KR101026715B1 - The fluorine ion and cyanide complexes and free cyanide a drug and the waste water treatment method which uses this - Google Patents

The fluorine ion and cyanide complexes and free cyanide a drug and the waste water treatment method which uses this Download PDF

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KR101026715B1
KR101026715B1 KR1020080035478A KR20080035478A KR101026715B1 KR 101026715 B1 KR101026715 B1 KR 101026715B1 KR 1020080035478 A KR1020080035478 A KR 1020080035478A KR 20080035478 A KR20080035478 A KR 20080035478A KR 101026715 B1 KR101026715 B1 KR 101026715B1
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cyanide
wastewater
fluorine
cyan
copper sulfate
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KR20090109962A (en
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김상수
김동민
박주형
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한수케미칼 주식회사
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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
    • 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
    • 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
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular 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
    • C02F1/58—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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/586—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing ammoniacal nitrogen
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • 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
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/18—Cyanides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH

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  • Hydrology & Water Resources (AREA)
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  • Inorganic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

본 발명은 폐수 중에 함유되어 있는 불소이온 및 시안이온들을 제거하기 위한 불소, 시안이온 제거제 및 이를 이용한 폐수 처리방법에 관한 것이다.The present invention relates to a fluorine, a cyan ion remover for removing fluorine ions and cyan ions contained in the waste water and a wastewater treatment method using the same.

그 목적하는 바는 불소이온과 시안이온이 함께 들어있는 폐수에 알루미늄화합물 및 알루미늄혼합물을 이용하여 불소이온을 제거하고, 시안이온제거제에 있어a) 황산구리 및 황산구리화합물 또는 혼합물 및 b) 황산구리 및 황산구리화합물과 황산철화합물과의 혼합물, c) 황산구리 및 황산구리화합물과 염화철화합물과의 혼합물, d)아황산수소나트륨을 이용하여 폐수 중에 함유되어 있는 시안착화합물 및 유리시안이온을 동시에 제거할 수 있어 비용절감 및 폐수처리공정의 단순화의 효과를 가진 불소이온 및 시안이온제거제 및 불소이온 및 시안이온함유폐수를 처리하는 방법을 제공하고자 하는데 목적이 있다.The purpose is to remove fluorine ions by using aluminum compound and aluminum mixture in wastewater containing fluorine ion and cyan ion, and in cyanide remover a) copper sulfate and copper sulfate compound or mixture and b) copper sulfate and copper sulfate compound C) a mixture of copper sulfate and iron sulfate compounds, c) a mixture of copper sulfate and iron chloride compounds, and d) sodium bisulfite to remove cyanide complexes and free cyanide in the wastewater at the same time. It is an object of the present invention to provide a method for treating fluorine and cyanide scavenger and fluorine and cyanate-containing wastewater having the effect of simplifying the treatment process.

또한 본 발명은 불소이온을 제거하기 위해 폐수에 불소이온제거제를 주입하고 폐수의 pH를 5~9로 제어하고, 시안이온을 제거하여 폐수를 처리하는 방법에 있어서 상기 폐수의 pH를 4~6으로 제어한 후 상기 용액을 이용하여 폐수를 처리하는 것을 특징으로 하는 시안이온 제거제를 이용한 폐수처리방법에 관한 것을 요지로 한다.In addition, the present invention injects a fluoride ion remover into the wastewater to remove the fluorine ions, and controls the pH of the wastewater to 5 ~ 9, in the method of treating the wastewater by removing the cyan ion to a pH of the wastewater to 4-6 The present invention relates to a wastewater treatment method using a cyan ion remover, characterized in that after the control, the wastewater is treated using the solution.

불소이온제거제, 시안착화합물제거제, 유리시안제거제, 폐수. Fluoride ion remover, cyanide complex remover, free cyanide remover, waste water.

Description

불소이온 및 시안착화합물과 유리시안 제거제 및 이를 이용한 폐수 처리방법{THE FLUORINE ION AND CYANIDE COMPLEXES AND FREE CYANIDE A DRUG AND THE WASTE WATER TREATMENT METHOD WHICH USES THIS}FLUORINE ION AND CYANIDE COMPLEXES AND FREE CYANIDE A DRUG AND THE WASTE WATER TREATMENT METHOD WHICH USES THIS}

본 발명은 공업용수 혹은 산업폐수에 포함되어있는 불소이온과 시안을 제거하기 위해 사용되는 제거용액 및 이를 이용한 폐수처리 방법에 관한 것으로, 보다 상세하게는 알루미늄 화합물을 이용하여 불소이온을 제거한 폐수에 황산구리와 아황산수소나트륨 또는 황산구리와 일정비율로 혼합한 황산철화합물 또는 염화철화합물과 아황산수소나트륨을 이용하여 시안착화합물 및 유리시안을 제거하여 수질환경보전법에서 규정하는 배출기준 즉, 불소 15ppm이하, 시안이온 및 시안화합물을 1ppm 이하로 폐수를 처리하는 방법에 관한 것이다.The present invention relates to a removal solution used to remove fluorine ions and cyanide contained in industrial water or industrial wastewater, and a wastewater treatment method using the same. More specifically, copper sulfate in wastewater from which fluorine ions are removed using an aluminum compound. And cyanide complexes and free cyanide are removed using ferric sulfate or ferric chloride compound and sodium bisulfite mixed with sodium hydrogen sulfite or copper sulfate at a constant ratio, ie less than 15 ppm of fluorine, cyan ion and The present invention relates to a method for treating wastewater with cyanide compounds of 1 ppm or less.

종래의 금속도금공장, 도시가스 생산공장, 철강제 조공장의 고로, 제강공정 및 코크스제조, 냉각공정에서 유출되는 불소이온과 시안이온 함유 폐수를 처리하는 방법으로는 집수조(1)에 집수 된 폐수(8)를 반응조(2)로 옮겨서 소석회 및 수산화칼슘 등의 1종 이상의 칼슘화합물을 가하여 불소이온을 불용화한 후 제 1응집조(3)에서 고체-액체 분리하여 불소이온을 제거하고, 제 2반응조(4)에서 차아염소산소다(NaOCl)를 가하여 시안이온을 불용화하여 제 2응집조(5)에서 고체-액체 분리에 의해 제거하여 방류조(6)으로 옮겨지는 방법으로 희토류화합물을 이용한 침전법, 이온교환수지와 다공질 알루미나를 이용한 흡착법 등이 주로 사용되고 있다.Wastewater collected in the sump (1) is a method of treating fluorine and cyanide-containing wastewater discharged from blast furnaces, steelmaking and coke production, and cooling processes in conventional metal plating plants, city gas production plants, and steel manufacturing plants. Transfer (8) to the reaction tank (2), add one or more calcium compounds such as hydrated lime and calcium hydroxide to insolubilize the fluorine ions, and solid-liquid separation in the first agglomeration tank (3) to remove the fluorine ions. Precipitate using rare earth compounds by adding sodium hypochlorite (NaOCl) in the reactor (4), insolubilizing the cyan ion, removing it by solid-liquid separation in the second flocculation tank (5), and transferring it to the discharge tank (6). The adsorption method using ion exchange resin and porous alumina is mainly used.

