KR20060012954A - Treatment method for fluorine-contained waste water - Google Patents
Treatment method for fluorine-contained waste water Download PDFInfo
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- KR20060012954A KR20060012954A KR1020040061688A KR20040061688A KR20060012954A KR 20060012954 A KR20060012954 A KR 20060012954A KR 1020040061688 A KR1020040061688 A KR 1020040061688A KR 20040061688 A KR20040061688 A KR 20040061688A KR 20060012954 A KR20060012954 A KR 20060012954A
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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
- C02F1/52—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
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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
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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Abstract
본 발명은, 불소함유폐수, 예를들어 제철소의 순환수, 금속표면처리공장, 반도체제조공장, 프리트기판제조공장, 세라믹제조공장, 스텐레스제조공장 등으로부터 배출되는 불소함유폐수를 정화처리하는 불소함유폐수의 처리방법에 관한 것이다.The present invention relates to a fluorine-containing wastewater for purifying fluorine-containing wastewater discharged from, for example, circulating water of a steel mill, a metal surface treatment plant, a semiconductor manufacturing plant, a frit board manufacturing plant, a ceramic manufacturing plant, a stainless steel manufacturing plant, and the like. It relates to a method for treating wastewater.
본 발명에 따른 불소함유폐수의 처리방법은, 소정의 불소함유폐수를 반응조안에 넣고 칼슘화합물을 첨가하여 폐수의 pH를 7이상으로 하여, 폐수중의 불소이온을 불화칼슘의 형태로 고형화시켜 고액분리하고, 이때 생성된 농축슬럿지의 일부를 반응조로 반송시켜 반응조 내에 생성되는 불화칼슘의 농도를 농축시킴과 동시에, 생성된 불화칼슘의 종결정효과에 의해, 불소함유폐수로부터 불소제거효율을 향상시키는 것이다. In the method for treating fluorine-containing wastewater according to the present invention, a predetermined fluorine-containing wastewater is placed in a reaction tank, calcium compound is added, and the pH of the wastewater is set to 7 or more. At this time, a part of the concentrated sludge is returned to the reaction tank to concentrate the concentration of calcium fluoride generated in the reaction tank and improve the fluorine removal efficiency from the fluorine-containing waste water by the seed crystallization effect of the produced calcium fluoride. .
불소,폐수, 칼슘화합물, 불화칼슘, 종결정효과Fluorine, wastewater, calcium compound, calcium fluoride, seed crystal effect
Description
본 발명은, 불소함유폐수, 예를들어 제철소의 순환수, 금속표면처리공장, 반도체제조공장, 프리트기판제조공장, 세라믹제조공장, 스텐레스제조공장 등으로부터 배출되는 불소함유폐수를 정화처리하는 불소함유폐수의 처리방법에 관한 것이다.The present invention relates to a fluorine-containing wastewater for purifying fluorine-containing wastewater discharged from, for example, circulating water of a steel mill, a metal surface treatment plant, a semiconductor manufacturing plant, a frit board manufacturing plant, a ceramic manufacturing plant, a stainless steel manufacturing plant, and the like. It relates to a method for treating wastewater.
기존의 불소함유폐수처리방법은, 불소함유폐수에 칼슘화합물과 알루미늄화합물 등의 1종 또는 그 이상의 약품을 가해 폐수중의 불소이온을 불화칼슘의 형태로 고형화시켜 고액분리하는 방식으로 폐수로부터 불소를 제거하는 방법이 있었다.Existing fluorine-containing wastewater treatment method adds one or more chemicals such as calcium compound and aluminum compound to the fluorine-containing wastewater to solidify the fluorine ion in the form of calcium fluoride to separate fluorine from the wastewater. There was a way to remove it.
그러나, 기존처리방법으로는, 약품사용량이 많고, 발생슬럿지량이 많은 문제점이 있었다. 또한 기존처리방법의 1단처리로는 폐수중의 불소농도를 8ppm이하로 처리하는 것이 곤란하였다.However, as the conventional treatment method, there is a problem in that the amount of chemicals used and the amount of generated slots are large. In addition, it was difficult to treat the fluorine concentration in the wastewater below 8 ppm by the single stage treatment of the existing treatment method.
