KR101656825B1 - Composition for removing fluorine component from waste water and method of removing fluorine component from waste water - Google Patents

Composition for removing fluorine component from waste water and method of removing fluorine component from waste water Download PDF

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KR101656825B1
KR101656825B1 KR1020150016725A KR20150016725A KR101656825B1 KR 101656825 B1 KR101656825 B1 KR 101656825B1 KR 1020150016725 A KR1020150016725 A KR 1020150016725A KR 20150016725 A KR20150016725 A KR 20150016725A KR 101656825 B1 KR101656825 B1 KR 101656825B1
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wastewater
fluorine
acid
compound
composition
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KR1020150016725A
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Korean (ko)
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KR20160095452A (en
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최윤진
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최윤진
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5209—Regulation methods for flocculation or precipitation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The present invention relates to a composition for removing a fluorine component from wastewater, comprising an Al compound, a ferric compound and an inorganic acid, wherein a mixing molar ratio of the Al compound, the ferric compound, and the inorganic acid is respectively Al conversion, Fe conversion, 1 to 0.1: 3.6 to 1.1: 4.0 in terms of H + , and a method of removing the fluorine component, particularly the refractory fluorine component, from the wastewater using the same. By using the composition of the present invention, it is possible to efficiently and economically and quickly decompose and remove fluorine components such as hydrofluoric acid and refractory hydrofluoric acid contained in wastewater in a continuous process.

Description

The present invention relates to a composition for removing fluorine components from wastewater and a method for removing fluorine components from waste water using the composition.

The present invention relates to a composition useful for treating a fluorine compound, that is, waste water containing a fluorine component, and a waste water treatment method using the same. Particularly, the present invention relates to a composition useful for efficiently removing the fluorine component from wastewater containing fluorine components such as borofluoric acid, hydrofluoric acid, hydrofluoric acid, and fluorine ions generated during the production or processing of a glass product and a wastewater treatment method .

BACKGROUND OF THE INVENTION Fluorine compounds are widely used in various industries and have recently been widely used as an etching agent or a cleaning agent in a semiconductor manufacturing process, a solar cell manufacturing process, a flat panel display manufacturing process, and a glass manufacturing process.

Particularly, in a glass panel factory or a glass manufacturing process of a flat panel display, a large amount of hydrofluoric acid wastewater containing a large amount of borofluoric acid or hydrofluoric acid is generated due to the B 2 O 3 component or the SiO 2 component contained in the glass. For example, in a thinning process for thinning a glass panel for a flat panel display, when a B 2 O 3 component or an SiO 2 component such as a component is etched into an etchant containing hydrofluoric acid, wastewater generated from this process includes hydrofluoric acid, , Fluoric acid, and fluorine ion.

For example, in this process, the free glass reacts with hydrofluoric acid to generate hydrofluoric acid, or hydrofluoric acid, as shown in the following reaction scheme.

[Reaction Scheme 1]

SiO 2 + 6HF = H 2 SiF 6 (hydrofluoric acid) + 2H 2 O.

However, as described above, the fluorine component which relatively easily reacts with the calcium compound such as hydrofluoric acid, hydrofluoric acid, and fluorine ion can be removed by adjusting the pH and the calcium compound such as calcium hydroxide, but a poorly decomposable fluorine compound such as boron- It is not removed by the method.

The generated borohydric acid acts as a strong acid and dissociates hydrogen ions in a wide pH range and exists in the form of borofluoride ion (BF 4 - ). Borofluoride ions are very stable and can react with calcium ions or Al ions under normal conditions It is a non-degradable fluorine compound that causes serious problems in waste water treatment.

Since silicofluoric acid forms aluminum silicate when it comes into contact with an Al compound which is known to be effective as a borofluoric acid dissolution agent and a fluorine scavenger, the ability of the Al compound to decompose or coagulate is poor when hydrofluoric acid coexists with borofluoric acid. In addition, since the CaAl compound is formed from the calcium ion to be introduced for removing the subsequent dissociated fluorine ion, the fluorine ion removal performance of the Ca ion is lowered by the amount formed.