이중 이온교환수지와 다공질 알루미나를 이용한 흡착법은 교환용량의 한계 때문에 대용량 폐수에는 적용이 어렵고, 희토류 화합물을 이용한 침전법은 수소이온농도(pH)를 조절하기 위해 황산 및 가성소다 용액이 다량 필요하고 불소제거는 탁월한 효율을 나타내지만 높은 농도의 유리시안 및 시안착화합물은 처리효율이 미흡한 단점이 있다.Adsorption using double ion exchange resin and porous alumina is difficult to apply to large-capacity wastewater due to the limitation of exchange capacity. Precipitation using rare earth compound requires much sulfuric acid and caustic soda solution to control hydrogen ion concentration (pH) and fluorine. Removal shows excellent efficiency, but high concentrations of free cyanide and cyanide complexes have disadvantages of poor treatment efficiency.

또한 소석회 및 수산화칼슘 등의 1종 이상의 칼슘 화합물과 차아염소산소다(NaOCl)를 이용한 방법은 불소이온 제거를 위해 많은 양의 소석회 및 수산화칼슘이 투입되므로 슬러지 발생량이 많은 단점과 2번의 여과분리과정을 거치는 2단계 처리과정으로 처리공정이 복잡하고 설비가 거대해지는 문제점이 있어 설비의 운전조작 및 유지관리에 많은 어려움이 있고, 또한 시안이온 처리를 위해 투입되는 차 아염소산소다는 상온에서 스스로 분해되어 염소가스를 다량 발생시키는 성질이 있어 저장, 투입과정에서 발생되는 염소가스에 의해 공기의 오염 및 설비부식, 악취발생, 작업자 호흡기 장애의 원인으로 작용하는 등의 많은 문제점이 있다.In addition, the method using one or more calcium compounds, such as hydrated lime and calcium hydroxide, and sodium hypochlorite (NaOCl), has a large amount of sludge and calcium hydroxide in order to remove fluorine ions. Due to the complicated treatment process and enormous facilities, the operation process and maintenance of the facility are difficult.In addition, the hypochlorite hypochlorite, which is injected for cyan ion treatment, decomposes itself at room temperature to produce chlorine gas. Due to the nature of generating a large amount of chlorine gas generated during storage and input process, there are many problems such as acting as a cause of air pollution and equipment corrosion, odor generation, worker respiratory failure.

또한 불소이온 제거를 위해 소석회 및 수산화칼슘 등의 1종 이상의 칼슘화합물과 시안이온 제거를 위해 황산철화합물 또는 염화철화합물을 이용한 방법은 불소이온 제거를 위해 많은 양의 소석회 및 수산화칼슘이 투입되므로 슬러지 발생량이 많은 단점과 2번의 여과분리과정을 거치는 2단계 처리과정으로 처리공정이 복잡하고 설비가 거대해지는 문제점이 있어 설비의 운전조작 및 유지관리에 많은 어려움이 있고, 폐수 중의 시안이온이 유리시안과 철 및 카드늄, 닉켈, 구리, 코발트 등의 중금속과 결합하여 난분해성 시안착화합물로 존재하는 폐수에서는 황산철화합물 또는 염화철화합물은 유리시안과는 반응하여 헥사훼로시안([Fe(CN)]⁴)으로 결합되어 난분해성 시안착화합물로 변화될 뿐 많은 양의 황산철화합물 및 염화철화합물을 투입해도 황산철화합물 및 염화철화합물 사용량 증가에 따라 전체의 시안이온의 감소효과는 극히 미미한 문제가 있다.In addition, the method of using one or more calcium compounds such as hydrated lime and calcium hydroxide to remove fluorine ions and ferrous sulfate or iron chloride compounds to remove cyanide has a large amount of sludge generated because a large amount of hydrated lime and calcium hydroxide is added to remove fluorine ions. Disadvantage and two-stage treatment process through two filtration separation process, which makes the process complicated and enormous equipment, which makes it difficult to operate and maintain the facility. Cyan ions in the waste water are free cyanide, iron and cadmium. In wastewater containing hardly decomposable cyanide compounds in combination with heavy metals such as nickel, nickel, copper, and cobalt, ferrous sulfate compounds or ferric chloride compounds react with free cyanide and bind to hexaferocyanate ([Fe (CN)] ⁴). It is changed into a hardly decomposable cyanide compound, and sulfuric acid can be Reduction of the total cyanide ions according to the compound and increase iron compound amount may be extremely subtle problem.

또한 불소이온 제거를 위해 소석회 및 수산화칼슘 등의 칼슘 화합과 시안이온 제거를 위해 황산구리와 아황산수소나트륨을 이용한 방법이 사용되고 있는데 이 방법은 불소이온제거를 위해 많은 양의 소석회 및 수산화칼슘이 투입되므로 슬러지 발생량이 많은 단점과 시안이온 제거의 pH조건을 형성하기 위해 많은 양의 황산이 사용되므로 저장, 운반에 비용이 소요되고 반응조의 부식이 심화되는 단점이 있다.In addition, a method using calcium sulfate and calcium hydroxide such as slaked lime and calcium hydroxide to remove fluorine ions and copper sulfate and sodium bisulfite is used to remove cyanide. This method uses a large amount of slaked lime and calcium hydroxide to remove fluorine ions. Many disadvantages and the amount of sulfuric acid is used to form the pH condition of the cyan ion removal, there is a disadvantage in that the cost of storage and transportation, and the corrosion of the reactor is intensified.

상기 방법들 중 하나의 예를 들면 제철 고로 공정에서 불소 및 시안을 함유 한 폐수의 처리에 사용되는 방법은 도 1에 나타난 공정도와 같이 40~60ppm의 불소와 25~45ppm의 시안을 함유하는 폐수를 집수조(1)에 집수하고, 제 1반응조(2)에서 수산화칼슘을 투입하여 pH10 ~ pH11로 조정하여 불소를 불화칼슘(CaF2)로 결합시킨 후 제 1응집조(3)에서 응집제를 투입하여 불소화합물을 침전시켜 불소농도를 15ppm이하까지 낮추고 상등액은 제 2반응조(4)로 보낸 다음, 황산을 이용하여 pH8~pH9로 조정한 후 차아염소산소다를 첨가하여 시안을 시안산(CNO-)형태로 변화시킨 다음 제 2응집조(5)에 보내 응집제를 첨가하여 시안산을 침전시켜 시안농도를 1ppm 이하로 낮추는 방법을 사용하고 있다. In one of the above methods, for example, the method used for the treatment of wastewater containing fluorine and cyanide in a steelmaking blast furnace process includes wastewater containing 40 to 60 ppm fluorine and 25 to 45 ppm cyan as shown in FIG. Collecting hydride in the water collecting tank (1), adding calcium hydroxide in the first reaction tank (2) to adjust the pH to 10 ~ 11, combining fluorine with calcium fluoride (CaF2), and then adding a flocculant in the first coagulation tank (3) to fluorine compound Precipitate to lower the fluorine concentration to 15ppm or less, and send the supernatant to the second reactor (4), adjust the pH to 8 ~ pH9 with sulfuric acid, and change the cyan to cyanic acid (CNO-) form by adding sodium hypochlorite. Then, it is sent to the second agglomeration tank (5) to add a flocculant to precipitate the cyanic acid to lower the cyan concentration to 1ppm or less.

