KR0150331B1 - Method for the treatment of fluorine waste water using calciumchloride and iron salt - Google Patents
Method for the treatment of fluorine waste water using calciumchloride and iron saltInfo
- Publication number
- KR0150331B1 KR0150331B1 KR1019950006988A KR19950006988A KR0150331B1 KR 0150331 B1 KR0150331 B1 KR 0150331B1 KR 1019950006988 A KR1019950006988 A KR 1019950006988A KR 19950006988 A KR19950006988 A KR 19950006988A KR 0150331 B1 KR0150331 B1 KR 0150331B1
- Authority
- KR
- South Korea
- Prior art keywords
- fluorine
- iron
- concentration
- treatment
- wastewater
- Prior art date
Links
Classifications
-
- 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
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F2001/007—Processes including a sedimentation step
Abstract
불소이온의 농도가 높은 경우에는 적당량의 철화합물(염화철, 황산철 등)을 첨가하고 반응 당량의 2∼3배 정도의 염화칼슘을 첨가하여 반응시간 10분 이내에 불소이온의 농도를 20∼40mg/L까지 낮추는 1차 처리를 하고 알루미늄 화합물을 넣고 반응액의 pH를 6.0∼7.2 사이로 한 후 잔여 불소이온을 고형물과 함께 공침시켜 침강분리하거나 고분자 응집제를 주입하여 침강분리하는 불소페수 처리방법.When the concentration of fluoride ion is high, an appropriate amount of iron compound (iron chloride, iron sulfate, etc.) is added, and calcium chloride which is about 2 to 3 times the reaction equivalent is added, and the concentration of the fluorine ion is 20-40 mg / L within 10 minutes of the reaction time. A method of treating fluorine waste water by firstly lowering the solution to an aluminum compound, adjusting the pH of the reaction solution to 6.0 to 7.2, and coagulating the remaining fluorine ions with solids to settle or separate the precipitates by injecting a polymer flocculant.
Description
제1도는 본 발명을 이용한 불소폐수 처리공정도1 is a fluorine wastewater treatment process chart using the present invention
제2도는 공지방법에 의한 불소폐수 처리공정도2 is a fluorine wastewater treatment process by a known method
제3도는 본 발명에 따라 염화칼슘과 철염을 사용한 경우 불소농도 변화를 도시한 도면3 is a view showing a change in fluorine concentration when using calcium chloride and iron salt in accordance with the present invention
본 발명은 폐수처리방법에 관한 것으로, 특히 불소가 다량 함유된 폐수를 염화칼슘과 철염으로 처리하여 폐수에 함유된 불소이온의 농도를 낮추는 방법에 관한 것이다.The present invention relates to a wastewater treatment method, and more particularly, to a method for lowering the concentration of fluorine ions contained in wastewater by treating wastewater containing a large amount of fluorine with calcium chloride and iron salt.
오늘날 산업의 고도화에 따라 산업계, 특히 반도체 제조공장, 제철공장, CFC·불산 등의 불소계 화합물 제조공장, 브라운관 제조공장, 인산 또는 비료 등을 제조하는 공장 등에서 불소를 다량 함유한 폐수가 많이 발생되고 있다. 이러한 불소폐수는 환경오염이라는 심각한 문제를 야기시키고 있으며 본 발명은 종래의 이러한 산업폐수를 처리하는 방법을 획기적으로 개선한 것이다.Today, with the advancement of the industry, wastewater containing a large amount of fluorine is generated in industries such as semiconductor manufacturing plants, steel manufacturing plants, fluorine-based compound manufacturing plants such as CFC and hydrofluoric acid, CRT manufacturing plants, and phosphoric acid or fertilizer manufacturing plants. . Such fluorine wastewater causes a serious problem of environmental pollution, and the present invention is a drastic improvement of the conventional method of treating such industrial wastewater.