Japanese Patent Application Laid-Open No. 2007-222817 discloses a method of decomposing refractory borohydric acid by adding Zr or a Ti compound and adjusting the pH to 1 to 4 and then treating the decomposed fluorine ions by calcium hydroxide treatment in the form of calcium fluoride / RTI > However, Zr or Ti compounds are too expensive to be used in wastewater treatment, which is a problem in economy.

Korean Patent Laid-Open Publication No. 2006-0004639 discloses a method of treating a fluorine component of a simple form with calcium hydroxide or the like and then decomposing a fluorine component such as borofluoric acid at a high temperature and a high pressure under a pH of 3 to 4 (110 to 130 ° C, 1.5 kg / cm 2 to 3 kg / cm < 2 >), and then calcium hydroxide is removed by adding calcium hydroxide. However, this method shows a problem requiring a special reactor and a problem requiring a large amount of energy for high temperature treatment.

Korean Patent No. 1293283 discloses a method of decomposing borofluoric acid or the like using a compound such as Al, Fe, La, Ce, or a mixture thereof in a first reaction and then removing the decomposed fluorine component The method comprising: However, since compounds such as La and Ce are expensive metals, they are not economical unless they are reused. Al compounds have a good decomposition property, but they have a problem of lowering the removal efficiency of decomposed fluorine ions by forming aluminum silicate or CaAl compounds. There is a characteristic of low precipitation efficiency because of cohesiveness. On the other hand, when an Fe compound is used, there is a disadvantage that decomposition efficiency of borohydric acid and the like is lowered and a lot of floc is formed and the amount of discharged solid waste increases.

Therefore, it is an object of the present invention to efficiently remove fluorine components present in various types of boron hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, and fluorine ions contained in wastewater generated in a flat panel display manufacturing process or a glass manufacturing process ≪ / RTI >

Another object of the present invention is to provide a method of efficiently removing fluorine components present in various types of boron hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, and fluorine ions contained in wastewater generated in a flat panel display manufacturing process or a glass manufacturing process The method comprising:

According to an aspect of the present invention,

A composition for removing fluorine components from wastewater,

Al compounds, ferric compounds and inorganic acids,

Wherein the mixed molar ratio of the Al compound, the ferric compound, and the inorganic acid is 1: 0.1 to 3.6: 1.1 to 4.0 in terms of Al, Fe, and H +, respectively.

The fluorine component may be present in at least one form selected from the group consisting of borofluoric acid, borofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, and fluorine ion.

The Al compound may be at least one selected from aluminum chloride, polyaluminum chloride (PAC), aluminum sulfate, aluminum powder, aluminum nitrate, and ammonium aluminum sulfate.

The ferric iron compound may be at least one selected from ferric chloride, ferric sulfate, and ferric nitrate.

The inorganic acid may be at least one selected from hydrochloric acid, sulfuric acid, and nitric acid.

Preferably, the composition is an aqueous composition.

According to another aspect of the present invention,

A method for removing fluorine components from wastewater,

(a) injecting the composition according to one aspect of the present invention into the wastewater; And

(b) adjusting the conditions of the wastewater to a pH of 1 to 3 and a temperature of 30 to 100 ° C while stirring the wastewater to decompose the fluorine component into hydrofluoric acid or fluorine ions.

further comprising the step of adding an acid or an alkali to the wastewater to adjust the pH of the wastewater to a range of 1 to 3 when the pH of the wastewater after the introduction of the composition in step (b) is out of the range of 1 to 3 can do.

and then precipitating the hydrofluoric acid or fluorine ions with calcium fluoride by introducing a calcium compound into the wastewater after the step (b).

The calcium compound is preferably calcium hydroxide.

And further adding a coagulant to coagulate the residual material remaining in the wastewater after the calcium compound is charged into the wastewater and stirring the wastewater.

The step (b) is carried out in a reaction tank for 0.5 to 2 hours, the wastewater is transferred from the reaction tank to the precipitation tank, and the supernatant liquid formed in the precipitation tank is discharged as treated water by performing the precipitation step, .

