KR100839589B1 - Producting method of liquefied water treatment material for removal of suspend solid, nitrate, phosphate and stench - Google Patents

Abstract

A preparation method of a liquid phase water treatment agent capable of minimizing secondary pollution and sludge flotation amount while increasing a water treatment effect by simultaneously removing suspended solids, nitrogen, phosphorous, and odor is provided. A preparation method of a liquid phase water treatment agent for the removal of suspended solids, nitrogen, phosphorous, and odor comprises the steps of: crushing and milling 17 to 23 wt.% of ocher, 9 to 11 wt.% of calcite, 9 to 11 wt.% of shell, 9 to 11 wt.% of limestone, 17 to 23 wt.% of feldspathic filter sand, 9 to 11 wt.% of zeolite, 6 to 8 wt.% of germanium, 6 to 8 wt.% of allanite, and 5 to 7 wt.% of Hwawoonseok to obtain a fine powder; sequentially injecting 0.1 to 5 wt.% of K2SiF6 and 10 to 15 wt.% of CaCl2 and BaCl2 into the fine powder based on the total powder weight; firing the mixture in a heating furnace at 600 deg.C for 5 hours; acid-treating the fired powder with citric acid at 60 deg.C for 2 hours; milling the acid-treated powder into a fine powder; sorting a powder with a particle size of not more than 10 mum only from the milled powder by using a cyclone; and adding deionized water to the sorted powder and rotating the mixture at a high speed to agitate the mixture.

Description

Manufacturing Method of Liquefied Water Treatment Material for Removal of Suspend Solid, Nitrate, Phosphate and stench

1 is a SEM photograph of powder particles before mixing with pure water prepared by the present invention,

2 is a graph of zeta potential measurement of powder particles before mixing with pure water produced by the present invention.

The present invention relates to a liquid water treatment agent, and more particularly, to a method for preparing a liquid water treatment agent that minimizes secondary pollution and slurry floating while simultaneously removing suspended solids, nitrogen, phosphorus, and odor using natural minerals.

Due to the increase in population, industrial development and the improvement of living standards, the generation of various wastewaters such as living sewage, industrial wastewater, and livestock wastewater has rapidly increased, and such wastewater flows into the river, so that the river can no longer be used for various waters Or pollute the water enough to cause serious damage to biological habitat.

Recently, the problem of small village sewage purification has become a social problem. The village sewerage is a waterway-type river section with no margin for exclusion, which can be found in most small streams. There is.

The causes of water pollution include household sewage and manure discharged from homes and buildings, industrial wastewater discharged from factories and workplaces, livestock wastewater and livestock manure discharged from livestock facilities, runoff from agricultural land and forests during rainfall, camps, fishing and There are oil, sewage, food waste, various garbage, pesticides and fertilizers from farms and golf courses.

In particular, suspended solids, nitrogen and phosphorus organic substances contained in such waste water are the main culprit of destroying the ecosystem by promoting algae reproduction and growth, promoting eutrophication of rivers and lakes, and generating odors. On the other hand, these destroyed ecosystems are almost impossible to recover or require a lot of time and money to recover, so it is necessary to remove these pollutants beforehand.

However, in order to treat polluted water at present, it is necessary to have facilities for treating suspended substances, nitrogen, phosphorus, and odor, respectively, and there is a problem in that investment cost and operation cost such as construction cost, site purchase cost, etc. are excessive due to the enlargement of facilities.

In addition, the prior art causes secondary pollution due to the input of chemicals, etc., and the sewage treatment company needs post-treatment in order to remove such secondary pollution sources, which is economically burdensome. Due to the generation of a large amount of sludge, the treatment cost is excessively generated, and the micro floc needs to be separated. In addition, the method using microorganisms has problems that are inefficient and inefficient and influenced by external conditions.

