KR20090119334A - Purificating process for outflow water of abandoned mine and the apparatus using them - Google Patents

Abstract

PURPOSE: A mine water purification process having a device for removing heavy metal materials and a purification device using the same are provided to offer easy usability using a narrow space efficiently. CONSTITUTION: A mine water purification process having a device for removing heavy metal materials includes the following steps of: oxidizing ionic metal materials included in mine water; collecting the oxidized metal materials; removing the oxidized metal materials after a precipitation process; filtering advanced water in which an aggregate is removed; and filtering the filtrate.

Description

Purification process using an iron manganese device and purification device using the same {purificating process for outflow water of abandoned mine and the apparatus using them}

The present invention relates to an intra-mineral water purification process having a steelmaking manganese device and a purification device using the same.

At present, the mines in the abandoned mines are leaking in large quantities, and a mining company in Gangwon-do has a daily average of about 23,000 m ³ / day of mines.

In the mine, the groundwater with suspended solids and heavy metals around the mines and mines comes out after inundating the mines within months or years, or the waste rocks and minerals containing chemical components and heavy metals used in the process of sorting minerals. Strong acidic contaminated water is leached out of the stockpiles where debris is stored. In this way, the acidic mine water generates a reddish brown or white sediment in the river, which gives a visual disgust but also contaminates heavy metal pollution, groundwater and surrounding farmland secondary due to bioconcentration.

At present, related laws are regulated to treat mine water generated from abandoned mines for artificial snow removal or to purify and discharge it by waste water treatment facilities, but most mine waters are not discharged by purified water, and treated as treated mine water. Inefficient efficiency and still contain harmful heavy metals, there is a problem that continues to pollute the river.

Common methods for purifying the mine water include natural purification and chemical flocculation sedimentation.

Natural purification scheme to stay in the gaengnaesu predetermined time to a large storage tank, suspended solids and a method of physical precipitation as a part of heavy metals, the chemical flocculation method is sodium hydroxide (NaOH), calcium hydroxide (Ca (OH) _2), alum (Alum ) Is added to react the ionized heavy metal with iron, etc., and then polymer is added to aggregate and precipitate. The natural purification method is difficult to precipitate ions and colloidal inorganic matters, and also complicated treatment of the deposited sediment, high iron content is not removed because the red color of the shaft water is not stable to use as treated water. In addition, there is a problem that is largely affected by the seasonal influence, occupy a large site and is unsuitable for applying to mines located mainly in narrow valleys.

In addition, the chemical flocculation sedimentation method is a chemical treatment method that was implemented in the 70's. The construction cost is low, but the consumption of chemicals is high, so the secondary and tertiary pollution caused by the input of chemicals and the consumption of chemicals are increased. There is a problem that the disposal cost is increased, and the operating and labor costs are high.

The above methods, as well as the above problems, consists only of drug aggregation and precipitation, there is a problem that can not completely remove the ionic dissolved metals and fine suspended substances such as iron, manganese.

The present inventors oxidize, aggregate and settle the ionic metals present in the mine water, and further include a steel manganese device to completely remove the harmful heavy metals and fine suspended solids, as well as the inclined plate settling tank The present invention was completed by minimizing the installation area of the purification device to develop a purification device that is easy to install even in a narrow space around the mine.

SUMMARY OF THE INVENTION An object of the present invention is to provide an intra-mineral water purification process having a steel manganese device.

It is another object of the present invention to provide a purification apparatus for performing an intra-mineral water purification process having a steelmaking manganese device.

The present invention provides a process for purification of in-gang water provided with a steel manganese device.

In addition, the present invention provides a purification apparatus for performing an intra-mineral water purification process having a steel manganese device.

The mine water purification process according to the present invention oxidizes and precipitates and removes a large amount of harmful heavy metals present in the mine water flowing into the stream, which is generated from the abandoned mines, and is further equipped with a steelmaking manganese device and a filter to maintain the remaining harmful heavy metals and fine particles. In addition to completely removing suspended solids, the inclined plate settling tank minimizes the installation area of the purifier, making it easy to install in narrow spaces around the mines. Also useful for.

