Natural Mineral Luminite Ecological Restoration Agent and Manufacturing Method

Abstract

Prevent the rapid pH drop of the target water area by the water treatment agent, remove the aluminum heavy metal toxicity which is the cause of dementia in the water area, remove the odor-causing organic substances, prevent the economic loss caused by the loss of inorganic substances such as sand, gravel and loess necessary for natural ecological restoration together with the odor-causing organic substances during large-scale dredging, prevent the phenomenon of deeply reducing the ecological restoration ability, protect precious water resources, and restore and maintain the natural water areas such as rivers, lakes, drinking water dams, and groundwater, which are polluted daily, to clean and safe water quality levels. 【Solution means】The present invention relates to a river respiration ecological restoration agent for polluted natural water areas and a manufacturing method thereof using natural mineral lumerite, and contains 65-75% by weight of clinoptilolite, 5-15% by weight of kaolinite, 3-10% by weight of montmorillonite, 2% by weight of romontite, 2% by weight of perlite, 0.1% by weight of light rare earths, 0.01% by weight of neodymium, 0.01% by weight of dysprosium, 1-2% by weight of quartz, 5-8% by weight of pozzolan, 2-3% by weight of makuban stone, the same proportion of freeze-dried hemp, polyglutamic acid (PGA) and 0.006-0.01% by weight of coconut sap.

Description

Technical Field

[0001] The present invention relates to a river respiration ecological restoration agent for polluted natural waters using lumilite, a natural mineral, and a method for producing the same.

Background Art

[0002] The main substances of natural silicon such as zeolite and bentonite used in the treatment of most water pollution and soil pollution use a considerable amount of aluminum-based flocculant as an adjuvant to double the cation exchange capacity for the aggregation of anionic turbidity, or use an algicide, a toxic chemical substance that kills green algae.

[0003] However, as a side effect of such aluminum-based flocculants, it not only contains aluminum heavy metal toxicity, a substance that causes dementia, but also the problem of a sharp decrease in the pH of the target water area has been continuously raised. Therefore, such aluminum-based flocculants are mainly used limitedly in water purification plants or wastewater treatment plants. However, although the aluminum-based flocculants used when an algae bloom warning is issued with a sudden occurrence of more than 1 million cells / mL of toxic-induced cyanobacteria cells in natural waters such as rivers, lakes, drinking water dams, reservoirs, and groundwater have a partial flocculation effect, the numerical value of aluminum in drinking water quality far exceeds 0.2 mg / L, which is the main cause of secondary pollution due to ecological environment destruction by heavy metal aluminum.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Prevent a sharp decrease in the pH of the target water area by the water treatment agent and remove the aluminum heavy metal toxicity, a substance that causes dementia in the water area, and prevent economic losses due to the loss of inorganic substances such as sand, gravel, and loess necessary for natural ecological restoration together with malodorous organic substances during a large amount of dredging for the removal of malodorous organic substances, and prevent the phenomenon of deeply reducing the ecological restoration power, protect water resources, and restore and maintain natural waters such as rivers, lakes, drinking water dams, and groundwater, which are increasingly polluted day by day, to an ecologically clean and safe water quality.

Means for Solving the Problem

[0005] It contains 65 - 75 wt% of clinoptilolite, 5 - 15 wt% of kaolinite, 3 - 10 wt% of montmorillonite, 2 wt% of romontite, 2 wt% of perlite, 0.1 wt% of light rare earths, 0.01 wt% of neodymium, 0.01 wt% of dysprosium, 1 - 2 wt% of quartz, 5 - 9 wt% of pozzolan, 2 - 3 wt% of makubanshi, the same proportion of freeze - dried hemp, polyglutamic acid (PGA) and 0.006 - 0.01 wt% of coconut sap.

[0006] A first step of sieving the pulverized clinoptilolite, kaolinite, montmorillonite, romontite, perlite, light rare earths, neodymium, dysprosium, quartz, pozzolan, makubanshi, freeze - dried hemp, polyglutamic acid (PGA) and coconut sap at 350 - 400 mesh; a second step of stirring the powder completed in the first step at 110 - 130 °C for 5 minutes and then naturally cooling it in room - temperature air for 24 hours; a third step of stirring the powder completed in the second step at 260 - 370 °C for 5 minutes and then naturally cooling it in room - temperature air for 24 hours; a fourth step of heating the powder completed in the third step at 410 - 470 °C for 5 minutes and then naturally cooling it in room - temperature air for 24 hours; a fifth step of stirring the powder completed in the fourth step for 5 minutes, cooling it for 24 hours and then packaging it; are included.