이에 따라 본 발명은 기존처리방법의 문제점을 해결하기 위해 이루어진 것으로서, 본 발명의 주된 목적은 기존의 처리방법과 비교하여 불소함유폐수중의 불소를 저농도로 제거할 수 있고, 약품사용량을 적게 할 수 있으며, 슬럿지의 발생량 을 적게 할 수 있는 불소함유폐수의 처리방법을 제공함에 있다.Accordingly, the present invention has been made to solve the problems of the existing treatment method, the main object of the present invention is to remove the fluorine in the fluorine-containing waste water in a low concentration, compared to the conventional treatment method, it is possible to reduce the drug usage In addition, the present invention provides a method for treating fluorine-containing wastewater which can reduce the amount of sludge produced.
상술한 목적을 달성하기 위하여 본 발명에 따른 불소함유폐수의 처리방법은, 소정의 불소함유폐수를 반응조안에 넣고 칼슘화합물을 첨가하여 폐수의 pH를 7이상으로 하여, 폐수중의 불소이온을 불화칼슘의 형태로 고형화시켜 고액분리하고, 이때 생성된 농축슬럿지의 일부를 반응조로 반송시켜 반응조 내에 생성되는 불화칼슘의 농도를 농축시킴과 동시에, 생성된 불화칼슘의 종결정효과에 의해, 불소함유폐수로부터 불소제거효율을 향상시키는 것이다. In order to achieve the above object, the method for treating fluorine-containing wastewater according to the present invention includes placing a predetermined fluorine-containing wastewater in a reaction tank, adding a calcium compound to raise the pH of the wastewater to 7 or more, and fluorine ions in the wastewater. Solidified in the form of and separated into solids, and a part of the concentrated sludge was returned to the reaction tank to concentrate the concentration of calcium fluoride generated in the reaction tank, and at the same time, the fluorine-containing wastewater It is to improve fluorine removal efficiency.
본 발명에 따르면, 적당한 반응조 (또는 폐수처리조) 안에 처리대상인 불소함유폐수를 연속 또는 간헐적으로 주입하고, 칼슘화합물을 첨가하여 폐수의 pH를 7이상으로 조정한다. 이때 염화 제2철등의 제2철이온을 첨가해서 생성된 수산화제2철과 불화칼슘과의 공침효과를 이용하는 것이 바람직하다. 통상 제2철이온은 수용액의 형태로 사용이 가능하다. 제2철이온을 사용하는 경우, 제2철이온의 사용량에는 특별한 제한은 없지만, 생성된 CaF2mol농도에 대해 0.12∼1.2배량 정도이고, 특히 0.23∼0.47배량이 바람직하다. 사용농도가 적으면 공침효과에 의한 불소처리효율의 향상은 기대할 수 없다. 반대로 과량으로 주입하는 경우에는 처리약품량이 많아지므로 바람직하지 않다.According to the present invention, the fluorine-containing wastewater to be treated is continuously or intermittently injected into a suitable reaction tank (or wastewater treatment tank), and the pH of the wastewater is adjusted to 7 or more by adding calcium compounds. At this time, it is preferable to use the co-precipitation effect of ferric hydroxide and calcium fluoride produced by adding ferric ions such as ferric chloride. Usually ferric ions can be used in the form of an aqueous solution. In the case of using ferric ion, the amount of ferric ion used is not particularly limited, but is about 0.12 to 1.2 times the amount of CaF 2 mol, and 0.23 to 0.47 times is particularly preferable. If the concentration is small, the improvement of the fluorine treatment efficiency by the coprecipitation effect cannot be expected. On the contrary, it is not preferable to inject excessively because the amount of chemicals to be processed increases.
본 발명에 따르면, 처리대상인 불소함유폐수에 수산화칼슘 (또는 석회유)를 첨가하여 폐수의 pH를 7이상, 10∼12정도(최적범위로는 10.5∼11)로 조정하여 폐수중의 불소이온을 불화칼슘(CaF2)로 만들어 침전시킨다. According to the present invention, calcium hydroxide (or lime oil) is added to the fluorine-containing wastewater to be treated to adjust the pH of the wastewater to 7 or more and about 10 to 12 (optimum range of 10.5 to 11) to adjust the fluoride ions in the wastewater. Precipitate with (CaF 2 ).