Wastewater containing fluorine components such as borofluoric acid and hydrofluoric acid generated in a glass panel manufacturing process for a flat panel display or a glass manufacturing factory is difficult to be removed by a general method such as a known calcium hydroxide treatment. However, when the composition of the present invention is used, even if a large amount of boron hydrofluoric acid and hydrofluoric acid such as hydrofluoric acid are contained in the wastewater, it can be efficiently and economically and quickly decomposed and removed in a continuous process. Particularly, in a glass panel manufacturing process for flat panel displays or a glass manufacturing plant, several hundreds to thousands of tons of fluorine-containing wastewater are produced per day, and therefore, it is highly desirable from the viewpoints of environmental aspects and energy to treat them continuously at low energy costs.

Hereinafter, a composition for removing fluorine components according to the present invention and a method for removing fluorine components from wastewater using the composition will be described in detail.

A composition according to one aspect of the present invention comprises an Al compound, a ferric compound, and an inorganic acid as a composition for removing a fluorine component from wastewater. Preferably, the composition is a water-based aqueous composition.

The fluorine component contained in the wastewater may be present in the form of at least one member selected from the group consisting of borofluoric acid, borofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, and fluorine ions.

The Al compound may be at least one selected from aluminum chloride, polyaluminum chloride (PAC), aluminum sulfate, aluminum powder, aluminum nitrate, and ammonium aluminum sulfate. The Al compound can effectively decompose the poorly decomposable fluorine compounds such as borofluoric acid. As the Al compound, PAC or aluminum chloride, which does not contain sulfate ions, is more preferable since Ca ions and sulfate ions to be added in a subsequent step can react.

The ferric compound may be at least one selected from ferric chloride, ferric sulfate, and ferric nitrate. The ferric compound can simultaneously exhibit fluorochemical decomposition performance and excellent flocculation performance.

The inorganic acid may be at least one selected from hydrochloric acid, sulfuric acid, and nitric acid. Preferably, the inorganic acid may be hydrochloric acid which does not contain sulfate ions, since Ca ions and sulfate ions introduced in a subsequent process can react. The inorganic acid can prevent the precipitation reaction between the Al compound and the ferric compound and provide a proper pH to maintain a high calcium ion concentration in the calcium compound. Therefore, the inorganic acid is useful for causing calcium ions derived from a calcium compound to be introduced in a subsequent step to react with fluorine ions including fluorine ions generated by decomposition of fluorine compounds such as borofluoric acid and silicofluoric acid, thereby effectively forming a precipitate .

Therefore, by using the composition according to one aspect of the present invention, the decomposition reaction process and the precipitation reaction process are continuously performed on wastewater having a large amount of hydrofluoric acid and hydrofluoric acid, so that the fluorine component in the wastewater can be efficiently And can be decomposed and removed economically quickly.

When the composition according to one aspect of the present invention is put into the wastewater to be in an aqueous solution state, Al ions are dissociated and released from the Al compound, and the ferric ions dissociate and release the ferric ions. In the presence of these ions, borofluoric acid can be decomposed into boric acid and hydrofluoric acid according to the following reaction formula (1).

BF 4 - + 4H 2 O ↔ B (OH) 3 + 4HF + OH - (1).

Al ions are superior to boron hydrofluoric acid in the decomposition performance of borohydric acid. However, Al ions are combined with Si to form aluminum silicate, and in subsequent processes, they form CaAl compounds by bonding with Ca ions introduced for fluorine removal, The performance and the removal performance of the decomposed fluorine ions are deteriorated. Also, the coagulation and precipitation formation characteristics in the coagulation and precipitation process are lower than that of ferric ion. However, since the composition according to an aspect of the present invention contains a ferric compound capable of releasing ferric ion capable of exhibiting excellent flocculing property and exhibiting excellent flocculation property, It is possible to improve the excellent fluorine removal effect.

The mixing molar ratio of the Al compound, the ferric compound and the inorganic acid in the composition according to an aspect of the present invention may be 1: 0.1 to 3.6: 1.1 to 4.0 in terms of Al conversion, Fe conversion, and H + , respectively. The mixing molar ratio of the Al compound, ferric compound and inorganic acid is, for example, in the case of using polyaluminum chloride (PAC) as the Al compound, ferric chloride as the ferric compound, and hydrochloric acid as the inorganic acid, , And in the range of 1: 0.2 to 2.4: 1.2 to 3.0 in terms of H +, may be preferable in terms of efficiently and economically removing the fluorine component.