Effect of the Invention

[0007] The present invention is free from the risk of a sharp pH drop in the target water area and aluminum heavy metal toxicity, which is a causative substance of dementia. By spraying a very small amount (100 - 200 ppm) by weight according to the pollution concentration, it not only improves the water quality of polluted natural water areas in the long and short terms, but also consists of natural minerals and has high particle strength. The composite natural silicon component of lumilite with a specific gravity of 2.4 sinks to the bottom, and due to the high surface charge of the positive ions on the surface, it adsorbs and aggregates with the suspended substances in the water and then settles by gravity to form a coating thickness sufficient to suppress the elution of nutrients and heavy metals from the bottom mud. It is deposited on the bottom floor surface about 1 mm thick, maintains a strong bridge state with the adsorbed suspended substances, and due to its high particle strength, lumilite plays a shielding role in suppressing the elution of nutrients and heavy metals from the bottom mud after sedimentation, thus suppressing re-elution. It shields odors and the elution of bottom mud, and together with the decomposition of odor-inducing organic substances, the porous form in the lumilite that has aggregated and precipitated on the bottom floor provides a habitat for microorganisms, which are aerobic bacteria that decompose the odor organic substances in the bottom mud. It plays the role of a habitat and nutrient supply source for microorganisms and aerobic bacteria, and a large number of phytomicroorganisms are propagated after precipitation. Such phytomicroorganisms act as decomposers of organic matter in the bottom mud to naturally decompose organic substances. After several months to half a year, a considerable part of the organic matter in the bottom mud is decomposed, activating the state of the bottom mud and exerting a natural restoration effect on the bottom mud. Therefore, it has excellent effects on odor improvement and bottom mud improvement and can be applied to a wide range of diverse and severely polluted water quality sites. In addition, it protects the environment simply by surface spraying on the polluted water surface instead of plant construction, and has the advantages of simple construction, low cost, and high efficiency.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Mode for Carrying Out the Invention

[0009] On the other hand, from October 12, 2021 to November 23, 2021, as a water quality improvement cooperation project in the Chanhyon Reservoir in Chanhyondong, Gangneung City, Gangwon Province, South Korea, which is managed by the Rural Development Administration of South Korea, the natural mineral lumilite, which is the natural water quality improver of the present invention, was used to improve the water quality, and the data was secured by analyzing the effects before and after the water quality improvement. As a result, the Chanhyon Reservoir showed very poor (VI) grade water quality in terms of TOC (9.4 mg / L), turbidity (2,520 NTU), total phosphorus (0.453 mg / L), and chlorophyll a (107.7 m / m3) based on September 29, 2021, and thus the situation required water quality management.

[0010] The water quality (COD, SS, TP, chlorophyll a, TOC, turbidity, transparency) of the Chanhyon Reservoir was greatly improved by using the natural mineral water treatment agent lumilite, and there was no ecological toxicity to cladocerans and luminescent bacteria. In addition, there was no impact on each biological group such as fish and benthic macroinvertebrates.

[0011] <Experimental Example> All tests were carried out with 70% by weight of clinoptilolite, 10% by weight of kaolinite, 5% by weight of montmorillonite, 2% by weight of romontite, 2% by weight of perlite, 0.1% by weight of light rare earths, 0.01% by weight of neodymium, 0.01% by weight of dysprosium, 1% by weight of quartz, 6% by weight of pozzolan, 2% by weight of makuban stone, the same ratio of freeze-dried hemp, polyglutamic acid (PGA) and coconut sap 0.007% by weight (see Figures 2 and 3).

[0012]

Table 1

[0013] <Water quality analysis results after spraying the lumilite of the present invention on the Chanhyun water storage area (21.10.12)>

[0014] Also, from October 21 to December 11, 2021, in Chuncheon Iwan Lake (a dam for drinking water source in the Seoul area), the natural water quality improver lumilite of the present invention was used as a water quality improvement cooperation project by the Korea Aquatic Restoration Association, Chuncheon City, and Korea Hydro & Nuclear Power to improve the water quality. The effects before and after the water quality improvement were objectively analyzed, and as a result of securing post - (environment) impact survey materials, in Chuncheon Iwan Lake (Kongji River), based on the standard of October 21, 2021, SS was 3.3 - 4.7 mg / L, appealing to the living environment standards of grades II - III, TP was also 0.034, 0.018, 0.038, and 0.015 mg / L, appealing to the living environment standards of grades II - III, and chlorophyll a (Chl.a) also showed around 6 μg / L. Thus, the numerical values of all water quality items were high at all locations.