본 발명에 따르면, 침전된 불화칼슘을 함유하는 고형분은, 예를 들면 침전조에서 통상의 방법으로 고액분리할 수 있다. 이와 같은 방법으로는 예를 들면, 침전조(Clarifier)또는 농축조(Thickener)등이 있다. 이렇게 응집처리해서 발생된 농축슬럿지는, 예를들면 침전조(Clarifier) 또는 농축조(Thicekner) 등의 방법으로 고액분리함과 동시에, 그 일부를 반응조로 반송시켜 반응조에서의 불화칼슘농도를 100ppm이상, 바람직하기로는 200ppm이상으로 존재하도록 한다. 이와같이, 본 발명에 따라 불화칼슘의 일부를 반응조로 반송시킴에 의해 종결정효과가 일어나고, 1단의 침전조에서 불소제거율이 대폭 증대되어, 처리수중의 불소농도를 8ppm이하(예를 들면 4.2∼7.2ppm)까지 처리할 수 있다.According to the present invention, the solid content containing precipitated calcium fluoride can be solid-liquid separated, for example, by a conventional method in a precipitation tank. Such a method includes, for example, a clarifier or a thickener. The concentrated sludge produced by the coagulation treatment is solid-liquid separated, for example, by a method such as a clarifier or a thickener, and a part thereof is returned to the reaction tank, whereby the calcium fluoride concentration in the reaction tank is 100 ppm or more, preferably. It is to be present in more than 200ppm. As described above, according to the present invention, a part of the calcium fluoride is returned to the reaction tank so that a seed crystal effect occurs, and the fluorine removal rate is greatly increased in the single-stage settling tank, and the fluorine concentration in the treated water is 8 ppm or less (for example, 4.2 to 7.2). ppm).
이하, 아래의 실시예를 참조하여 본 발명을 상세하게 설명한다. 그러나 본 발명의 권리범위는 이들 실시예로 한정하는 것이 아니다.Hereinafter, the present invention will be described in detail with reference to the following examples. However, the scope of the present invention is not limited to these examples.
<실시예1>Example 1
표 1에 나타낸 것과 같은 성상의 철강플랜트로부터의 불소함유폐수, 즉, 탈수폐수 주조냉각폐수, 전로집연폐수 및 압연폐수를 처리대상수로서 불소제거처리를 실시하였다.Fluorine-removing treatment was carried out using fluorine-containing waste water from the steel plant having the properties as shown in Table 1, that is, dehydration waste water casting cooling waste water, converter condensate waste water and rolled waste water.
<표1><Table 1>
처리대상수로서 상기 각 폐수를 아래와 같은 비율로 혼합하여 사용하였다. As the water to be treated, each wastewater was mixed and used in the following ratio.
탈수폐수 : 960m3/DDewatering Wastewater: 960m 3 / D
주조냉각폐수 : 1,200m3/DCasting Cooling Wastewater: 1,200m 3 / D
전로집연폐수 : 1,200m3/D Converter wastewater: 1,200m3 / D
압연폐수 : 2,400m3/DRolling Wastewater: 2,400m 3 / D
이 처리대상수의 불소함량은 15.8ppm이었다.The fluorine content of this treated water was 15.8 ppm.
반응조에 수도수 200ml를 넣고, 여기에 FeCl3 5.410ppm(Fe(OH)3로 3,560ppm상당)을 첨가하고, 5% Ca(OH)2로 pH를 10으로 맞춘 후, 이것을 FK Floc-D (강음이온성 고분자응집제)로 응집처리하였다. 처리수중의 불소함량은 0.2ppm이었다.200 ml of tap water was added to the reactor, and FeCl 3 5.410 ppm (3,560 ppm equivalent with Fe (OH) 3 ) was added thereto, and the pH was adjusted to 10 with 5% Ca (OH) 2 , followed by FK Floc-D ( Coagulated with strong anionic polymer coagulant). The fluorine content in the treated water was 0.2 ppm.