The present invention comprises the steps of oxidizing the ionic metal material contained in the abandoned mine shaft water (step 1);

Agglomerating the metal material oxidized in step 1 (step 2);

Precipitating and removing the metal oxide aggregated in step 2 (step 3);

Primary filtration of the supernatant from which the aggregate is removed in step 3 (step 4); and

It provides a coal mine wastewater purification process comprising the step of performing a second filtration (step 5) of the filtrate first filtered in step 4.

Hereinafter, the present invention will be described in detail step by step.

Step 1 of the mine water purification process according to the present invention is a step of oxidizing the ionic metal material contained in the mine mine mine water.

In step 1, hypochlorite or calcium hydroxide is added to the mine water generated in the abandoned mine to oxidize iron ions, adjust the acidity of the mine water, and oxidize and replace the ionic metal material. can do. At this time, the aeration to perform step 1 is to increase the reaction efficiency of the gangsu water, air and chemicals. At this time, the oxidant is injected so that the redox potential is 300 to 400 mV, the acidity is 7 to 8, and the amount of residual chlorine is 0.5 to 1.5 ppm.

Step 2 according to the present invention is a step of agglomerating the metal material oxidized in step 1.

In step 2, a flocculant consisting of an aluminum salt or ferric acid salt is added to the pit water and reacted first with a rapid stirrer to agglomerate the metal oxide generated in the form of a suspended solid in step 1 into a small floc, and further add a flocculating aid. This can be done by slowing down the addition to form larger flocs.

At this time, the flocculent aid is preferably a polymer flocculation aid of polyethyleneimine or polyaluminum chloride.

Next, step 3 according to the present invention is a step of precipitating and removing the metal oxide aggregated in step 2.

Step 3 may be removed by gravity settling the floc increased in the step 2, in this case, it can be carried out using a gradient plate settling tank is reduced to 1/10 of the settling tank area compared to the conventional general settling tank.

At this time, the flocculent aid is preferably a polymer flocculation aid of polyethyleneimine or polyaluminum chloride.

Step 4 according to the present invention is a step of primary filtration of the supernatant from which the aggregates are removed in step 3.

Step 4 is a step of removing the fine suspended solids that did not precipitate in step 3, the filter layer is composed of 1 to 5 stages of anthracite / sand / gravel to be performed with high efficiency Can

Step 5 according to the present invention is a step of second filtration of the filtrate first filtered in step 4.

Step 5 is a step of removing the residual fine metal material in the first filtrate filtered in the step 4 using the steelmaking manganese device, the steelmaking manganese device may include BIRM as a medium. The BIRM is available in steelmaking and manganese by the following principle.

Seasonal

In general, iron is dissolved in the form of iron bicarbonate in high alkalinity water and is stable because an appropriate amount of CO ₂ is present.

<Scheme 1>

Fe (HCO ₃ ) ₂ ↔ FeCO ₃ + CO ₂ H ₂ O

At this time, when CO ₂ decreases, the equilibrium is broken, and the reaction proceeds to the right side, and iron carbonate is produced, which is hydrolyzed to produce ferrous hydroxide.

<Scheme 2>

FsCO ₃ + H ₂ O ↔ Fe (OH) ₂ + CO ₂

At this time, the produced Fe (OH) ₂ is easily soluble in water and easily oxidized to produce poorly soluble ferric hydroxide having a solubility of 0.01 PPM or less.

<Scheme 3>

Fe (OH) ₂ + 1 / 2O ₂ + H ₂ O Fe (OH) ₂

The oxidation reaction by FEROX is as follows.

<Scheme 4>

K ₂ Z.MnO.Mn ₂ O ₇ + 4Fe (HCO ₃ ) ₂ → K ₂ Z + 3MnO ₂ + 2Fe ₂ O ₃ ↓ + 8CO ₂ + 4H ₂ O

      (Z is zeolite)

 As above, the catalytically oxidized iron becomes insoluble and thus filtered off through the FEROX layer and separated off from the raw water.