In addition, water treatment must be dispersed in water for most treatments. Most water treatments are powders, which are mixed with a small amount of water and sprayed into contaminated water before being sprayed directly onto contaminated or contaminated water. do. However, even if sprayed with a water treatment agent as a powder directly on the contaminated water, or mixed with a small amount of water to make a liquid and sprayed into the contaminated water, the powder particles are not evenly dispersed in the contaminated water, there is a problem that can not achieve the desired effect .

The present invention has been made in order to solve the above problems, while simultaneously removing a floating material, nitrogen, phosphorus and odor to increase the water treatment effect, while the second method of producing a water treatment agent to minimize the pollution and sludge flotation. The purpose is to provide.

The preparation method of the liquid water treatment agent for removing suspended solids, nitrogen, phosphorus and odor according to the present invention is 17-23wt% wort clay, 9-11wt% calcite, 9-11wt% waste, 9-11wt% limestone, feldspar filter 17 Crushing and milling -23 wt%, 9-11 wt% zeolite, 6-8 wt% germanium, 6-8 wt% brown salt, 5-7 wt% calcite, to obtain a fine powder; Sequentially adding 0.1-5 wt% K ₂ SiF ₆ and 10-15 wt% CaCl ₂ and BaCl ₂ relative to the total powder to the powder; Firing at 600 ° C. for 5 hours in a heating furnace; Acid-treated the calcined powder at 60 ° C. for 2 hours with citric acid; Milling the acid treated powder into fine powder; Selecting only the powder of 10 탆 or less using the cyclone with the milled powder; The selected powder is characterized in that it comprises the step of stirring by rotating at high speed in pure water.

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Hereinafter, the method for preparing the liquid water treatment agent according to the present invention will be described in detail.

First, pulsar, calcite, waste shell, limestone, feldspar filter, zeolite, germanium, brown salt and calcite are crushed and milled to obtain fine powder. In this process, the ore is collected and crushed, and the crushed mineral is milled to a few hundred nm to several tens of micrometers using a zirconium ball mill.

The mixing ratio of each mineral is 17-23wt% maltite, 9-11wt%, pulverized 9, considering economical efficiency, raw material supply and demand, simultaneous removal of suspended nitrogen, phosphorous odor, and water treatment effect according to numerous experiments. Most preferred is -11wt%, limestone 9-11wt%, feldspar filter 17-23wt%, zeolite 9-11wt%, germanium 6-8wt%, brown salt stone 6-8wt%, pyranite 5-7wt% . If the gannite is more than 23wt%, the viscosity is high, there is an effect that the dispersion is not properly in water, if less than 17wt%, there is a problem that the aggregation is not properly, the waste shell and limestone is too high pH when the excess amount for pH adjustment, If a small amount enters, there is a problem that the pH is too low, and potassium calcite zeolite germanium gallbladder calcite does not have a removal effect on the odor of suspended solids nitrogen when entered in a small amount; . The milled fine minerals include SiO _{2 ,} CaCo ₃ , Ca (OH) ₂ , Al ₂ O ₃ , MgO, Fe ₂ O _{3 ,} TiO ₂ , and the like.

Next, K ₂ SiF ₆ , CaCl ₂ and BaCl ₂ are sequentially added to the powder. In general, the firing temperature for maximizing the specific surface area of the lumber should be 1,200 ° C. or more. Such furnaces are not common and have disadvantages in terms of cost and energy. To overcome this problem, K ₂ SiF ₆ is administered as a flux to be fired at a low temperature, which is preferably administered at 0.1-5% of the total powder weight. If it is less than 0.1%, there is no effect as a flux, and if it exceeds 5%, it is economical. In addition, CaCl ₂ and BaCl ₂ are injected at 10-15% of the total powder weight in order to disperse the powder smoothly in water. . If it is added below 10%, coagulation occurs between particles and settles, and if it exceeds 15%, the effect of cost increase is insignificant.