불소폐수의 처리방법에 관한 연구는 그 동안 많이 있어 왔으며, 가장 일반적인 방법은 수산화칼슘(Ca(OH)2)을 사용하는 방법이다. 그러나 이 방법은 불소제거효율이 낮고 반응시간이 1시간 이상으로 오래 걸리며 많은 양의 소석회를 사용해야 하고, 이에 따른 폐기물(소석회+형석)의 발생량이 많다는 단점이 있다. 또한 이러한 공지방법으로 불소폐수를 처리할 경우 처리수에 함유된 잔류불소농도를 20mg/L이하로 감소시키기가 극히 어려워 환경규제치를 초과하므로 그대로 방류할 수 있다. 따라서 공지방법은 반드시 2차 처리가 필요하다.There have been many studies on the treatment of fluorine wastewater, and the most common method is the use of calcium hydroxide (Ca (OH) 2 ). However, this method has a disadvantage in that the fluorine removal efficiency is low, the reaction time is longer than 1 hour, and a large amount of slaked lime must be used, and the amount of waste (slaked lime + fluorite) is generated accordingly. In addition, when treating the fluorine wastewater by such a known method it is extremely difficult to reduce the residual fluorine concentration contained in the treated water to less than 20mg / L, so it can be discharged as it is because it exceeds the environmental regulations. Therefore, the known method necessarily requires secondary treatment.
그외 공지된 불소폐수 처리방법으로는 염화칼슘을 이용하는 방법이 있는데 수산화칼슘 처리방법보다 슬러시 발생량이 적고 반응시간도 짧지만 이 방법 역시 많은 양의 염화칼슘 필요로하고 불소이온의 환경규제치인 15mg/L이하의 처리수를 얻기 어려워 2차 처리가 필요하다. 2차 처리로 많이 쓰는 방법은 명반을 사용하는 것으로 제거효율은 명반투입량에 비례하지만 많은 양의 폐기물이 발생되어 그 적용이 쉽지 않다(일본특개평 3-4987).Other well-known methods for treating fluorine wastewater include calcium chloride, which has a lower amount of slush and a shorter reaction time than calcium hydroxide, but this method also requires a large amount of calcium chloride and treats less than 15 mg / L of environmental regulation of fluoride ions. The number is difficult to obtain and requires secondary processing. The most commonly used method of secondary treatment is alum, and the removal efficiency is proportional to alum input, but a large amount of waste is generated, making it difficult to apply (Japanese Patent Laid-Open No. 3-4987).
또한 공지방법 중 대한민국 특허공개번호 92-624(발명의 명칭: 코우크스폐수 중 불소제거방법)가 있는데 이 방법은 코우크스 폐수에 염화제2철을 투입하여 pH3.4∼4.5에서 1차 반응시키고, 소석회를 투입하여 pH8∼9로 조절 2차반응을 시킨 다음 칼륨명반과 PAA(Poly Acryl Amide)를 가하고 pH를 5.0∼8.5로 낮추어 불소이온을 제거하는 것인바, 이 방법은 공정이 복잡하며 용해도가 낮은 소석회를 사용하므로써 반응이 느리고 많은 폐슬러지를 발생시킨다.In addition, Korean Patent Publication No. 92-624 (name of the invention: a method for removing fluorine from coke wastewater) includes ferric chloride in coke wastewater, followed by primary reaction at pH 3.4 to 4.5. In addition, slaked lime was added to adjust pH 8-9, followed by secondary reaction, potassium alum and PAA (Poly Acryl Amide) were added, and the pH was lowered to 5.0-8.5 to remove fluorine ions. The use of low calcined lime slows down the reaction and generates a lot of waste sludge.
이에 본 발명은 종래기술의 단점들을 개선한 발명으로서 본 발명의 목적은 불소가 다량 함유된 폐수를 염화칼슘과 철염으로 1차 처리한 후 알루미늄 화합물로서 2차 처리하여 폐수에 함유된 불소이온의 농도를 현저하게 낮추는 불소폐수 처리방법을 제공하기 위한 것이다.Therefore, the present invention improves the disadvantages of the prior art, and an object of the present invention is to first treat wastewater containing a large amount of fluorine with calcium chloride and iron salt, and then to treat the concentration of fluorine ions in the wastewater by secondary treatment as an aluminum compound. It is to provide a method for treating fluorine wastewater significantly lowered.