<Manganese>

Manganese exists in water in a state very similar to iron, and generally coexists with iron or alone. However, the amount is not as high as that of iron, and the removal of manganese is almost iron-like, often with iron.

Scheme 5

K ₂ Z.MnO.Mn ₂ O ₇ + 2Mn (HCO ₃ ) ₂ → K ₂ Z + 5MnO ₂ + 4CO ₂ + 2H ₂ O

MnO ₂ ㆍ H ₂ O + Mn ^{2 +} → MnO ₂ ㆍ MnO + 2H ⁺

    Oxidation reaction is much slower than iron and precipitation is completed at pH 10

In addition, the mine water purification process according to the invention may be carried out further comprising the step of concentrating and dehydrating the precipitate removed in step 3.

In step 3, the precipitate removed by the inclined plate settling tank contains water, and thus has a large volume and weight. Therefore, the precipitate may be concentrated and dehydrated to be removed to form a dehydrated cake.

In the intra-mineral water purification process according to the present invention, the filtration of the above steps 4 to 5 may be performed by further including a backwashing process, and the generated wastewater may be refined by being injected into the step 1.

The backwashing process is a process to solve the problem of the suspended solids filtered by the filter media to reduce the filtration efficiency by closing the filter media layer, by forming a flow from the bottom of the media layer to the top at regular intervals to desorb the suspended material from the media layer. . The backwashed wastewater including the desorbed media layer may be injected into step 1 and may be refined and used without generating a separate wastewater.

In addition, the present invention is a raw water collection tank for the collection of the mine;

An oxidation tank for oxidizing the ionic metal material collected in the raw water collection tank;

A reaction tank for agglomerating the metal material oxidized in the oxidation tank;

An agglomeration tank for agglomerating the reactants reacted in the reactor;

An inclined plate settling tank for precipitating aggregates aggregated in the flocculating tank;

A device for first treating and filtering wastewater from which sediment is removed from the sedimentation tank; And

Provided is a purification apparatus for performing an intra-mineral water purification process comprising a device for performing secondary treatment and filtration of the primary treated and filtered wastewater (see FIG. 1 ).

The internal water in the raw water collection tank is sent to the oxidation tank by the raw water transfer pump, and in the reaction tank, a flocculant is added to form a small floc, and the internal water including the small floc is overflowed to the flocculation tank. The flocculation aid is added to the gangster water that flowed into the flocculation tank to form a larger floc and then flows into the gradient plate precipitation tank.

The present invention, the oxidation tank, the reaction tank and the coagulation tank can be made further provided with chemical dissolution and injection equipment. The drug dissolving and injecting equipment is a device for automatically injecting chemicals into the oxidizing tank, the reaction tank and the coagulation tank, and when the injected chemical is a liquid, it is provided with a storage tank, a chemical supply pump, and a powder if the chemical dissolving equipment Input tank, may be provided as a chemical supply pump.

Furthermore, the present invention is a concentration tank for concentrating the precipitate of the gradient plate settling tank;

Improvement tank for improving the precipitate concentrated in the concentration tank; And

It provides a purifying apparatus for performing the intra-mineral water purifying process, characterized in that it further comprises a dehydration facility for removing water from the improved precipitate.

The concentration tank, the improved tank and the dehydration facility to contain the water to minimize the weight and volume in the form of dehydrated cake precipitated weight and volume to be discarded.

In addition, there is provided a purification apparatus for performing a mine water purification process further comprises a backwash waste water storage tank for storing the backwash waste water discharged from the primary or secondary treatment and filtration device. The backwashing process is a process to solve the problem of the suspended solids filtered by the filter media to reduce the filtration efficiency by closing the filter media layer, by forming a flow from the bottom of the media layer to the top at regular intervals to desorb the suspended material from the media layer. . The backwashed wastewater including the desorbed media layer may be injected into step 1 and may be refined and used without generating a separate wastewater.