Next, it is calcined at 600 ° C. for 5 hours in a heating furnace. After firing, the acid is treated with citric acid (C ₆ H ₈ O ₇ ) at 60 ° C. for 2 hours and then washed with distilled water and dried. Through firing, the specific surface area of the particles is maximized, and the firing temperature can be lowered by adding a flux. Even if the firing is carried out at least 600 ° C. for 5 hours, the desired purpose can be achieved. The purpose of the acid treatment is to smooth the surface of the roughened particles after firing to prevent degradation of the inter-particle physicochemical properties, and to remove organic substances that may be introduced during some processes. It is advantageous to use a conventional weak acid such as a sphere operation, and the experimental results show that the acid treatment at 60 ℃ for 2 hours shows the optimum efficiency on the electrical conductivity after stirring with water.

The dried powder is again milled into fine powder of 10 μm or less by air jet milling or the like. Through plastic processing, the specific surface area of the particles is maximized to have excellent adsorption capacity, and through air jet milling, the powder becomes small particles of 10 μm or less, thereby maximizing the contact area in water. Figure 1 is a SEM picture of the powder so pulverized, as shown in the photograph is a powder in the form of a hexagonal structure, each has a negative charge has a strong pulling force has the effect of safety and flotation suppression of sludge.

The milled powder is selected using only the particles of 10 μm or less using cyclone. The optimum particle size (theoretical value) for securing the dispersion stability of the formulation is 0.12 ㎛ or more, but the experimental results showed that the dispersion stability was secured even from several μm to 10 μm or less. Therefore, only particles of 10 μm or less are used to make the liquid water treatment agent, and particles of 10 μm or more are fed back and regrind.

Finally, the milled fine powder is placed in deionized water and stirred at a high speed of at least 300 RPM to obtain a liquid water treatment agent. The amount of pure water is such that the milled fine powder can be sufficiently dissolved, and its concentration can be adjusted according to the degree of contamination of the waste water. In general, it is most preferable to put about 10KG of powder in 1 ton of pure water.

When explaining the water treatment action of the liquid water treatment agent according to the present invention, the removal of nitrogen in the present invention uses ammonia degassing method, the ammonia degassing method is the equilibrium equation of NH ₄ ⁺ ion and NH ₃ (Formula 1) When pH rises above 7, the equilibrium shifts to the left, and NH ₄ ⁺ ions change to NH _3, where limestone and waste angle play a role in raising the pH of the wastewater by removing the wastewater by degassing it into the atmosphere. .

_{NH 3 + H 2 O <=> NH} 4 + + OH -

In addition, abundant aluminum components, iron, calcium and magnesium components contained in the liquid water treatment agent according to the present invention are aluminum salt (Al ^{3 +} ), iron salt (Fe ^{3 +} ), calcium salt (Ca ^{2 +} ), magnesium salt (Mg ²⁺ ). These metal ions allow the phosphate to precipitate out in the form of Al (PO ₄ ), Fe (PO ₄ ), Ca ₃ (PO ₄ ) ₂ , and to aggregate organic phosphorus in the form of organic particles. Same as

_{^{Al 3 + ++ PO 4 3 -}} → Al (PO 4)

_{^{Fe 3 + + PO 4 3 -}} → Fe (PO 4)

_{^{3Ca 2 + + 2PO 4 3 -}} → Ca 3 (PO 4) 2

Coagulation reactions, on the other hand, occur through two successive kinetic processes called physical transport and chemisorption. Physical movement is the movement of the surface of one colloidal particle to the surface of another colloidal particle, which is caused by Brownian motion, shear force of the solution, gravity, and the like.

 The force acting between the two particles is inversely related to the distance between the particles, and the chemical adsorption reaction occurs in which the two particles condense due to the equilibrium of new forces formed by physical movement.

 Since the physical movement and chemical adsorption reactions occur in water, the particles of the powder undergo coagulation reactions of colloidal suspended solids, eutrophic substances, and algae.

The water treatment powder according to the present invention has a micro pore through pulverization and firing of natural materials and adsorbs and removes colloidal suspended solids.

