sulfate, iron chloride (I), a group consisting of various iron compounds such as iron chlorides such as iron (II) chloride, transition metals such as copper, manganese, cobalt and nickel, salts, oxides or hydroxides of transition metals such as copper, manganese, cobalt or nickel A material that can be used with one or more metal catalysts selected from
The sodium persulfate (Na ₂ S ₂ O ₈ ) is a powdery substance that produces sulfate radicals together with the metal catalyst, the metal catalyst is iron, ferrous oxide, ferric oxide, ferrous chloride, chloride An iron compound containing ferric ions (Fe ²⁺ ) such as ferric iron, ferrous hydroxide, ferric hydroxide, ferrous sulfate, and ferric sulfate,
The heavy metal elution agent is a Na ₃ T a material of a strong chelating bond is precipitated with Metal-T ₃ Na compound reacts with the heavy metals in an aqueous solution,
The functional clay has a function of increasing the value of the product while reducing the rejection of dark gray sludge by reminiscent of natural soils in color and texture,
The mixture for clay is 65 to 85% by weight of purified soil and 15 to 35% by weight of functional clay as a material having the same components as ordinary clay,
The OPC (Ordinary Portland Cement) is usually a portland cement, one of gray and white portland cement or a mixture thereof may be used and added for fixing heavy metals and enhancing strength,
The blast furnace slag powder is a molten non-ferrous component contained in iron ore, coke and limestone charged in the blast furnace (furnace) to produce iron (high pressure) to quench with a high-pressure water mill mill (mill) It refers to the crushed to a certain powder at, the powder also refers to more than 7,000cm ² / g,
The fly ash is a fly ash generated from by-products of less than 1% moisture content collected in an electric dust collector after combustion of pulverized coal pulverized into small particles of 0.7 mm or less in a coal-fired power plant. Saying,
The natural anhydrous gypsum has a chemical composition of CaSO ₄ , and is usually composed of bulky fibrous granular granules, and is tasteless, odorless, colorless, and nontoxic. It is a stable compound that controls the coagulation of cement (delays coagulation), promotes hardening (improves initial strength), and improves the resistance to sulfate and reduces the expansion and shrinkage after drying. ),
The soil binder is a high performance water reducing agent per 100 parts by weight of pure water (H ₂ O) as the first polycarboxylic acid-based water-soluble polymer (Polycarboxylic Copolymer (CP-WB)) and the second polycarboxylic acid-based water-soluble polymer (Polycarboxylic Copolymer: CP-WRM) 1 : 1-12 parts by weight of a mixture, selected from aluminum sulphate (Al ₂ (SO ₄ ) ₃ ) and ferrous sulfate monohydrate (FeSO ₄ OH ₂ O) or hexate (FeSO ₄ ㅇ 7H ₂ O) 5 to 15 parts by weight of any one, and 0.1 to 2 parts by weight of methyl cellulose is included, and 5 to 15 parts by weight of the clay mixture mixture, characterized in that the composition used for further purification.

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