[0015] With water quality improvement using the natural mineral water treatment agent lumilite, in Chuncheon Iwan Lake (Kongji River), the water quality (COD, SS, TP, chlorophyll a, TOC, turbidity, transparency) was greatly improved, and there was no ecological toxicity to cladocerans and luminescent bacteria. Furthermore, there was no impact on aquatic organisms such as medaka (see Figures 4 and 5).

[0016]

Table 2

[0017] <Water quality analysis results after spraying the lumilite of the present invention on Iwan Lake (Kongji River) (21.10.21)>

[0018] Before presenting and explaining in detail the embodiments of the invention in which the technical idea of the present application is specifically embodied, the terms or words used in the specification and claims of the present application should not be construed as being limited to their ordinary or dictionary meanings. The scope of protection of this specification should not be construed as a meaning and concept that conforms to the technical idea of the invention. Furthermore, since the objects or effects presented in the present invention do not mean that a specific embodiment should include all of them or only such effects, the scope of the rights of the present invention should not be understood as being limited thereby.

[0019] All terms used in this specification shall have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains, unless otherwise defined. Terms defined in commonly used dictionaries should be construed as consistent with the meaning in the context of the related art, and should not be construed as having an ideal or overly formal meaning not clearly defined in the present invention.

[0020] The present invention relates to a natural mineral lumilite ecological restoration agent and a manufacturing method.

[0021] The present invention will be described in detail below.

[0022] The lumilite of the present invention is selected from natural zeolites, and in particular, clinoptilolite with high adsorption capacity and ion exchange ability and excellent water purification of 65 - 75%, kaolinite which is kaolin 5 - 10%, montmorillonite which is a monoclinic mineral and a kind of clay mineral 3 - 10%, romontite which is a kind of zeolite belonging to the monoclinic system 2%, perlite made of pearlite, obsidian 2%, light rare earths 0.1%, neodymium which is a medium rare earth 0.01%, dysprosium 0.01%, quartz 1 - 2%, pozzolan which is a kind of concrete admixture composed of mineral powder such as volcanic ash 5 - 9%, makuban stone 2 - 3%, PGA (polyglutamic acid) from frozen and dried hemp, sake lees and natto in the same ratio, and sap of coconut 0.006 - 0.01%.

[0023] The lumilite of the present invention is a water purification agent produced based on clinoptilolite, a fine porous mineral that is naturally formed by the solidification of volcanic lava. When phosphorus (P) that induces the greening phenomenon and suspended substances (SS) that cause water pollution are adsorbed by ion exchange in a porous manner, the clinoptilolite that has become heavy due to the aggregation of phosphorus and suspended substances sinks to the bottom and promotes the water quality improvement effect. By utilizing the excellent adsorption characteristics of the ion-exchanged lumilite, water pollutants, which are plankton that cause green algae in the water, are adsorbed, precipitated, and removed, thereby purifying the water quality.

[0024] The present invention includes a first step of pulverizing 65 to 75% by weight of clinoptilolite, 5 to 15% by weight of kaolinite, 3 to 10% by weight of montmorillonite, 2% by weight of romontite, 2% by weight of perlite, 0.1% by weight of light rare earths, 0.001% by weight of neodymium, 0.001% by weight of dysprosium, 1 to 2% by weight of quartz, 5 to 9% by weight of pozzolan, 2 to 3% by weight of makubanite, 0.002 to 0.0033% by weight of freeze-dried hemp, 0.002 to 0.0033% by weight of freeze-dried polyglutamic acid (PGA), and 0.002 to 0.0033% by weight of freeze-dried coconut sap, and then sieving to 350 to 400 mesh. A second step of stirring the powder completed in the first step at 110 to 130 °C for 5 minutes and then naturally cooling it in normal temperature air for 24 hours. A third step of stirring the powder completed in the second step at 260 to 370 °C for 5 minutes and then naturally cooling it in normal temperature air over 24 hours. A fourth step of heating the powder completed in the third step at 410 to 470 °C for 5 minutes and then naturally cooling it in normal temperature air for 24 hours. A fifth step of stirring the powder completed in the fourth step for 5 minutes, cooling it for 24 hours, and then packaging it.