Hereinafter, the embodiment of the present invention will be described in more detail. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

< Example >

As a result of testing using the abandoned mine shaft water purification device of the present invention provided as described above, the results shown in Table 1 and FIG .

Water Purification Items Water tank Backwash Wastewater Storage Tank 2nd treatment tank Iron (ppm) 30 40 0.3 Manganese (ppm) 10 25 0.1 Suspended solids (ppm) 30 45 1.0 COD (ppm) 20 15 10 pH 5.5 to 6.5 6.5 to 7.5 6.5 to 7.5

(COD: chemical oxygen demand)

As shown in Table 1, the iron concentration of the filtrate after the final secondary treatment according to the present invention was reduced to 1/100 compared to the iron concentration of the untreated mine mine mine water, manganese also similar to iron Suspended matter was reduced to 1/30 and chemical oxygen demand was also reduced below 50%.

Furthermore, the pH of the filtrate after the final secondary treatment according to the present invention was 6.5 to 7.5, and the pH of the initial abandoned mine mine water had a weak acidity of 5.5 to 6.5. It was.

1 is a purification process according to the present invention;

2 is a water quality test table of the purified water according to the present invention.

Claims (16)

Oxidizing the ionic metal material contained in the abandoned mine water (step 1); Agglomerating the metal material oxidized in step 1 (step 2); Precipitating and removing the metal oxide aggregated in step 2 (step 3); Primary filtration of the supernatant from which the aggregate is removed in step 3 (step 4); and And filtering the primary filtrate firstly filtered in step 4 (step 5). The process according to claim 1, wherein the oxidation of step 1 is performed by adding and aeration of an oxidizing agent of hypochlorous acid or calcium hydroxide. The process of claim 1, wherein the coagulation of step 2 is performed by adding a coagulant made of aluminum salt or ferric acid salt. The method of claim 3, wherein the agglomeration of step 2 is an intra-mineralization purification process, characterized in that further adding a polymer coagulant aid consisting of polyethyleneimine or polyaluminum chloride. The process of claim 1, wherein the precipitation of step 3 is performed by precipitating and removing the aggregate of step 2 using a gradient plate settling tank. The mine shaft water purification process according to claim 5, wherein the precipitate removed in step 3 is concentrated and dehydrated. The process of claim 1, wherein the primary filtration of step 4 removes fine suspended solids by passing the supernatant from which the aggregates have been removed in step 3 through the filter media layer. The process of claim 7, wherein the media layer comprises anthracite, sand, and gravel in one to five stages. The process of claim 1, wherein the secondary filtration of step 5 removes the residual fine metal material using a steelmaking manganese device. 10. The process of claim 9, wherein the steel manganese device comprises BIRM as a medium. The process of claim 1, wherein the filtration of steps 4 to 5 further comprises a backwashing process. 12. The mine shaft water purification process according to claim 11, wherein the wastewater generated by the backwashing process is injected into step 1 and subjected to a repurification process. An oxidizing tank for oxidizing ionic metal materials in coal mine wastewater; A reaction tank for reacting the metal material oxidized in the oxidation tank; An agglomeration tank for agglomerating the reactants reacted in the reactor; An inclined plate settling tank for precipitating aggregates aggregated in the flocculating tank; A device for first treating and filtering wastewater from which sediment is removed from the sedimentation tank; An intra-mineral water purifying apparatus for performing the purifying process according to claim 1, comprising an apparatus for secondary treating and filtering the filtered and filtered wastewater. The method of claim 13, wherein the concentration tank for concentrating the precipitate of the gradient plate settling tank; Improvement tank for improving the precipitate concentrated in the concentration tank; And a dehydration facility for removing water from the improved precipitate. 15. The mine shaft water purification device according to claim 13, further comprising a backwash waste water storage tank for storing the backwash waste water discharged from the primary or secondary treatment and filtration apparatus. 16. The mine shaft water purification apparatus according to claim 15, wherein the backwash waste water is injected into the oxidation tank of claim 1.

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