The composition according to one aspect of the present invention is characterized in that the mixing molar ratio of the Al compound, the ferric compound and the inorganic acid is 1: 0.1 to 3.6: 1.1 to 4.0 in terms of Al, Fe and H + . The mixing order of these three components is not particularly limited. For example, the composition according to one aspect of the present invention can be obtained by adding the Al compound and the ferric compound into an aqueous solution of an inorganic acid and stirring the mixture. The order of introducing the Al compound and the ferric compound into the aqueous solution of the inorganic acid is not particularly limited.

The composition according to one aspect of the invention is preferably an aqueous composition. At this time, the aqueous composition contains an Al compound, a ferric compound and an inorganic acid in an amount of 1: 0.1 to 3.6: 1.1 to 4.0 in terms of Al conversion, Fe conversion and H +, respectively, based on 25 to 100 moles of water (H 2 O) As shown in FIG.

Next, a method of removing fluorine components from wastewater according to another aspect of the present invention will be described in detail.

According to another aspect of the present invention, there is provided a method for removing fluorine components comprising the steps of: (a) injecting a composition according to one aspect of the present invention into wastewater; And (b) adjusting the conditions of the wastewater to a pH of 1 to 3 and a temperature of 30 to 100 ° C while stirring the wastewater to decompose the fluorine component into hydrofluoric acid or fluorine ions.

Specifically, in step (a), the composition according to one aspect of the present invention is first introduced into the wastewater. The amount of the composition according to one aspect of the present invention may be 7.0 to 8.0 grams (g) based on 400 ml of wastewater containing 550 ppm of fluorine component present in the form of borohydric acid, hydrofluoric acid, hydrofluoric acid, But is not limited thereto. Specifically, the amount of the Al compound, the ferric iron compound, and the inorganic acid in terms of Al conversion, Fe conversion, and H + in a ratio of 1: 0.1 to 3.6: 1.1 to 4.0, respectively, based on 25 to 100 moles of water (H 2 O) To prepare an aqueous composition according to one aspect of the present invention. An appropriate amount of the composition according to one aspect of the present invention can be determined by measuring the fluoride ion concentration in the treated wastewater filtrate after the specific amount of the aqueous composition of the present invention is applied to the specimen of a specific weight from the wastewater to be treated have. Specifically, an appropriate dosage of the composition according to one aspect of the present invention may be determined such that the fluoride ion concentration in the treated wastewater filtrate is less than 15 ppm (by weight), the emission standard.

In step (b), while the wastewater is stirred, the condition of the wastewater is adjusted to a pH of 1 to 3 and a temperature of 30 to 100 ° C to decompose the fluorine component into hydrofluoric acid or fluorine ion. For example, when the wastewater is adjusted to a pH of 1 to 3 and a temperature of 40 to 80 ° C while stirring the wastewater, the fluorine component can be efficiently decomposed into hydrofluoric acid or fluorine ions.

If the pH is less than 1, there is a great concern about erosion of the equipment, and if the pH exceeds 3, the degree of decomposition of the fluorine compound such as borofluoric acid may be lowered.

The temperature of the wastewater is maintained at a temperature range of 40 to 80 ° C, for example, 40 ° C to 70 ° C, specifically 50 ° C to 70 ° C or 60 ° C to 70 ° C in terms of smooth reaction progress and excessive energy consumption prevention desirable.

Under such conditions, when the wastewater in the reaction tank in the continuous type reactor is stirred for a residence time of 0.5 to 2 hours, the poorly decomposable fluorine compounds such as borohydric acid in the wastewater can be almost completely decomposed. The reaction tank retention time of the wastewater may be 0.5 to 2 hours, for example, 1 to 1.5 hours in terms of smooth reaction progress and excessive energy consumption.

In this step, when the pH of the wastewater after the composition according to one aspect of the present invention is out of the range of 1 to 3, it is preferable to adjust the pH of the wastewater to 1 to 3 by adding an acid or an alkali to the wastewater . The additional acid to be introduced may be at least one inorganic acid selected from, for example, hydrochloric acid, sulfuric acid and nitric acid. The alkali added further may be, for example, an inorganic alkali compound such as sodium hydroxide, potassium hydroxide, and calcium hydroxide.