On the other hand there is a liquid water treatment agent according to the present invention, the TiO ₂ comprises a part, such TiO ₂ is As a photocatalyst, it shows strong deodorization performance by irradiation of sunlight, fluorescent lamps, and removes the causative agents of odors such as ammonia, formaldehyde, hydrogen sulfide.

The liquid water treatment agent according to the present invention lowers the base substitution capacity by lowering the content of SiO2 compared to the existing natural zeolite, and increases the alkali wave by adding waste shells. Excellent cation exchange capacity in a wide pH range (see Figure 2).

Example

Berserk 3.6Kg, calcite 1.8Kg, pulverized stone 1.8Kg, limestone 1.8Kg, feldspar filtration 3.6Kg, zeolite 1.8Kg, germanium 1.26Kg, brown salt 1.26Kg, pyrite 1.08Kg The mill was milled to a few hundred nm to tens of micrometers. Here K ₂ SiF ₆ 0.54Kg was added and again CaCl ₂ and BaCl ₂ 1.9Kg was added. Next, the mixture was calcined at 600 ° C. for 5 hours, acid-treated with citric acid at 60 ° C. for 2 hours, washed with distilled water, dried, and air jet milled. The milled fine powder was put in pure water and stirred at a speed of 300 RPM to obtain a liquid water treatment agent.

As a result of experimenting with the liquid water treatment agent thus obtained, the following experimental results were obtained.

1 liter of sewage was collected and 1 mg of liquid water treatment agent was collected 10 minutes later. Also, to compare the effects of liquid and powder, 1 mg of powder immediately before mixing mineral powder with pure water was added after 10 minutes. Also described together.

Test Items Before treatment After treatment with liquid water treatment After treatment with powder water treatment agent COD 102.8 62.9 67.5 BOD5 337.5 67.8 71.8 T-N 129.13 84.17 106.65 T-P 11.00 2.66 4.57 Fe 1.22 1.86 1.30 Mn 0.06 0.02 0.06 Zn 0.26 0.93 0.50 Cu 0.14 0.13 0.14

 Note) It is the result of water pollution test.

As shown in the above results, it can be seen that the liquid water treatment agent has an excellent water treatment effect than the powder.

In addition, when the water treatment agent according to the present invention is used as a secondary deodorization action, the experimental results are shown in Table 2.

Test Items Elapsed time (minutes) BLANK Concentration (PPM) Sample concentration (PPM) Deodorization rate (%)   Deodorization test Early 500 500 - 30 490 65 87 60 480 45 91 90 460 30 93 120 450 25 94

(Note) 1. BLANK: Measured without sample.

     2. Test Method: KIFA-FI-1004

As can be seen from the results, the odor removal effect is also significant.

By using the liquid water treatment agent according to the present invention, it is possible to remove suspended solids, nitrogen, phosphorus and odor at the same time, while minimizing secondary pollution due to the use of natural minerals. It can be suppressed.

Claims (3)

Berserk 17-23wt%, calcite 9-11wt%, agglomerate 9-11wt%, limestone 9-11wt%, feldspar filter 17-23wt%, zeolite 9-11wt%, germanium 6-8wt%, brown salt 6- Crushing and milling 8 wt% and 5-7 wt% of calcite to obtain a fine powder; Sequentially adding 0.1-5 wt% K ₂ SiF ₆ and 10-15 wt% CaCl ₂ and BaCl ₂ relative to the total powder to the powder; Firing at 600 ° C. for 5 hours in a heating furnace; Acid-treated the calcined powder at 60 ° C. for 2 hours with citric acid; Milling the acid treated powder into fine powder; Selecting only the powder of 10 탆 or less using the cyclone with the milled powder; Method of producing a liquid water treatment agent for removing suspended solids, nitrogen, phosphorus and odors comprising the step of putting the selected powder in pure water and rotating at high speed. delete delete

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