이어서 상기 농축슬럿지 80ml전량을 전술한 처리대상수 200ml (F=15.8ppm)에 투입하고, 여기에 FeCl3 200ml를 첨가하고, 5% Ca(OH)2)로 pH를 11로 맞추어 상온에서 15분간 교반시킨 후, FK Floc-D로 응집처리하였다. 이때 얻어진 처리수의 불소함량은 9.8ppm이었다. 이 경우의 불소제거율을 계산하면 아래와 같다.Subsequently, the total amount of the concentrated sludge 80ml was added to 200ml (F = 15.8ppm) of the above-mentioned treatment water, 200ml of FeCl 3 was added thereto, and the pH was adjusted to 11 with 5% Ca (OH) 2 ) at room temperature for 15 minutes. After stirring, the mixture was coagulated with FK Floc-D. The fluorine content of the treated water obtained at this time was 9.8 ppm. The fluorine removal rate in this case is calculated as follows.
처리대상폐수 200ml (F=15.8ppm)에 농축슬럿지 80ml (F=0.2ppm)를 투입했을 때의 액중 불소농도는 11.3ppm이 되므로, 불소제거율은 아래 계산식과 같이 13.3%가 된다.When the concentrated sludge 80ml (F = 0.2ppm) is added to 200ml (F = 15.8ppm) of the wastewater to be treated, the fluorine concentration in the liquid becomes 11.3ppm, so the fluorine removal rate is 13.3% as shown in the following formula.
F제거율=［(11.3-9.8)/11.3］×100=13.3%F removal rate = [(11.3-9.8) /11.3] × 100 = 13.3%
<실시예2>Example 2
수도수에 NaF 108ppm (CaF2로 100ppm상당)을 용해한 액 (F=48.0ppm) 200ml를 반응조에 넣고, 여기에 FeCl3 5,410ppm (Fe(OH)3로 3,560ppm상당)을 첨가하고, 5% Ca(OH)2로 pH를 10으로 맞추어 상온에서 15분간 교반시킨 후, FK Floc-D로 응집처리하였다. 얻어진 처리수의 불소함량은 7.6ppm이었다.200 ml of a solution (F = 48.0 ppm) in which NaF 108 ppm (100 ppm equivalent in CaF 2 ) was dissolved in tap water was added to a reactor, and 5,410 ppm FeCl 3 (3,560 ppm equivalent in Fe (OH) 3 ) was added thereto, and 5% The pH was adjusted to 10 with Ca (OH) 2 and stirred at room temperature for 15 minutes, followed by flocculation with FK Floc-D. The fluorine content of the obtained treated water was 7.6 ppm.
다음으로, 상기 농축슬럿지 80ml전량을 <실시예1>에서 사용한 처리대상수 200ml (F=15.8ppm)에 투입하고, 여기에 FeCl3 200ml를 첨가하고, 5% Ca(OH)2로 pH를 11로 맞추어 상온에서 15분간 교반시킨 후, FK Floc-D로 응집처리하였다. 얻어진 처리수의 불소함량은 8.4ppm이었다. 이 경우의 불소제거율은 계산하면 아래와 같다.Next, the entire amount of 80 ml of the concentrated sludge was added to 200 ml (F = 15.8 ppm) of water to be used in <Example 1>, and 200 ml of FeCl 3 was added thereto, and the pH was adjusted to 5% Ca (OH) 2 . After stirring at room temperature for 15 minutes, the mixture was coagulated by FK Floc-D. The fluorine content of the obtained treated water was 8.4 ppm. In this case, the fluorine removal rate is calculated as follows.
처리대상폐수 200ppm(F=15.8ppm)에 농축슬럿지 80ml (F=7.6ppm)를 투입했을 때의 액중 불소농도는 13.5ppm이 되므로 불소제거율은 아래의 계산식과 같이 37.8%가 된다.When 80ml (F = 7.6ppm) of concentrated sludge is added to 200ppm (F = 15.8ppm) of wastewater to be treated, the concentration of fluorine in the liquid is 13.5ppm, so the fluorine removal rate is 37.8% as shown in the following formula.