According to another aspect of the present invention, there is provided a method for removing a fluorine component, which may further include a precipitation step of introducing a calcium compound into wastewater after step (b) to precipitate hydrofluoric acid or fluorine ions with calcium fluoride or the like.

The calcium compound may be, for example, calcium hydroxide (calcium hydroxide (Ca (OH) 2 ), calcium carbonate or calcium chloride (CaCl 2 ). For example, calcium hydroxide is added to adjust the pH of the wastewater to 6 to 8, for example about 7.

According to another aspect of the present invention, in the method for removing fluorine components, for example, the decomposition reaction in step (b) is performed in a decomposition reactor in a continuous reactor for about 0.5 to about 2 hours, To the precipitation tank in the continuous reactor to carry out the precipitation step. When the fluoride component precipitates in the precipitation reaction tank, a fluoride component-free supernatant is produced. This supernatant is discharged as treated wastewater, and the precipitated precipitate is discarded.

According to another aspect of the present invention, there is provided a method for removing a fluorine component, comprising: introducing a calcium compound as described above to adjust the pH of the wastewater to 6 to 8, for example, about 7 and then adding a flocculant Further adding to the wastewater and stirring.

The flocculant may be at least one water-soluble polymer flocculant selected from, for example, polyacrylic acid, polyacrylamide, and polyvinyl alcohol. These polymer flocculants can increase the transparency of the supernatant by flocculating and precipitating the remaining substances such as fine particles floating in the wastewater. Fluorine components including hydrofluoric acid and fluorine ions produced by the decomposition reaction in the decomposition reaction tank by the action of the calcium compound and the flocculant in the precipitation reaction tank are formed in the form of calcium fluoride (CaF 2 ) and aluminum fluoride (AlF 3 ) It coalesces and precipitates. The obtained precipitate can be separated by filtration and solid-liquid separation. The filtration method is not particularly limited, and known methods such as centrifugation, vacuum filtration, pressure filtration, gravity filtration and the like can be used.

Since the precipitate obtained above contains a lot of calcium fluoride, it can be recycled as useful industrial raw material such as cement additive for increasing the strength of cement or glaze used for manufacturing ceramics.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to further illustrate the present invention and not to limit the scope of the present invention. The scope of the present invention is determined by the matters set forth in the claims and the matters reasonably inferred therefrom.

Example  6

In a 1000 ml flask equipped with a mechanical stirrer, 208.3 g of polyaluminum chloride (PAC) at a concentration of 10% based on Al 2 O 3, 208.3 g of a 38% ferric chloride solution and 83.3 g of a 36% strength aqueous hydrochloric acid solution were mixed and stirred, 500 g of a homogeneously mixed composition was obtained.

Thus, a composition in which the mixing molar ratio of polyaluminum chloride (PAC), ferric chloride, and hydrochloric acid was 1.0 to 1.2: 2.0 in terms of Al, Fe and H +, respectively was prepared.

A 1000 ml three-necked flask equipped with a mechanical stirrer, thermometer and reflux condenser was placed in a heating mantle. 400 ml of the fluorine-containing wastewater discharged from the glass substrate etching process of the liquid crystal display device manufacturing factory was placed in the flask. This wastewater was wastewater containing 550 ppm by weight of fluorine component present in the form of borohydric acid, hydrofluoric acid, hydrofluoric acid, and fluorine ion.

7.2 g of the prepared composition was placed in the flask and the flask was heated with a heating mantle to raise the temperature of the waste liquid to about 70 캜. Stirring was continued for about 1.5 hours while maintaining this temperature.

Subsequently, 2.5 g of slaked lime was added to the flask, and the stirring was continued for about 30 minutes to neutralize and proceed with flocculation and precipitation.

Then, the fluorine concentration of the treated wastewater (filtrate) was measured based on the fluorine concentration of the supernatant by the water quality process test method.

Example  1 to 5 and 7 to 21

The procedure of Example 1 was repeated, except that the addition amount of polyaluminum chloride (PAC), ferric chloride, and a hydrochloric acid aqueous solution at a concentration of 36% was changed so as to be the composition molar ratio shown in Table 1, 5 and 7 to 21 were prepared.