[0025] The clinoptilolite of the present invention contains 67 to 68% of silicic acid (SiO2), 11 to 14% of aluminum (Al2O3), 1 to 1.67% of iron oxide (Fe2O3), 0.6 to 0.7% of magnesium oxide (MgO), 2 to 3.42% of calcium oxide (CaO), 1 to 1.25% of sodium oxide (Na2O), 2.92% of potassium oxide (K2O), and 0.064% of zinc oxide (P2O5), and has a very large cation exchange capacity with a CEC (cation exchange capacity) of 140 to 155 (meg / 100g).

[0026] In the above clinoptilolite, when Si4+ is partially substituted by Al3+ within the tetrahedron, the balance between negative (-) and positive (+) charges is disrupted, and it shows a structurally negatively charged state. By substituting cations for the negatively charged state, the surface is substituted with a positive (+) charge state. Therefore, the cations on these surfaces can easily be substituted with other surrounding cations, resulting in a high cation substitution rate and enabling anion substitution as well.

[0027] Therefore, it is a mineral commonly used as additives in catalysts, adsorbents, detergents, etc., because it has a good substitution of nitrogen oxides present in the gas phase, detoxifies active oxygen through anion substitution, and contributes to the neutralization of pollutants, thus having the function of removing odors. It is a solid oxide with a crystalline composite oxide structure where the basic unit is TO4 centered around silicon and aluminum atoms, which is very simple. However, these can form a variety of three-dimensional bonding structures. The silicon and aluminum atoms form a regular tetrahedral coordination structure with oxygen atoms. Even when heated or exhausted, it does not break.

[0028] Also, the surface exposed on the granular surface, which is unrelated to the pores, is called the surface of the surface pores, and the surface inside the pores is called the inner surface of the pores. Even if clinoptilolite is in a very fine powder form, the inner surface of the pores is very large, and when used as an adsorbent or catalyst, it is mostly the inner surface of the pores. This does not break even when heated or exhausted.

[0029] Kaolinite is represented by the general formula Al2Si2O5(OH)4 and is variously called depending on its crystal structure. For example, it is called kaolinite, halloysite, dickite, nacrite, etc. This kaolinite helps the precipitation ability of microorganisms, is provided as a limiting source of nitrifying microorganisms in a biological reaction tank, and plays a role in assisting the activity of nitrifying microorganisms. That is, it supplies trace components necessary for the growth and energy metabolism of nitrifying microorganisms to accelerate the growth rate and promote energy metabolism. In particular, this component must be used in the treatment process while maintaining the water content at the time of injection below 35%, and the efficiency may decrease as this fraction increases. Therefore, a drying time of 2 hours or more is required. These selected components can be used as a microbial support. That is, in the case of nitrifying microorganisms, not only in the floating process but also in the process where the SRT (Sludge Retention Time) becomes long, an increase in the amount of these components can be induced so that growth is preferably affected on the attached growth microorganisms.

[0030] Montmorillonite is a kind of refractory clay and is a SiO2 - Al2O3 component system mineral containing about 59% SiO2, about 14% Al2O3, and about 3.5% Na2O. It is widely distributed in domestic feldspar or clay minerals. Due to the adsorption action and ion exchange action due to the porosity, which are characteristics of SiO2 - Al2O3 component system minerals, it has a complementary effect when used in combination with non - stone group minerals.

[0031] Also, montmorillonite does not dissolve in water but has the property of absorbing moisture in an aqueous solution and swelling to about 8 to 12 times its particle size, and through this, it has a complementary effect on pollutant adsorption. As a high - CEC clay mineral, among clay minerals, it has a wide surface area and excellent cation exchange capacity (CEC). Water can freely come out between crystal units, and expansion and contraction occur depending on the water content, and it prevents algae from re - multiplying from the sediment precipitated by the bacteriostatic action.

[0032] Romontite is calculated in cavities of basic igneous rocks such as basalt and diabase tuff, or in thermal poles, and sometimes exists as a secondary mineral in granite and gneiss. It may also occur in gold veins and other veins. Structurally, the bonds between atoms are loose, and even when the water filling the space is released by high heat, the skeleton remains intact, so it can adsorb other particulate substances. Utilizing this property, it is used as an adsorbent and as a molecular sieve for separating particulate substances of different sizes.

[0033] Perlite has a large specific surface area as an adsorbent in the reaction tank, is easy for microorganisms to adhere to, and by using light and highly porous perlite to form a carrier, microorganisms exist in a form uniformly adsorbed on the surface and internal pores of perlite, which is advantageous for the formation of microbial communities. It helps the stable growth of microorganisms and provides a carrier with excellent resistance to environmental changes such as temperature, moisture, and pH, and excellent colonization ability.