F제거율 = ［(13.5-8.4)/13.5］× 100=37.8%F removal rate = [(13.5-8.4) /13.5] x 100 = 37.8%
<실시예3>Example 3
수도수에 NaF 215ppm(CaF2로 200ppm상당)을 용해한 액 (F=97.0ppm) 200ml를 반응조에 넣고, 여기에 FeCl3 5,410ppm (Fe(OH)3로 3,560ppm상당)을 첨가하고 5% Ca(OH)2로 pH를 10으로 맞추어 상온에서 15분간 교반시킨 후, FK Floc-D로 응집처리하였다. 얻어진 처리수의 불소함량은 5.7ppm이었다.200 ml of a solution (F = 97.0 ppm) in which NaF 215 ppm (200 ppm equivalent in CaF 2 ) was dissolved in tap water was added to a reaction tank, and 5,410 ppm FeCl 3 (3,560 ppm equivalent in Fe (OH) 3 ) was added thereto and 5% Ca The pH was adjusted to 10 with (OH) 2 and stirred at room temperature for 15 minutes, followed by coagulation with FK Floc-D. The fluorine content of the obtained treated water was 5.7 ppm.
이어, 상기 농축슬럿지 60ml전량을 <실시예1>에서 사용한 처리대상수 200ml(F=15.8ppm)에 투입하고, 여기에 FeCl3 200ml를 첨가하고, 5% Ca(OH)2로 pH를 11로 맞추어 상온에서 15분간 교반시킨 후, FK Floc-D로 응집처리하였다. 얻어진 처리수의 불소함량은 4.7ppm이었다. 이 경우의 불소제거율은 아래와 같다.Subsequently, the total amount of 60 ml of the concentrated sludge was added to 200 ml (F = 15.8 ppm) of water to be used in <Example 1>, and 200 ml of FeCl 3 was added thereto, and the pH was adjusted to 11 with 5% Ca (OH) 2 . The mixture was stirred at room temperature for 15 minutes and then coagulated by FK Floc-D. The fluorine content of the obtained treated water was 4.7 ppm. The fluorine removal rate in this case is as follows.
처리대상폐수 200ml (F=15.8ppm)에 농축슬럿지 60ml (F=5.7ppm)를 투입했을 때의 액중 불소농도는 13.2ppm이 되므로, 불소제거율은 아래 계산식과 같이 64.3%가 된다. When 60ml (F = 5.7ppm) of concentrated sludge is added to 200ml (F = 15.8ppm) of the wastewater to be treated, the fluorine concentration in the liquid becomes 13.2ppm, so the fluorine removal rate is 64.3% as shown in the following formula.
F제거율 = ［(13.2-4.7)/13.2］×100 = 64.3%F removal rate = [(13.2-4.7) /13.2] x 100 = 64.3%
<실시예4>Example 4
반응조에 수도수 200ml를 넣고, 여기에 FeCl3 5,410ppm (Fe(OH)3로 3,560ppm상당)을 첨가하고, 5% Ca(OH)2로 pH를 10으로 맞추어 상온에서 15분간 교반시킨 후, FK Floc-D로 응집처리하였다. 얻어진 처리수의 불소함량은 0.4ppm이었다.200 ml of tap water was added to the reactor, and 5,410 ppm of FeCl 3 (3,560 ppm equivalent to Fe (OH) 3 ) was added thereto, the pH was adjusted to 10 with 5% Ca (OH) 2, and stirred at room temperature for 15 minutes. Aggregated with FK Floc-D. The fluorine content of the obtained treated water was 0.4 ppm.