본 발명은 불소이온의 농도가 높은 경우에는 적당량의 철화합물(염화철, 황산철 등)을 첨가하고, 반응 당량의 2∼3배 정도의 염화칼슘을 첨가하여 반응시간 10분 이내에 불소이온의 농도를 20∼40mg/L까지 낮추는 1차 처리를 하고, 알류미늄 화합물을 넣고 반응액의 pH를 6.0∼7.2사이로 한 후 잔여 불소이온을 고형물과 함께 공침시켜 침강분리하거나 고분자 응집제를 주입하여 침강분리하는 불소폐수 처리방법이다.In the present invention, when the concentration of fluorine ions is high, an appropriate amount of iron compounds (iron chloride, iron sulfate, etc.) is added, and calcium chloride is added at about 2 to 3 times the reaction equivalent to increase the concentration of fluorine ions within 10 minutes. Fluorine wastewater treatment with primary treatment lowering to ~ 40mg / L, adding aluminum compound, pH of the reaction solution is between 6.0 ~ 7.2, and coagulating the remaining fluorine ions with solids to settle or separate the precipitate by injecting polymer flocculant. It is a way.
이하 첨부한 도면과 실시예를 참조하여 본 발명에 대해 보다 상세히 설명한다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings and embodiments.
[실시예1]Example 1
불소이온의 농도 381mg/L인 알칼리 폐수에 황산철(Fe2(SO4)3)을 1,000mg/L 농도가 되도록 넣었을 때 pH가 7.5였다. 여기에 염화칼슘을 반응 당량의 1∼10배까지 주입하고 150rpm에서 10분간 반응시킨 후, 침전 여과하여 얻은 처리수의 농도는 40mg/L이하로 90%이상의 불소이온 제거효과를 얻었으며, 상기 폐수에 염화철(FeCl3)을 1,000mg/L 농도로 주입하고 염화칼슘을 반응 당량의 2.5∼12.5배 투입하여 위와 동일한 조건으로 실험한 결과 그림3과 같은 결과를 얻었으며 두 경우 모두 불소이온의 제거효율은 비슷하다.The pH was 7.5 when iron sulfate (Fe 2 (SO 4 ) 3 ) was added in an amount of 1,000 mg / L to an alkaline wastewater having a concentration of fluorine ion of 381 mg / L. Here, calcium chloride was injected to 1 to 10 times the reaction equivalent weight and reacted at 150 rpm for 10 minutes, and the concentration of the treated water obtained by precipitation filtration was 40 mg / L or less to obtain 90% or more of fluorine ion removal effect. Iron chloride (FeCl 3 ) was injected at a concentration of 1,000 mg / L and calcium chloride was added at 2.5 to 12.5 times the reaction equivalent. Experimental results were obtained as shown in Figure 3. The removal efficiency of fluoride ion was similar in both cases. Do.
[비교예1]Comparative Example 1
불소이온의 농도 200mg/L인 폐수에 기존의 방법대로 소석회를 불소농도의 20배 당량만큼 주입한 경우와 본 발명 방법인 열화칼슘 3배 당량 및 염화철 100mg/L를 주입한 경우와의 불소제거효율, 슬러지 발생량, 반응시간을 각각 비교하여 표1에 나타내었다.Fluoride removal efficiency compared to the case of injecting 20 times the equivalent of fluorine concentration into the wastewater having the concentration of fluorine ion 200 mg / L and the three times the equivalent amount of calcium deterioration and 100 mg / L of iron chloride according to the present method. Table 1 compares the sludge generation and reaction time.
[실시예2]Example 2
불소이온의 농도가 174mg/L인 중성(pH=7.3)페수에 염화철(FeCl)을 800mg/L의 농도로 넣고 염화칼슘을 반응 당량의 5∼17배 주입한 후 액의 pH를 6.0으로 조절하였다. 이 액에서 고형물을 침전분리한 후 얻은 처리수의 불소농도와 불소제거효율은 표2와 같다.Iron chloride (FeCl) was added at a concentration of 800 mg / L in neutral (pH = 7.3) waste water having a fluorine ion concentration of 174 mg / L, and calcium chloride was injected 5 to 17 times the reaction equivalent, and the pH of the liquid was adjusted to 6.0. The fluorine concentration and fluorine removal efficiency of the treated water obtained after sedimentation and separation of solids from this solution are shown in Table 2.