A 1000 ml three-necked flask equipped with a mechanical stirrer, thermometer and reflux condenser was placed in a heating mantle. Into the flask, 400 ml of the same fluorine-containing wastewater as described in Example 6 was placed.

The flask was charged with any one of the compositions according to Examples 1 to 5 and 7 to 21 shown in Table 1, and the flask was heated with a heating mantle to raise the temperature of the waste solution to about 70 캜. Stirring was continued for about 1.5 hours while maintaining this temperature.

Subsequently, 2.5 g of slaked lime was added to the flask, and stirring was continued for about 30 minutes to neutralize and carry out agglomeration and precipitation reaction.

Then, the fluorine concentration of the treated wastewater (filtrate) was measured based on the fluorine concentration of the supernatant by the water quality process test method.

The fluorine concentrations of the wastewater treated using the compositions according to Examples 1 to 21 thus obtained are summarized in Table 1 below.

Comparative Example  1 to 11

Comparative Example 1 to Comparative Example 1 were repeated, except that the addition amounts of polyaluminum chloride (PAC), ferric chloride, and a hydrochloric acid aqueous solution having a concentration of 36% were changed so as to be the composition molar ratios shown in Table 1, 11 was prepared.

All of the compositions according to Comparative Examples 1 to 11 were either not added with at least one of the addition amounts of ferric chloride or an aqueous hydrochloric acid solution having a concentration of 36%, or the addition amounts of any of them exceeded the content ranges according to the composition of the present invention .

Then, a 1,000 ml three-necked flask equipped with a mechanical stirrer, a thermometer and a reflux condenser was placed in a heating mantle. Into the flask, 400 ml of the same fluorine-containing wastewater as described in Example 6 was placed.

In the flask, any one of the compositions according to Comparative Examples 1 to 11 shown in Table 1 was added according to the amount of the feed composition shown in Table 1, and the flask was heated with a heating mantle to raise the temperature of the waste solution to about 70 캜 . Stirring was continued for about 1.5 hours while maintaining this temperature.

Subsequently, 2.5 g of slaked lime was added to the flask, and stirring was continued for about 30 minutes to neutralize and carry out agglomeration and precipitation reaction.

Then, the fluorine concentration of the treated wastewater (filtrate) was measured based on the fluorine concentration of the supernatant by the water quality process test method.

The fluorine concentrations of the wastewater treated using the compositions according to Comparative Examples 1 to 11 thus obtained are summarized in Table 1 below.

[Method for measuring fluorine concentration of filtrate]

Fluorine concentrations of the filtrates obtained in Examples 1 to 21 and Comparative Examples 1 to 22 were measured as follows using the procedures and reagents specified in the water quality process test method.

Ultraviolet / visible light spectroscopy (ES04351.1) was used for fluoride concentration analysis. After distillation purification process for direct distillation device and sulfuric acid solution, 300 ml of sample solution was distilled and received in a 500 ml volumetric flask and filled with purified water to make 500 ml. After that, the diluted solution was developed with lanthanum alizarin complex solution, and the absorbance at 620 nm was measured and fluorine concentration was analyzed based on the calibration curve.