상기한 종래의 방법은 불소이온 및 시안이온의 처리공정이 2번의 여과, 분리과정을 거치는 2단계 처리과정으로 처리과정이 복잡하고, 불소이온 제거에 사용되는 수산화칼슘에 의해 발생하는 다량의 슬러지 처리에 인력과 비용이 많이 소요되고, 차아염소산소다가 공기 중에 분해되면서 발생하는 염소가스에 의해 설비부식이 심화되고 악취로 인한 공기오염 및 작업환경이 열악해 지는 문제가 있다.The conventional method described above is a two-stage process in which the fluorine ion and cyan ion treatment process undergoes two filtration and separation processes, and the treatment process is complicated, and a large amount of sludge treatment generated by calcium hydroxide used for fluorine ion removal is performed. It takes a lot of manpower and cost, and there is a problem that the corrosion of equipment is intensified by the chlorine gas generated by the decomposition of sodium hypochlorite in the air, and the air pollution and the working environment due to odor are poor.

또 하나의 예로서 도 2에 나타난 공정도와 같이 40~60ppm의 불소와 25~45ppm의 시안을 함유하는 폐수(8)를 집수조(1)에 집수하고 제 1반응조(2)에서 수산화칼슘을 투입하여 pH10~pH11로 조정하여 불소를 불화칼슘(CaF2)로 결합시킨 후 제 1응집조(3)에서 응집제를 투입하여 불소화합물을 침전시켜 불소농도를 15ppm이하까지 낮추고 상등액은 제 2반응조(4)로 보낸 다음 황산을 이용하여 pH를 6이하로 조정한 후 황산철화합물을 주입하여 시안이온을 제거하는 방법을 사용하고 있다. As another example, wastewater 8 containing 40 to 60 ppm of fluorine and 25 to 45 ppm of cyan is collected in the collecting tank 1 and calcium hydroxide is introduced in the first reactor 2 as shown in the process diagram shown in FIG. fluorine is combined with calcium fluoride (CaF2) by adjusting ~ pH11, and a flocculant is added in the first agglomeration tank (3) to precipitate the fluorine compound. Next, the pH is adjusted to 6 or less using sulfuric acid, and then iron oxide compounds are injected to remove cyan ions.

상기한 종래의 방법은 불소이온 및 시안이온의 처리공정이 2번의 여과분리과 정을 2단계 처리과정으로 처리과정이 복잡하고 설비운전조작 및 유지관리에 인력과 비용이 많이 소요되고 발생되는 불소이온 제거에 사용되는 수산화칼슘에 의해 발생하는 다량의 슬러지 처리에 많은 어려움이 있고, 황산철화합물로는 유리시안만이 헥사훼로시안([Fe(CN)]⁴)으로 변화되어 난용성 시안착화합물로 폐수 중에 잔존하므로 폐수 중의 시안제거 반응효율은 저하되어 황산철화합물 사용량 증가에 따라 시안이온은 감소하지 않는 문제점이 있다.In the conventional method described above, the fluorine ion and cyan ion treatment process has two filtration separation processes in two stages, and the treatment process is complicated, and manpower and cost are required to operate and maintain the equipment. There is a lot of difficulty in treating a large amount of sludge caused by calcium hydroxide, which is converted into hexaferocyanate ([Fe (CN)] ⁴) as an iron sulfate compound. Since the reaction efficiency of cyanide removal in the waste water remains, the cyan ion does not decrease as the amount of ferrous sulfate compound is increased.

본 발명은 적정농도의 알루미늄화합물과 적정농도의 황산구리 또는 황산구리와 일정비율로 혼합한 황산철화합물 또는 염화철화합물과 적정농도의 아황산수소나트륨을 순차적으로 가하여 폐수 중에 함유되어 있는 불소 이온 및 시안착화합물과 유리시안을 제거할 수 있는 최적의 농도조건과 pH조건을 선정한 불소 및 시안이온 제거용액을 제공하며 또한 본 발명은 상기 용액을 이용하여 폐수를 처리하는 방법을 제공한다. The present invention sequentially adds an aluminum compound at an appropriate concentration, an iron sulfate compound or an iron chloride compound mixed with an appropriate concentration of copper sulfate or copper sulfate, and an appropriate concentration of sodium bisulfite in order to fluorine ions and cyanide compounds contained in the wastewater. The present invention provides a fluorine and cyan ion removal solution in which the optimal concentration and pH conditions for removing cyanide are selected. The present invention also provides a method for treating wastewater using the solution.

본 발명에 의한 새로운 불소 및 시안이온 처리제 및 처리방법에 준하여 폐수를 처리할 경우 1단계 처리과정만으로 시안이온을 방류기준 이하로 제거할 수 있어 이에 따라 불소 및 시안처리공정의 단순화를 꽤하여 설비운전 및 관리에 필요한 인력및 비용을 절감하는 효과가 제공된다.When treating wastewater according to the new fluorine and cyan ion treatment agent and treatment method according to the present invention, it is possible to remove cyan ions below the discharge standard by only one step treatment process, thus simplifying the process of fluorine and cyanide treatment. And the effect is to reduce the manpower and costs required for management.

본 발명은 상기 목적을 달성하기 위하여 0.5~20%알루미늄 화합물 또는 혼합 수용액, 물 및 불가피한 불순물로 이루어진 불소 이온 제거제를 제공하고 황산구리와 아황산수소나트륨을 시안 이온제거제로 포함할 수 있으며, 황산구리와 황산철화합물과의 혼합물, 황산구리와 염화철화합물과의 혼합물과 아황산수소나트륨 수용액을 시안이온 제거제로 포함할 수 있다.The present invention provides a fluorine ion remover consisting of 0.5 to 20% aluminum compound or mixed aqueous solution, water and inevitable impurities to achieve the above object, and may include copper sulfate and sodium hydrogen sulfite as cyanide remover, copper sulfate and iron sulfate A mixture with a compound, a mixture with a copper sulfate and an iron chloride compound, and an aqueous sodium hydrogen sulfite solution may be included as a cyanide remover.

또한 본 발명은 불소 이온 제거방법에 있어서 a단계는, 폐수에 알루미늄화합물 또는 혼합물을 가하여 pH9이하, pH5이상로 조절하는 단계를 포함할 수 있다,In addition, in the present invention, step a in the method for removing fluorine ions may include adjusting aluminum to waste water by adding an aluminum compound or mixture to pH 9 or below and pH 5 or above.

또한 본 발명은 시안이온 제거방법에 있어서 b단계는, 상기 a단계 폐수에 산성물질을 가하여 pH6이하로 조절하는 단계를 포함할 수 있다.In addition, the present invention, step b in the cyan ion removal method may include the step of adjusting the pH 6 or less by adding an acidic substance to the waste water of step a.

또한 본 발명은 시안이온 제거방법에 있어서 c단계는, 상기 a단계 폐수에 pH6이하로 조정하기 위해 산성물질을 투입하는 대신 시안이온제거제인 황산구리와 아황산수소나트륨을 주입하여 pH가 6 이하로 조절하는 단계를 포함할 수 있다.In the present invention, step c in the cyan ion removal method is to adjust the pH to 6 or less by injecting copper sulfate and sodium bisulfite as cyanide remover instead of adding an acidic substance to adjust the pH 6 or less in the waste water of the step a It may include a step.