다음으로, 상기 농축슬럿지 50ml전량을 <실시예1>에서 사용한 처리대상폐수로부터 압연폐수를 제외한 처리대상폐수 200ml (F=26.0ppm)에 투입하고 여기에 FeCl3 200ml를 첨가하고, 5% Ca(OH)2로 pH를 11로 맞추어 상온에서 15분간 교반시킨 후, FK Floc-D로 응집처리하였다. 얻어진 처리수의 불소함량은 4.3ppm이었다. 이 경우의 불소제거율을 계산하면 아래와 같다.Next, the entire amount of 50 ml of the concentrated sludge was added to 200 ml (F = 26.0 ppm) of the wastewater to be treated except for the rolling wastewater from the wastewater to be treated in <Example 1>, and 200 ml of FeCl 3 was added thereto, and 5% Ca ( OH) 2 , the pH was adjusted to 11, and stirred at room temperature for 15 minutes, followed by coagulation with FK Floc-D. The fluorine content of the obtained treated water was 4.3 ppm. The fluorine removal rate in this case is calculated as follows.
처리대상폐수 200ml (F=26.0ppm)에 농축슬럿지 50ml(F=0.4ppm)를 투입했을 때의 액중 불소농도는 20.9ppm이 되므로, 불소제거율은 아래 계산식과 같이 31.6%가 된다. When the concentrated sludge 50ml (F = 0.4ppm) is added to 200ml (F = 26.0ppm) of the wastewater to be treated, the concentration of fluorine in the liquid becomes 20.9ppm, so the fluorine removal rate is 31.6% as shown in the following formula.
F제거율 = ［(20.9-14.3)/20.9］×100 = 31.6%F removal rate = [(20.9-14.3) /20.9] × 100 = 31.6%
<실시예5>Example 5
수도수에 NaF 108ppm(CaF2로 100ppm상당)을 용해한 액(F=49.0ppm) 200ml를 반응조에 넣고, 여기에 FeCl35,410ppm (Fe(OH)3로 3,560ppm상당)을 첨가하고 5% Ca(OH)2로 pH를 10으로 맞추어 상온에서 15분간 교반시킨 후, FK Floc-D로 응집처리하였다. 얻어진 처리수의 불소함량은 8.6ppm이었다. 200 ml of a solution (F = 49.0 ppm) of NaF 108 ppm (100 ppm equivalent to CaF 2 ) was added to the tap water in a reaction tank, and 5,410 ppm FeCl 3 (3,560 ppm equivalent to Fe (OH) 3 ) was added thereto and 5% Ca The pH was adjusted to 10 with (OH) 2 and stirred at room temperature for 15 minutes, followed by coagulation with FK Floc-D. The fluorine content of the obtained treated water was 8.6 ppm.
다음으로, 상기 농축슬럿지 50ml전량을 <실시예4>에서 사용한 처리대상수 200ml(F=26.0ppm)에 투입하고, 여기에 FeCl3 200ml를 첨가하고, 5% Ca(OH)2로 pH를 11로 맞추어 상온에서 15분간 교반시킨 후, FK Floc-D로 응집처리하였다. 얻어진 처리수의 불소함량은 10.6ppm이었다. 이 경우의 불소제거율을 계산하면 아래와 같다.Next, the entire amount of 50 ml of the concentrated sludge was added to 200 ml (F = 26.0 ppm) of water to be used in <Example 4>, and 200 ml of FeCl 3 was added thereto, and the pH was adjusted to 5% Ca (OH) 2 . After stirring at room temperature for 15 minutes, the mixture was coagulated by FK Floc-D. The fluorine content of the obtained treated water was 10.6 ppm. The fluorine removal rate in this case is calculated as follows.
처리대상폐수 200ml(F=26.0ppm)에 농축슬럿지 50ml(F=8.6ppm)를 투입했을 때의 액중 불소농도는 22.5ppm이 되므로, 불소제거율은 아래 계산식과 같이 52.9%가 된다.When the concentrated sludge 50ml (F = 8.6ppm) is added to 200ml (F = 26.0ppm) of the wastewater to be treated, the fluorine concentration in the liquid becomes 22.5ppm, so the fluorine removal rate is 52.9% as shown in the following formula.