process
Waste water volume
(ml) Composition mole ratio input
Composition amount
(g) Treatment wastewater
Fluorine concentration
(Ppm by weight) Al compound
(Al conversion) Fe compound
(In terms of Fe) Hydrochloric acid
(H + conversion) Comparative Example 1 400 1.0 0.0 1.0 7.2 15 Example 1 400 1.0 0.1 1.1 7.2 12 Example 2 400 1.0 0.2 1.2 7.2 10 Example 3 400 1.0 0.4 1.3 7.2 9 Example 4 400 1.0 0.6 1.5 7.2 10 Example 5 400 1.0 0.9 1.7 7.2 10 Example 6 400 1.0 1.2 2.0 7.2 9 Example 7 400 1.0 1.7 2.4 7.2 11 Example 8 400 1.0 2.4 3.0 7.2 11 Example 9 400 1.0 3.6 4.0 7.2 13 Comparative Example 2 400 1.0 6.0 6.0 7.2 15 Comparative Example 3 400 1.0 13.1 12.1 7.2 17 Comparative Example 4 400 1.0 0.0 0.6 7.9 12 Comparative Example 5 400 1.0 0.2 0.8 7.9 9 Comparative Example 6 400 1.0 0.5 0.9 7.9 8 Example 10 400 1.0 0.7 1.0 7.9 5 Example 11 400 1.0 0.9 1.1 7.9 6 Example 12 400 1.0 1.2 1.3 7.9 5 Example 13 400 1.0 1.6 1.5 7.9 8 Example 14 400 1.0 2.1 1.8 7.9 12 Example 15 400 1.0 3.0 2.3 7.9 11 Comparative Example 7 400 1.0 7.2 4.5 7.9 13 Comparative Example 8 400 1.0 0.0 1.5 6.5 26 Example 16 400 1.0 0.1 1.7 6.5 22 Example 17 400 1.0 0.3 1.9 6.5 19 Example 18 400 1.0 0.5 2.2 6.5 18 Example 19 400 1.0 0.8 2.5 6.5 17 Example 20 400 1.0 1.2 3.0 6.5 15 Example 21 400 1.0 1.8 3.8 6.5 19 Comparative Example 9 400 1.0 2.8 5.0 6.5 23 Comparative Example 10 400 1.0 4.8 7.5 6.5 27 Comparative Example 11 400 1.0 10.7 15.1 6.5 28

Referring to Table 1, when the results of Examples 1 to 9 and Comparative Examples 1 to 3 in which the amount of the added composition is fixed to 7.2 g are compared, the compositions of Examples 1 to 9 according to the present invention show that the fluorine concentration of the treated wastewater is It can be seen that the fluorine concentration of the wastewater treated using the compositions of Comparative Examples 1 to 3 is higher than the waste water discharge limit of 15 ppm or more.

Comparing the results of Examples 10 to 15 and Comparative Examples 4 to 7 in which the amount of feed composition was fixed to 7.9 g, the amount of the feed composition was increased. Therefore, the results of Examples 10 to 15 and Comparative Examples 4 to 7 It can be seen that the fluorine concentration is lowered to less than 15 ppm, which is the waste water discharge limit. Nevertheless, it can be seen that the treatment with the compositions of Examples 10 to 15 can remove the fluorine component much more effectively. However, there is a problem that the fluorine removal efficiency is improved as the amount of the process-introduced drug increases, but the treatment cost increases.

It can be seen from the above results that when the same amount of the composition is added, the case where the Al compound and the ferric compound are contained in an appropriate ratio shows a favorable treatment result, rather than an excessive amount of the Al compound and the ferric compound.

Comparing the results of Examples 16 to 21 and Comparative Examples 8 to 11, in which the amount of the added composition was reduced to 6.5 g, not only the case where the compositions of Comparative Examples 8 to 11 were used, The fluorine concentration of the treated wastewater was more than 15 ppm, which is the waste water discharge limit.

From the above experimental results, the amount of the composition according to one aspect of the present invention is 7.0 to 8.0 grams (based on 400 ml of wastewater containing 550 ppm of fluorine component present in the form of borohydric acid, hydrofluoric acid, hydrofluoric acid, g), specifically about 7.0 to 7.9 grams (g).

Example  22 to 34

Based on the above experimental results, a composition having a composition of a relatively good molar ratio of fluorine treatment capacity in terms of Al: converted to Fe: converted to H + in a ratio of 1.0: 1.2: 2.0 was prepared according to the method described in Example 6, Were investigated through the following experiments.

For this purpose, a 1,000 ml three-necked flask equipped with a mechanical stirrer, thermometer and reflux condenser was placed in a heating mantle. Into the flask, 400 ml of the same fluorine-containing wastewater as described in Example 6 was placed. Subsequently, 7.2 g of each of the above compositions was placed in the flask, the flask was heated with a heating mantle, and the wastewater was heated to the respective temperatures shown in Table 2 below and allowed to react for each indicated time. At this time, the pH of the wastewater was changed. The pH of the wastewater was adjusted using 36% hydrochloric acid or 10% NaOH.

Subsequently, 2.5 g of slaked lime was added to the flask, and stirring was continued for about 30 minutes to neutralize and carry out agglomeration and precipitation reaction.