또한 본 발명은 시안이온 제거 방법에 있어서 d단계는, 상기 b단계의 폐수에 황산구리와 아황산수소나트륨을 가하여 교반하는 단계를 포함할 수 있다.In addition, the d step in the present invention cyan ion removal method, may include the step of adding copper sulfate and sodium hydrogen sulfite to the waste water of the b step.

또한 본 발명은 시안이온 제거방법에 있어서 e단계는, 상기 b단계의 폐수에 황산구리와 황산철화합물과의 혼합물과 아황산수소나트륨을 가하여 교반하는 단계를 포함 할 수 있다.In addition, in the present invention, the step e in the method for removing cyan ions may include adding a mixture of copper sulfate and iron sulfate compound and sodium hydrogen sulfite to the waste water of step b.

또한 본 발명은 시안이온 제거방법에 있어서 f단계는, 상기 b단계의 폐수에 황산구리와 염화철화합물과의 혼합물과 아황산수소나트륨을 가하여 교반하는 단계를 포함 할 수 있다.In the present invention, step f in the cyan ion removal method may include adding a mixture of copper sulfate and ferric chloride compound and sodium hydrogen sulfite to the waste water of step b.

또한 본 발명은 시안 이온제거방법에 있어서 g단계는, 상기 c, d, e, f단계의 폐수에 소정의 고분자 응집제를 투입하여 생성된 슬러지를 응집하여 침강시키고 액상의 폐수에 가성소다를 투입하여 pH6.5~pH7.5로 조절하여 배출하는 단계를 포함하여 폐수를 처리하는 것을 특징으로 하는 불소이온 및 시안이온 제거용액을 이용한 폐수처리방법에 관한 것이다.In the present invention, step c in the cyan ion removal method, a predetermined polymer flocculant is added to the wastewater of the c, d, e, f stage to aggregate and settle the sludge produced by adding a caustic soda to the liquid wastewater It relates to a wastewater treatment method using a fluorine ion and a cyan ion removal solution, characterized in that to treat the wastewater, including the step of controlling to pH6.5 ~ pH7.5 to discharge.

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명에 의한 불소, 시안이 함유된 폐수를 처리하는 과정은 도 3에 나타난 공정도와 같이 집수조(1)에 집수 된 폐수에 알루미늄 함유량 7%인 염화알루미늄을 투입하여 pH5~9로 조절하면 하기의 반응식 1에 의거하여 불소가 15ppm이하로 제거되고 다시 2차 반응조(4)로 보내진 폐수에 5~10%황산구리수용액과 6.6~13.1%아황산수소나트륨 수용액을 가하여 하기 반응식 2에 의거하여 난분해성 시안착화합물과 유리하는 시안이온을 1ppm 이하로 제거할 수 있게 된다.In the process of treating wastewater containing fluorine and cyan according to the present invention, aluminum chloride having 7% aluminum content is added to the wastewater collected in the sump tank 1 to adjust the pH to 5-9 as follows. According to Scheme 1, 5-10% copper sulfate aqueous solution and 6.6 ~ 13.1% sodium hydrogen sulfite aqueous solution were added to the wastewater removed to 15 ppm or less after fluorine was removed to the secondary reactor (4). It is possible to remove cyan ions and advantageous to less than 1ppm.

또한, 도 4에 나타난 공정도와 같이 집수조(1)에 집수 된 폐수에 알루미늄 함유랑 7%인 염화알루미늄을 투입하여 pH 5~9로 조절하면 하기의 반응식 1에 의거하여 불소가 15ppm이하로 제거되고 다시 2차 반응조(4)로 보내진 폐수에 5~10%황산구리수용액과 1~10%황산철화합물 수용액을 혼합한 용액 또는, 5~10%황산구리수용액과 1~10%염화철화합물 수용액을 혼합한 용액과 6.6~13.1%아황산수소나트륨 용액을 가하여 하기 반응식 2에 의거하여 난분해성 시안착화합물과 유리하는 시안이온을 1ppm이하로 제거할 수 있게 된다. In addition, as shown in the process diagram shown in FIG. 4, when aluminum chloride containing 7% aluminum chloride is added to the wastewater collected in the water collecting tank 1 and adjusted to pH 5-9, fluorine is removed to 15 ppm or less based on Scheme 1 below. Again, a solution containing 5-10% copper sulfate solution and 1-10% ferrous sulfate solution or 5-10% copper sulfate solution and 1-10% ferric chloride solution And 6.6 ~ 13.1% sodium hydrogen sulfite solution can be added to remove the hardly decomposable cyanide compound and advantageous cyan ions below 1 ppm based on the following Scheme 2.

[반응식 1]Scheme 1

AICI3 + 3HF- = AIF3AICI3 + 3HF- = AIF3

[반응식 2]Scheme 2

CN + CN² = CuCN ---- 유리시안과 황산구리와 반응CN + CN² = CuCN ---- reaction with free cyanide and copper sulfate

CN + Fe² = [Fe(CN)]⁴ ---- 유리시안과 황산철 또는 염화철과 반응CN + Fe² = [Fe (CN)] ⁴ ---- Reacts with free cyanide and iron sulfate or iron chloride

CuSO₄+ 2NaHSO₄= Na₂SO₃+ H₂SO₄+ Cu² ---- Cu 환원반응CuSO₄ + 2NaHSO₄ = Na₂SO₃ + H₂SO₄ + Cu² ---- Cu Reduction

[Fe(CN)]⁴-+ 2Cu²= Cu₂(Fe(CN)] ---- 시안착화합물과 반응 [Fe (CN)] ⁴ - + 2Cu² = Cu₂ (Fe (CN)] ---- cyan complex and the reaction

[Co(CN)]⁴-+ 2Cu² = Cu₂[Co(CN)] [Co (CN)] ⁴ - + 2Cu² = Cu₂ [Co (CN)]

Ni[CN)₄]²-+ 2Cu² = Cu₂[Ni(CN)] Ni [CN) ₄] ² - + 2Cu² = Cu₂ [Ni (CN)]

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

먼저, 본 발명의 불소이온과 시안착화합물 및 유리시안 이온 제거 용액에 대 해 설명한다.First, the fluorine ion and the cyanide compound and the free cyan ion removal solution of the present invention will be described.

폐수 중에 함유되어 있는 불소는 염화알루미늄과 결합하여 침전을 형성하여 제거되는데, 염화알루미늄 투입량에 비례하여 불소이온이 제거되며, 폐수 중에 불소이온과 시안착화합물 및 유리시안 이온이 포함되어 있는 경우는 염화알루미늄과 황산구리 수용액과 아황산수소나트륨 수용액을 가하여 불소와 시안착화합물 및 유리시안 이온을 제거할 수 있다. The fluorine contained in the waste water is removed by forming precipitates by combining with aluminum chloride, and the fluorine ion is removed in proportion to the amount of aluminum chloride injected. If the waste water contains fluorine ion, cyanide compound and free cyanide, aluminum chloride Aqueous copper sulfate solution and sodium bisulfite solution may be added to remove fluorine, cyanide complex, and free cyanide.