F제거율 = ［(22.5-10.6)/22.5］×100 = 52.9%F removal rate = [(22.5-10.6) /22.5] x 100 = 52.9%
<실시예6>Example 6
수도수에 NaF 215ppm(CaF2로 200ppm상당)을 용해한 액 (F=98.0ppm) 200ml를 반응조에 넣고, 여기에 FeCl3 5,410ppm (Fe(OH)3로 3,560ppm상당)을 첨가하고 5% Ca(OH)2로 pH를 10으로 맞추어 상온에서 15분간 교반시킨 후, FK Floc-D로 응집처리하였다. 얻어진 처리수의 불소함량은 5.9ppm이었다. 200 ml of a solution of 215 ppm NaF (200 ppm equivalent in CaF 2 ) dissolved in tap water (F = 98.0 ppm) was added to the reactor, and 5,410 ppm FeCl 3 (3,560 ppm equivalent in Fe (OH) 3 ) was added thereto, followed by 5% Ca. The pH was adjusted to 10 with (OH) 2 and stirred at room temperature for 15 minutes, followed by coagulation with FK Floc-D. The fluorine content of the obtained treated water was 5.9 ppm.
이어, 상기 농축슬럿지 50ml전량을 <실시예4>에서 사용한 처리대상수 200ml(F=26.0ppm)에 투입하고, 여기에 FeCl3 200ml를 첨가하고, 5% Ca(OH)2로 pH를 11로 맞추어 상온에서 15분간 교반시킨 후, FK Floc-D로 응집처리하였다. 얻어진 처리수의 불소함량은 7.2ppm이었다. 이 경우의 불소제거율은 계산하면 아래와 같다.Subsequently, 50 ml of the concentrated sludge was added to 200 ml (F = 26.0 ppm) of water to be used in <Example 4>, 200 ml of FeCl 3 was added thereto, and the pH was adjusted to 11 with 5% Ca (OH) 2 . The mixture was stirred at room temperature for 15 minutes and then coagulated by FK Floc-D. The fluorine content of the obtained treated water was 7.2 ppm. In this case, the fluorine removal rate is calculated as follows.
처리대상폐수 200ml (F=26.0ppm)에 농축슬럿지 50ml(F=5.7ppm)를 투입했을 때의 액중 불소농도는 22.0ppm이 되므로, 불소제거율은 아래 계산식과 같이 67.3%가 된다.When the concentrated sludge 50ml (F = 5.7ppm) is added to 200ml (F = 26.0ppm) of the wastewater to be treated, the concentration of fluorine in the liquid becomes 22.0ppm, so the fluorine removal rate is 67.3% as shown in the following formula.
F제거율 = ［(22.0-7.2)/22.0］×100 = 67.3% F removal rate = [(22.0-7.2) /22.0] × 100 = 67.3%
이상의 결과를 정리하면 표2 및 표3에 나타내는 것과 같다.The above results are summarized as shown in Tables 2 and 3.
<표2> <Table 2>
상기 표와 같이, 농축슬럿지 중의 CaF2함량이 200ppm이상 존재하면, 처리수불소농도 8ppm이하를 만족한다. As shown in the above table, if the CaF 2 content in the concentrated slot is present in 200ppm or more, the treated water fluorine concentration is 8ppm or less.
<표3> <Table 3>
상기로부터, 농축슬럿지중의 CaF2함량이 200ppm이상 존재하면 처리수불소농도 8ppm이하를 만족한다. From the above, when the CaF 2 content in the concentrated slot land is 200 ppm or more, the treated water fluorine concentration is 8 ppm or less.
상술한 바와 같이 본 발명에 따르면, 불소함유폐수중의 불소함량을 기존의 응집처리법과 비교해서, 저농도까지 제거할 수 있고, 폐수처리를 위한 약품사용량도 적고, 더구나 슬럿지 발생량도 적게 하는 효과가 있다. As described above, according to the present invention, the fluorine content in the fluorine-containing wastewater can be removed to a low concentration, compared with the existing flocculation treatment method, and the amount of chemicals used for wastewater treatment is reduced, and the sludge generation amount is also reduced. .
또한 기존의 불소고도처리는 2단처리를 하는 것이 일반적이지만, 본 발명에 따르면, 불소함유폐수의 1단에서 안정적인 처리가 가능하게 된다.
In addition, the conventional fluorine advanced treatment is generally a two-stage treatment, according to the present invention, a stable treatment in the first stage of the fluorine-containing waste water is possible.
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