[실시예3]Example 3
실시예1과 같이 처리하여 얻은 불소농도 38.5mg/L인 1차 처리수에 명반처리를 하여 표2와 같은 결과를 얻었으며 불소이온의 최저농도는 2.1mg/L이었다. 이 때 처리수의 pH는 명반 주입량에 따라 6.0∼7.2사이였다.The alum treatment was performed on the primary treated water having a fluorine concentration of 38.5 mg / L obtained in the same manner as in Example 1 to obtain the results shown in Table 2. The minimum concentration of fluorine ion was 2.1 mg / L. At this time, the pH of the treated water was between 6.0 and 7.2 depending on the amount of alum injection.
상기한 실시예들에서 나타난 바와 같이 본 발명에서는 불소이온의 농도가 높은 폐수의 경우 철화합물과 염화칼슘을 사용하여 1차 처리하므로써 기존의 소석회나 염화칼슘으로 처리하는 방법보다 약품의 사용량이 대폭 감소되고 이에 따른 폐슬러지 발생량 역시 현저히 감소되는 효과가 있다. 또한 반응 시간이 10분 정도로 매우 짧아 처리장치의 크기를 현저히 줄일 수 있으며 철화합물과 염화칼슘을 동일한 반응조에서 처리하므로써 공정을 단순화하고 불소이온의 농도를 20∼40mg/L 정도로 낮춘 폐수를 알루미늄 화합물로 처리하여 불소이온의 제거효율도 높이고 알루미늄 슬러지의 발생량도 줄일 수 있다.In the present invention, as shown in the above embodiments, the wastewater having a high concentration of fluorine ions is used in the first treatment with iron compounds and calcium chloride, thereby significantly reducing the amount of chemicals used compared to the conventional method of treating with lime or calcium chloride. The amount of waste sludge produced is also significantly reduced. In addition, the reaction time is very short, about 10 minutes, and the size of the treatment device can be significantly reduced. By treating the iron compound and the calcium chloride in the same reactor, the process is simplified and the wastewater with the fluorine ion concentration lowered to 20-40 mg / L is treated with aluminum compound. Therefore, the efficiency of removing fluorine ions can be improved and the amount of aluminum sludge can be reduced.
Claims (2)
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019950006988A KR0150331B1 (en) | 1995-03-30 | 1995-03-30 | Method for the treatment of fluorine waste water using calciumchloride and iron salt |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019950006988A KR0150331B1 (en) | 1995-03-30 | 1995-03-30 | Method for the treatment of fluorine waste water using calciumchloride and iron salt |
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| KR960034095A KR960034095A (en) | 1996-10-22 |
| KR0150331B1 true KR0150331B1 (en) | 1998-08-17 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000011702A (en) * | 1998-07-15 | 2000-02-25 | 가네꼬 히사시 | Fluoride Including Waste Water Processing Device and Method Capable of Processing Fluoride Including Waste Water to Have Low Concentration of Fluoride |
| KR100390159B1 (en) * | 1999-03-09 | 2003-07-04 | (주)니드켐 | Treatment agent and method for treating industrial waste-water including flourine |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19980086123A (en) * | 1997-05-31 | 1998-12-05 | 엄길용 | Foshan Wastewater Treatment Method |
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1995
- 1995-03-30 KR KR1019950006988A patent/KR0150331B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20000011702A (en) * | 1998-07-15 | 2000-02-25 | 가네꼬 히사시 | Fluoride Including Waste Water Processing Device and Method Capable of Processing Fluoride Including Waste Water to Have Low Concentration of Fluoride |
| KR100390159B1 (en) * | 1999-03-09 | 2003-07-04 | (주)니드켐 | Treatment agent and method for treating industrial waste-water including flourine |
Also Published As
| Publication number | Publication date |
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| KR960034095A (en) | 1996-10-22 |
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