또한, 시안착화합물 침 유리시안 이온을 제거하는 데는 황산구리 수용액 대신에 황산구리 수용액과 황산철화합물 수용액과의 혼합물 또는, 황산구리 수용액과 염화철화합물과의 혼합물과 아황산수소나트륨 수용액을 투입하면 불소이온과 시안착화합물 및 유리시안 이온이 순차적으로 제거된다. In addition, to remove the free cyanide ions of the cyanide complex, a mixture of an aqueous solution of copper sulfate and an aqueous solution of ferrous sulfate instead of an aqueous solution of copper sulfate, or a mixture of an aqueous solution of copper sulfate and an iron chloride, and an aqueous solution of sodium bisulfite is added thereto. Free cyan ions are removed sequentially.

본 발명의 불소이온 제거용액에 있어서, 불소는 알루미늄 화합물 및 혼합물량에 비례하여 제거 되고, 황산구리 수용액과 아황산수소나트륨 수용액 또는 황산구리 수용액과 황산철화합물 수용액과의 혼합물 또는, 황산구리 수용액과 염화철화합물 수용액과의 혼합물은 시안이온을 제거 하는데, 이를 제거하기 위해서는 제거효율이 최적이 되는 농도가 존재한다.In the fluorine ion removal solution of the present invention, fluorine is removed in proportion to the amount of aluminum compound and the mixture, and a mixture of an aqueous copper sulfate solution and an aqueous sodium bisulfite solution or an aqueous copper sulfate solution and an aqueous iron compound solution or an aqueous copper sulfate solution and an iron chloride solution The mixture of removes cyan ions, and to remove them, there is a concentration at which the removal efficiency is optimal.

본 발명에 있어, 상기 염화알루미늄은 불소와 결합하여 침전물을 형성시키기 위하여 첨가하는 성분으로, 그 함량이 0.5%미만인 경우에는 불소처리능력이 저하되어 처리효과가 미미하여 불소를 제거를 위해서는 많은 용량이 필요하여 운반 및 저장 능력이 증가하는 문제가 있고, 40%를 초과하는 경우에는 알루미늄이 염산에 용해되지 않고 불포화상태로 존재하고 첨가 효과가 포하되기 때문이며, 본 발명에 있 어 염화알루미늄을 제시하고 있으나 동일한 효과를 갖는 알루미늄 화합물은 모두 적용할 수 있다.In the present invention, the aluminum chloride is a component added to form a precipitate by combining with fluorine. When the content is less than 0.5%, the fluorine treatment capacity is lowered and the treatment effect is insignificant. This is because there is a problem in that the transport and storage capacity is increased, and if it exceeds 40%, aluminum is not dissolved in hydrochloric acid but is present in an unsaturated state and the addition effect is included. Any aluminum compound having an effect can be applied.

본 발명의 시안이온 제거용액에 있어서, 시안착화합물 및 유리시안 이온은 황산구리수용액과 아황산수소나트륨 수용액 량에 비례하여 제거되는데 이를 제거하기 위해서는 제거효율이 최적이 되는 농도가 필요하며 이를 위하여 상기 황산구리 수용액은 0.5중량%이상 25중량%이하로 한정하는 것이 바람직하다. In the cyan ion removal solution of the present invention, the cyanide complex and the free cyan ion are removed in proportion to the amount of copper sulfate aqueous solution and sodium hydrogen sulfite aqueous solution. In order to remove the cyanide compound, the copper sulfate aqueous solution is required. It is preferable to limit it to 0.5 weight% or more and 25 weight% or less.

이 같은 함량 범위는 황산구리 수용액은 0.5중량%미만인 경우에는 시안이온 처리능력이 저하되어 첨가 효과가 미미하여 시안이온 제거를 위해서는 많은 용량이 필요하여 운반 및 저장 능력이 증가하는 문제가 있고, 25중량%를 초과하는 경유에는 황산구리가 용해되지 않고 불포화상태로 존재하여 첨가 효과가 포화되기 때문이다.The content range of the copper sulfate solution is less than 0.5% by weight of cyan ion treatment capacity is reduced and the effect of addition is insignificant to remove the cyan ion requires a large capacity, there is a problem that the transport and storage capacity is increased, 25% by weight This is because copper sulfate is not dissolved in the excess diesel oil, and the additive effect is saturated because the sulfate remains in an unsaturated state.

본 발명에 있어, 상기 아황산수소나트륨 수용액은 황산구리를 환원시키기 위하여 첨가하는 성분으로, 그 함량이 0.5중량%이상 32.75중량%이하로 한정하는 것이 바람직하며, 이 같은 함량 범위는 아황산수소나트륨 수용액은 0.5중량% 미만인 경우에는 황산구리 환원능력이 저하되어 첨가 효과가 미미하여, 32.75중량%를 초과하는 경우에는 황산구리 함량 최대 25중량%를 환원시키는 충분량이 되므로 32.75중량%이상은 효과가 없기 때문이다.In the present invention, the sodium bisulfite aqueous solution is a component added to reduce copper sulfate, the content is preferably limited to more than 0.5% by weight to 32.75% by weight, such a content range is sodium bisulfite aqueous solution is 0.5 If it is less than the weight% copper sulfate reduction capacity is reduced and the effect of addition is insignificant, if it exceeds 32.75% by weight it is sufficient to reduce the content of copper sulfate up to 25% by weight because more than 32.75% by weight is ineffective.

이는 황산구리 1당량 즉, 159그램을 환원시키기 위해서 아황산수소나트륨 2당량 즉, 208그램이 필요하므로 황산구리와 아황산수소나트륨의 비율을 1.31배에 근거한 것이며, 본 발명에 있어 황산구리로 명명하고 있으나 동일한 효과를 갖는 황산구리화합물은 모두 적용할 수 있다.This is based on the ratio of copper sulfate and sodium hydrogen sulfite based on 1.31 times, since two equivalents of sodium hydrogen sulfite, 208 grams, is required to reduce one equivalent of copper sulfate, that is, 159 grams. The copper sulfate compound which has it can apply all.

또한 본 발명은 시안이온 제거용액에 있어서 황산구리화합물 수용액에 황산철화합물 수용액 또는 염화철화합물 수용액을 혼합한 수용액의 사용도 가능하며, 이때의 황산구리화합물에 혼합하는 황산철화합물 및 염화철화합물의 량은 폐수 중에 포함된 유리시안의 량에 따라서 증감이 가능하고 그 량은 0.5이상 10%미만이 바람직하며 이는 유리시안의 함량이 전체 시안화합물 중 10%미만인 도금, 광산,제철공정에서 발생하는 폐수에는 유리시안은 극히 미량이고 다량의 난분해성 시안착화합물로 존재하기 때문에 유리시안과 반응하는 황산철화합물 및 염화철화합물은 0.5% 이상, 10% 미만으로 유리시안을 제거할 수 있는 충분한 량이다.In addition, the present invention can also be used in the solution of cyan ion removal solution in which the iron sulfate compound solution or ferric chloride solution solution is mixed with the copper sulfate compound solution, the amount of the iron sulfate compound and iron chloride compound mixed with the copper sulfate compound at this time Depending on the amount of free cyanide contained, it is possible to increase or decrease the amount, and the amount is preferably 0.5 or more and less than 10%. This means that free cyanide is used in the wastewater generated in the plating, mining and steelmaking processes where the content of free cyanide is less than 10% of all cyanide compounds. Due to the extremely small amount and a large amount of hardly decomposable cyanide compounds, the iron sulfate compound and the iron chloride compound reacting with the free cyan are sufficient to remove the free cyan by 0.5% or more and less than 10%.