[0034] Break up perlite, obsidian, etc., and sequentially bake them at around 1000 °C to make them porous for use.

[0035] Rare earths are classified into light rare earths and medium rare earths, and light rare earths, neodymium, and dysprosium are used. They are natural clay components and have no impact on the aquatic ecosystem. By removing the pollutant phosphorus through the "adsorption and precipitation" mechanism, it prevents eutrophication in rivers and lakes and cuts off the source of greening. In particular, the phosphorus removal function does not stop in the short term and can capture the inflowing phosphorus while acting in water for 2 to 3 years, making it an economical and easy-to-use product.

[0036] Quartz is a type of silicate mineral with a silica content of 95 - 97 wt% or more. Quartz plays a role in water purification and oxygen supply in water. Also, quartz emits far-infrared rays, having effects such as deodorization and antibacterial properties, and the effect of converting water quality into alkaline water.

[0037] Pozzolan has highly reactive silica, which combines with Ca(OH)2 to form CSH.

[0038] Macuban stone is a soft stone belonging to quartz porphyry, belonging to granodiorite among igneous rocks. Its main components are anhydrous silicic acid and aluminum oxide, and it contains a small amount of ferric oxide. In addition, Macuban stone consists of 30,000 to 150,000 pores per 1 cm3 and has strong adsorbability. Therefore, it can not only adsorb and remove toxic substances and suspended substances contained in water quality, but also exchange heavy metals with ions, so it is used as a water purifier to remove harmful metals.

[0039] Frozen-dried hemp, polyglutamic acid (PGA), and coconut sap in the same ratio are derivatized and improved so that a low concentration (e.g., <500 ppm) of formaldehyde remaining by a reaction in the form of a normal phenol / aldehyde or Mannich reaction can be obtained. Alum and iron(II)(III) chloride, which are inorganic flocculants, are blended to produce a wastewater treatment agent containing plant components, which can easily flocculate and sediment refractory wastewater such as dyeing wastewater, leather wastewater, and food wastewater to form insoluble precipitates for purification. In particular, it can not only perform flocculation removal treatment on the dyes contained in the wastewater, but also bind and immobilize vegetable tannins to solid waste (shaving scrap). Typically, vegetable tannins have the advantage of having a plurality of phenolic hydroxyls that are structurally adjacent and having a special affinity for most metal ions. Therefore, vegetable tannins can be usefully applied as an adsorbent component for removing various metal ions in an aqueous solution.

Claims

1. A natural mineral LUMILITE ecological restoration agent, characterized by containing 65-75% by weight of clinoptilolite, 5-15% by weight of kaolinite, 3-10% by weight of montmorillonite, 2% by weight of romontite, 2% by weight of perlite, 0.1% by weight of light rare earths, 0.01% by weight of neodymium, 0.01% by weight of dysprosium, 1-2% by weight of quartz, 5-9% by weight of pozzolan, 2-3% by weight of makubanshi, 0.002-0.0033% by weight of freeze-dried hemp, 0.002-0.0033% by weight of freeze-dried polyglutamic acid (PGA), and 0.002-0.0033% by weight of freeze-dried coconut sap.

2. The first step of sieving the powder obtained after pulverizing 65-75% by weight of clinoptilolite, 5-15% by weight of kaolinite, 3-10% by weight of montmorillonite, 2% by weight of romontite, 2% by weight of perlite, 0.1% by weight of light rare earths, 0.01% by weight of neodymium, 0.01% by weight of dysprosium, 1-2% by weight of quartz, 5-9% by weight of pozzolan, 2-3% by weight of makubanshi, 0.002-0.0033% by weight of freeze-dried hemp, 0.002-0.0033% by weight of freeze-dried polyglutamic acid (PGA), and 0.002-0.0033% by weight of freeze-dried coconut sap to 350-400 mesh; The second step of stirring the powder completed in the first step at 110-130°C for 5 minutes and then naturally cooling it in room temperature air for 24 hours; The third step of stirring the powder completed in the second step at 260-370°C for 5 minutes and then naturally cooling it in room temperature air for 24 hours; The fourth step of heating the powder completed in the third step at 410-470°C for 5 minutes and then naturally cooling it in room temperature air for 24 hours; The fifth step of stirring the powder completed in the fourth step for 5 minutes, cooling it for 24 hours, and then packaging it; A method for manufacturing a natural mineral LUMILITE ecological restoration agent, characterized by including the above steps.

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