Thereafter, the concentration of the supernatant was measured based on the water quality test method, and the fluorine concentration of the treated wastewater (filtrate) was measured.

The fluorine concentrations of the wastewater treated using the compositions according to Examples 22 to 34 thus obtained are summarized in Table 2 below.

Waste water volume
(ml) input
Composition amount
(g) reaction
pH Temperature
(° C) gun
Heating time
(HR) Treatment wastewater
Fluorine concentration
(ppm) Example 22 400 7.2 1.5 40 1.5 15 Example 23 400 7.2 1.5 50 1.5 14 Example 24 400 7.2 1.5 60 1.5 10 Example 25 400 7.2 1.5 70 1.5 9 Example 26 400 7.2 1.5 80 1.5 3 Example 27 400 7.2 1.5 70 0.5 22 Example 28 400 7.2 1.5 70 One 14 Example 29 400 7.2 1.5 70 2 5 Example 30 400 7.2 1.5 70 2.5 3 Example 31 400 7.2 1.0 70 1.5 9 Example 32 400 7.2 2.0 70 1.5 10 Example 33 400 7.2 2.5 70 1.5 10 Example 34 400 7.2 3.0 70 1.5 10

Referring to Table 2, it can be seen that the higher the reaction temperature, the higher the decomposition rate of the fluorine component per unit time, the lower the fluorine concentration in the treated wastewater, and the lower the reaction temperature, the greater the reaction time (residence time) . It can be seen that the pH of the reaction tank does not greatly affect the treatment performance within the range of 1 to 3.

From this, it was found that adjusting the conditions of the wastewater to a pH of 1 to 3, a total heating time of 1 hour to 2 hours, and a reaction bath temperature of 40 to 80 ° C is economically and effectively effective in removing fluorine components.

Claims (12)

A composition for removing fluorine components from wastewater,
Al compounds, ferric compounds and inorganic acids,
Wherein the mixing molar ratio of the Al compound, the ferric compound, and the inorganic acid is 1: 0.1 to 3.6: 1.1 to 4.0 in terms of Al, Fe, and H + , respectively. The composition according to claim 1, wherein the fluorine component is present in at least one form selected from the group consisting of borofluoric acid, borofluoric acid, hydrofluoric acid, hydrofluoric acid, hydrofluoric acid, and fluorine ion. The composition according to claim 1, wherein the Al compound is at least one selected from aluminum chloride, polyaluminum chloride (PAC), aluminum sulfate, aluminum powder, aluminum nitrate, and ammonium aluminum sulfate. The composition according to claim 1, wherein the ferric compound is at least one selected from ferric chloride, ferric sulfate, and ferric nitrate. The composition according to claim 1, wherein the inorganic acid is at least one selected from hydrochloric acid, sulfuric acid, and nitric acid. The composition of claim 1, wherein the composition is an aqueous composition. A method for removing fluorine components from wastewater,
(a) injecting the composition according to any one of claims 1 to 6 into the wastewater; And
(b) adjusting the conditions of the wastewater to a pH of 1 to 3 and a temperature of 30 to 100 ° C while stirring the wastewater to decompose the fluorine component into hydrofluoric acid or fluorine ions. The method according to claim 7, wherein, in step (b), when the pH of the wastewater after the introduction of the composition is out of the range of 1 to 3, an acid or an alkali is added to the wastewater to adjust the pH of the wastewater to 1 to 3 Further comprising the step of: The removing method according to claim 7, further comprising a precipitation step of introducing a calcium compound into the wastewater after step (b) to precipitate the hydrofluoric acid or fluorine ions into calcium fluoride. The method of claim 9, wherein the calcium compound is calcium hydroxide. 10. The removing method according to claim 9, further comprising the step of adding a coagulant to coagulate the residual material remaining in the wastewater after the introduction of the calcium compound into the wastewater and stirring the wastewater. The method according to claim 9, wherein the step (b) is performed in a reaction tank for 0.5 to 2 hours, the wastewater is transferred from the reaction tank to a precipitation tank, and the precipitation step is performed to discharge the supernatant, Characterized in that the precipitation is discarded.
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