다음으로 상기의 불소이온과 시안착화합물 및 유리시안 이온 제거용액을 이용하여 폐수를 처리하는 방법에 대하여 설명한다.Next, a method of treating wastewater using the fluorine ion, the cyanide complex and the free cyanide ion removal solution will be described.

본 발명의 불소이온 제거용액을 폐수에 처리하는 경우에는 폐수의 pH를 5~9로 제어한 후 행하며, 이는 알루미늄화합물과 불소의 반응효율이 가장 활발하게 이루어지는 영역으로 상기 범위를 초과하거나 미만일 경우 불소제거 효율이 떨어지기 때문이다.When the fluorine ion removal solution of the present invention is treated in wastewater, the pH of the wastewater is controlled to 5 to 9, which is a region where the reaction efficiency of the aluminum compound and fluorine is most active. This is because the removal efficiency is lowered.

상기에서 알루미늄 화합물은 염산 또는 황산 등 강산의 용액과 결합한 화합물로 알루미늄화합물 수용액의 pH는 산성을 나타내므로 원 폐수의 pH가 9이상인 경우 알루미늄화합물 수용액의 투입만으로 불소를 처리할 수 있는 pH범위를 형성할 수도 있다. Since the aluminum compound is a compound combined with a strong acid solution such as hydrochloric acid or sulfuric acid, and the pH of the aluminum compound aqueous solution shows acidity, when the pH of the raw wastewater is 9 or more, it forms a pH range capable of treating fluorine only by adding an aluminum compound aqueous solution. You may.

다음으로, 상기의 시안착화합물 및 유리 시안이온 제거 용액을 이용하여 폐 수를 처리하는 방법에 대하여 설명한다.Next, the method of treating wastewater using the cyanide complex and the free cyanide removal solution will be described.

시안착화합물 및 유리 시안이온 제거 용액을 이용하여 폐수를 처리하는 경우에는 폐수의 pH를 6이하로 제어한 후, 바람직하게는 pH를 4~6으로 제어한 후 행하며, 이는 폐수의 pH가 4~6의 범위에서 황산구리와 아황산수소나트륨의 반응효율이 가장 활발하게 이루어져 환원되는 구리이온과 시안착화합물 및 유리 시안이온의 결합이 왕성해지기 때문이며, 또한 폐수의 pH가 4 미만, 6 이상 되면 구리이온의 환원반응 효율이 감소하여 시안착화합물 및 유리 시안이온의 제거효율이 감소된다.When the wastewater is treated using a cyanide compound and a free cyanide removal solution, the pH of the wastewater is controlled to 6 or less, preferably after the pH is controlled to 4-6, and the pH of the wastewater is 4-6. This is because the reaction efficiency of copper sulfate and sodium bisulfite is most active in the range of, and the combination of reduced copper ions, cyanide compounds, and free cyanide becomes vigorous. The reaction efficiency is reduced, thereby reducing the removal efficiency of the cyanide compound and the free cyan ion.

이하, 실시 예를 통하여 본 발명을 구체적으로 설명한다. 단, 실시 예는 본 발명을 예시하기 위한 것이지 이들만으로 한정하는 것이 아니다. Hereinafter, the present invention will be described in detail through examples. However, the examples are only for illustrating the present invention and are not limited thereto.

<실시 예 1>&Lt; Example 1 >

본 실시 예는 불소이온과 시안이온이 함유된 폐수에 먼저 불소이온을 제거하기 위하여 염화알루미늄의 적용 농도를 조사하기 위한 것으로 염화알루미늄 농도를 0.0, 0.5, 1.0, 3.0, 5.0, 7.0, 10.0, 13.0, 15.0, 20.0, 25.0, 30.0, 35.0, 40.0% 가 되도록 용액을 조제한 후 pH7.5이고 불소이온이 35ppm, 시안이온이 25ppm함유된 폐수 1,000mℓ에 3,000ppm씩 첨가하고 80rpm으로 5분간 교반한 다음 여기에 고분자물질(Polymer)을 소량 주입하고 다시 80rpm으로 5분간 교반하여 상등액의 불소농도를 수질오염 공정시험방법에 따라 측정하고 그 결과를 [표 1]에 나타내었다.This example is to investigate the applied concentration of aluminum chloride to remove fluorine ions in the wastewater containing fluorine and cyan ions first. The aluminum chloride concentration is 0.0, 0.5, 1.0, 3.0, 5.0, 7.0, 10.0, 13.0 , 15.0, 20.0, 25.0, 30.0, 35.0, 40.0% of the solution to prepare a solution after adding pH 3,000, 35ppm fluorine ion, 25ppm cyanide containing 3,000ppm to 1,000mℓ of wastewater and stirred at 80rpm for 5 minutes Inject a small amount of polymer (Polymer) and stirred again at 80rpm for 5 minutes to measure the fluorine concentration of the supernatant according to the water pollution process test method and the results are shown in [Table 1].

[표 1]TABLE 1


구분
division
염화알루미늄Aluminum chloride 폐수중 불소Fluorine in Wastewater 농도
(중량 %)density
(weight %) 주입량
(ppm)Injection volume
(ppm) 처리전 농도
(ppm)Concentration before treatment
(ppm) 처리후 농도
(ppm)Concentration after treatment
(ppm) 처리효율
(%)Processing efficiency
(%) 실시예 1Example 1 0.00.0 3,0003,000 3535 35.035.0 00 실시예 2Example 2 0.50.5 3,0003,000 3535 31.431.4 10.2910.29 실시예 3 Example 3 1.01.0 3,0003,000 3535 28.528.5 18.5718.57 실시예 4 Example 4 3.03.0 3,0003,000 3535 22.122.1 36.8636.86 실시예 5Example 5 5.05.0 3,0003,000 3535 17.517.5 50.0050.00 실시예 6Example 6 7.07.0 3,0003,000 3535 14.114.1 59.7159.71 실시예 7Example 7 9.09.0 3,0003,000 3535 12.712.7 63.7163.71 실시예 8Example 8 11.011.0 3,0003,000 3535 11.511.5 67.1467.14 실시예 9Example 9 13.013.0 3,0003,000 3535 10.810.8 69.1469.14 실시예 10Example 10 15.015.0 3,0003,000 3535 10.410.4 70.2970.29 실시예 11Example 11 17.017.0 3,0003,000 3535 10.110.1 71.1471.14 실시예 12 Example 12 20.020.0 3,0003,000 3535 9.69.6 72.5772.57 실시예 13Example 13 25.025.0 3,0003,000 3535 9.59.5 72.8672.86 실시예 14Example 14 30.030.0 3,0003,000 3535 9.49.4 73.1473.14 실시예 15Example 15 35.035.0 3,0003,000 3535 9.49.4 73.1473.14 실시예 16Example 16 40.040.0 3,0003,000 3535 9.59.5 72.8672.86

상기 [표 1]에서 알 수 있는 바와 같이 폐수 중의 불소이온은 염화알루미늄의 농도가 높을수록 제거효율이 증가 되어 처리효율이 72%까지 향상됨을 알 수 있으며 불소이온 제거를 위한 염화알루미늄 농도는 0.5% 이상 40% 이하로 한정함이 바람직하다. As can be seen in [Table 1], the higher the concentration of aluminum chloride, the higher the concentration of aluminum chloride, the higher the removal efficiency, so that the treatment efficiency can be improved to 72%. The aluminum chloride concentration for fluorine ion removal is 0.5%. It is preferable to limit to 40% or less.

<실시 예 2><Example 2>

본 실시 예는 불소이온과 시안이온이 함유된 폐수에서 염화알루미늄을 이용하여 pH조건변화에 따른 불소이온 제거효율 및 적정 pH조건을 도출하기 위한 것으로, 7%의 염화알루미늄 용액을 불소이온이 35ppm, 시안이온이 25ppm 함유된 폐수 1,000mℓ에 3,000ppm씩 첨가하고 황산과 가성소다를 이용하여 폐수용액의 pH를 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0이 되도록 조정한 다음 각각의 pH조건에 서 80rpm으로 5분간 교반한 다음 여기에 고분자물질(Polymer)을 소량 주입하고 다시 80rpm으로 5분간 교반하여 상등액의 불소농도를 수질오염공정시험방법에 따라 측정하고 그 결과를 [표 2]에 나타내었다.The present embodiment is to derive fluorine ion removal efficiency and proper pH condition according to pH condition change by using aluminum chloride in wastewater containing fluorine ion and cyan ion, and 7% aluminum chloride solution is 35ppm, 3,000ppm was added to 1,000ml of wastewater containing 25ppm of cyan ion and the pH of wastewater was adjusted to 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0 using sulfuric acid and caustic soda. After stirring at 80 rpm for 5 minutes under the condition, a small amount of polymer was added thereto and stirred at 80 rpm for 5 minutes to measure the fluorine concentration of the supernatant according to the water pollution process test method. The results are shown in [Table 2]. Indicated.

[표 2]TABLE 2


구분
division
염화알루미늄
주입량(ppm)Aluminum chloride
Injection amount (ppm) pH조건
pH condition
폐수중 불소Fluorine in Wastewater 처리전
농도(ppm)Before treatment
Concentration (ppm) 처리후
농도(ppm)After treatment
Concentration (ppm) 처리효율
(%)Processing efficiency
(%) 실시예 17Example 17 3,0003,000 4.04.0 3535 27.627.6 21.1421.14 실시예 18Example 18 3,0003,000 5.05.0 3535 18.518.5 47.1447.14 실시예 19Example 19 3,0003,000 6.06.0 3535 14.814.8 57.7157.71 실시예 20Example 20 3,0003,000 7.07.0 3535 14.514.5 58.5758.57 실시예 21Example 21 3,0003,000 8.08.0 3535 14.214.2 59.4359.43 실시예 22Example 22 3,0003,000 9.09.0 3535 19.119.1 45.4345.43 실시예 23Example 23 3,0003,000 10.010.0 3535 21.721.7 38.0038.00 실시예 24Example 24 3,0003,000 11.011.0 3535 26.526.5 24.2924.29

상기 [표 2]에 나타난 바와 같이 불소이온 및 시안이온을 함유한 폐수에서 염화알루미늄을 이용하여 불소이온을 제거할 때 pH5이하, 9이하에서는 처리효율이 상대적으로 낮으나 pH5이상 9이하에서 처리효율이 상대적으로 높게 나타남을 알 수 있다.As shown in [Table 2], when the fluoride ion is removed from the wastewater containing fluorine ion and cyan ion by using aluminum chloride, the treatment efficiency is relatively low at pH 5 and below 9, but the treatment efficiency is lower at pH 5 and above 9 It can be seen that it is relatively high.

따라서 본 발명에서는 염화알루미늄을 이용한 불소이온 및 시안이온이 함유된 폐수에서 불소이온을 제거를 위해서는 pH를 5이상,9이하로 조절하여 침전반응을 촉진시켜 주는 것이 바람직하며 또한, 불소이온 제거를 위해 주입하는 염화알루미늄 만으로도 폐수의 pH를 5이상, 9이하로 조절이 가능한 경우 별도의 황산 및 가성소다의 주입은 생략할 수 있다.Therefore, in the present invention, in order to remove fluorine ions from wastewater containing fluorine ions and cyan ions using aluminum chloride, it is preferable to promote the precipitation reaction by adjusting the pH to 5 or more and 9 or less, and to remove fluorine ions. If only the aluminum chloride to be injected can control the pH of the wastewater to 5 or more and 9 or less, separate injection of sulfuric acid and caustic soda may be omitted.

<실시 예 3>&Lt; Example 3 >

본 실시 예는 불소이온과 시안이온이 함유된 폐수에서 염화알루미늄을 이용하여 불소이온을 제거한 폐수에서 시안이온을 제거하기 위한 시안이온 제거제에 있어서 황산구리의 환원에 필요한 아황산수소나트륨량을 조사하기 위한 것으로, 최적의 황산구리 중 구리이온을 환원시키는데 필요한 아황산수소나트륨양을 구하기 위한 실험방법은 다음과 같다.This embodiment is to investigate the amount of sodium hydrogen sulfite required for the reduction of copper sulfate in the cyanide remover for removing cyanide from wastewater from which fluorine is removed using aluminum chloride in wastewater containing fluorine and cyanide. In order to determine the optimal amount of sodium bisulfite required to reduce copper ions in copper sulfate, the experimental method is as follows.

pH7.5이고 불소이온이 35ppm, 시안이온이 25ppm 함유된 폐수 1,000mℓ에 7% 염화알루미늄 3,000ppm을 투입하여 상기 실시 예 20에 따라 불소이온을 제거하고 난 다음 98%황산 0.5ml를 주입하여 폐수의 pH를 6이하로 조절하고, 황산구리를 2,000ppm씩 첨가하고 교반하여 용해한 후 아황산수소나트륨을 [표 3]과 같이 단계적으로 첨가하고 80rpm으로 5분간 교반한다. 여기에 고분자물질(Polymer)을 소량 주입하고 다시 80rpm으로 5분간 교반하여 상등액의 시안농도를 수질오염 공정시험방법에 따라 측정하고 그 결과를 [표 3]에 나타내었다.3,000 ppm of 7% aluminum chloride was added to 1,000 ml of wastewater containing pH 7.5 and 35 ppm of fluorine ions and 25 ppm of cyan ions to remove fluorine ions according to Example 20, followed by injecting 0.5 ml of 98% sulfuric acid. The pH of the mixture was adjusted to 6 or less, and 2,000 ppm of copper sulfate was added, stirred, and dissolved. Then, sodium hydrogen sulfite was added stepwise as shown in [Table 3] and stirred at 80 rpm for 5 minutes. Herein, a small amount of polymer was injected and stirred at 80 rpm for 5 minutes to measure the cyan concentration of the supernatant according to the water pollution process test method. The results are shown in [Table 3].

[표 3][Table 3]

구분division 황산구리첨가량
(ppm)-ACopper sulfate addition amount
(ppm) -A 아황산수소나트륨
첨가량(ppm)-BSodium bisulfite
Addition amount (ppm) -B 비율
(A : B)ratio
(A: B) 시안농도
(ppm)Cyan concentration
(ppm) 실시예 25Example 25 2,0002,000 2,4002,400 1 : 1.21: 1.2 10.410.4 실시예 26Example 26 2,0002,000 2,5002,500 1 : 1.251: 1.25 7.87.8 실시예 27Example 27 2,0002,000 2,5502,550 1 : 1.2751: 1.275 5.75.7 실시예 28Example 28 2,0002,000 2,5702,570 1 : 1.2851: 1.285 3.93.9 실시예 29Example 29 2,0002,000 2,5902,590 1 : 1.2951: 1.295 2.62.6 실시예 30Example 30 2,0002,000 2,6002,600 1 : 1.31: 1.3 1.81.8 실시예 31Example 31 2,0002,000 2,6102,610 1 : 1.3051: 1.305 1.11.1 실시예 32Example 32 2,0002,000 2,6202,620 1 : 1.311: 1.31 0.300.30 실시예 33Example 33 2,0002,000 2,6302,630 1 : 1.3151: 1.315 0.310.31 실시예 34Example 34 2,0002,000 2,6402,640 1 : 1.321: 1.32 0.300.30 실시예 35Example 35 2,0002,000 2,6502,650 1 : 1.3251: 1.325 0.300.30 실시예 36Example 36 2,0002,000 2,6602,660 1 : 1.331: 1.33 0.290.29 실시예 37Example 37 2,0002,000 2,6702,670 1 : 1.3351: 1.335 0.310.31 실시예 38Example 38 2,0002,000 2,6802,680 1 : 1.341: 1.34 0.300.30

상기 [표 3]에서 알 수 있는 바와 같이 황산구리 일정량에 대하여 아황산수소나트륨이 1.31배 이상에서 시안이온 제거율이 최대가 됨을 알 수 있고 1.31배 이상에서는 1.31배와 동일한 효과가 나타남을 알 수 있었다.As can be seen from the above [Table 3], it can be seen that the cyan ion removal rate is maximized at a predetermined amount of sodium hydrogen sulfite of 1.31 times or more with respect to a certain amount of copper sulfate, and the same effect as that of 1.31 times is obtained at 1.31 times or more.

<실시 예 4><Example 4>

본 실시 예는 시안이온 제거제에 있어 시안제거제 사용시 pH의 영향을 보기 위한것이다.This embodiment is to see the effect of pH when using the cyanide remover in the cyan ion remover.

pH7.5이고 불소이온이 35ppm, 시안이온이 25ppm 함유된 폐수 1,000mℓ에 7%염화알루미늄을 3,000ppm 주입하여 불소이온을 제거하고 난 다음 98% 황산 및 45% 가성소다를 이용하여 pH를 1~14까지 단계적으로 조절하고 황산구리 2,000ppm과 아황산수소나트륨 2,620ppm을 주입하고 80rpm으로 5분간 교반하였다.3,000 ppm of 7% aluminum chloride is injected into 1,000 ml of wastewater containing pH 7.5 and 35 ppm of fluorine ions and 25 ppm of cyan ions to remove fluoride ions, and then the pH is adjusted to 1 ~ using 98% sulfuric acid and 45% caustic soda. Stepwise until 14, 2,000ppm copper sulfate and 2,620ppm sodium bisulfite were injected and stirred at 80rpm for 5 minutes.

여기에 소량의 고분자물질(Polymer)을 주입하고 다시 80rpm으로 5분간 교반하여 상등액의 시안이온을 수질오염 공정시험방법에 따라 측정하고 그 결과를 [표 4]에 나타내었다.Inject a small amount of polymer (Polymer) and stirred again at 80rpm for 5 minutes to measure the cyan ion of the supernatant according to the water pollution process test method and the results are shown in [Table 4].

[표 4][Table 4]

구분division 황산구리
첨가량(ppm)Copper sulfate
Addition amount (ppm) 아황산수소나트륨
첨가량(ppm)Sodium bisulfite
Addition amount (ppm) pHpH 시안이온
농도(ppm)Cyan ion
Concentration (ppm) 실시예 39Example 39 2,0002,000 2,6202,620 1One 25.125.1 실시예 40Example 40 2,0002,000 2,6202,620 22 25.025.0 실시예 41Example 41 2,0002,000 2,6202,620 33 19.419.4 실시예 42Example 42 2,0002,000 2,6202,620 44 2.52.5 실시예 43Example 43 2,0002,000 2,6202,620 55 0.390.39 실시예 44Example 44 2,0002,000 2,6202,620 66 0.310.31 실시예 45Example 45 2,0002,000 2,6202,620 77 8.218.21 실시예 46Example 46 2,0002,000 2,6202,620 88 17.2717.27 실시예 47Example 47 2,0002,000 2,6202,620 99 20.5020.50 실시예 48Example 48 2,0002,000 2,6202,620 1010 23.7323.73 실시예 49Example 49 2,0002,000 2,6202,620 1111 25.125.1 실시예 50Example 50 2,0002,000 2,6202,620 1212 25.025.0 실시예 51Example 51 2,0002,000 2,6202,620 1313 25.025.0

상기 [표 4]에서 알 수 있는 바와 같이 pH4 미만의 영역에서 시안이온 제거효율이 떨어지고, 또한 pH6을 초과하는 영역에서도 시안이온 제거효율이 떨어지므로 본 발명의 시안이온제거제를 이용한 폐수 중 시안이온 제거제 사용의 pH범위는 4 이상 6이하의 약산성에서 최대 효율을 나타냄을 확인할 수 있었다.As can be seen in Table 4, the cyan ion removal efficiency is lowered in the region below pH4, and the cyan ion removal efficiency is lowered even in the region exceeding pH6, so that the cyan ion remover in the wastewater using the cyan ion remover of the present invention. The pH range of use was found to show the maximum efficiency at weak acidity of 4 or more and 6 or less.

<실시 예 5>Example 5

본 실시 예는 상기한 실시 예들에 기초하여 본 발명에 의한 시안이온 제거제에 있어 시안 제거를 위한 최적의 황산구리 첨가량과 아황산수소나트륨의 첨가량을 조사하기 위한 것이다.This embodiment is to investigate the optimum amount of copper sulfate and sodium hydrogen sulfite addition amount for cyanide removal in the cyan ion remover according to the present invention based on the above embodiments.

먼저 황산구리 농도를 10.0 중량 %가 되도록 용액을 조제하고 아황산수소나 트륨 농도를 13.1 중량 %가 되도록 조제하여 단계적으로 투입하고 시안제거 효율을 조사하였다.First, the solution was prepared so that the concentration of copper sulfate was 10.0% by weight, and the concentration of hydrogen sulfite or sodium was 13.1% by weight.

시안제거에 필요한 최적의 황산구리 및 아황산수소나트륨 첨가량을 조사하기 위한 실험방법은 다음과 같다.Experimental method for investigating the optimum amount of copper sulfate and sodium hydrogen sulfite addition required for cyanide removal is as follows.

불소이온과 시안이온이 함유된 제철 고로 폐수 1,000mℓ에 7% 염화알루미늄 3,000ppm 을 주입하여 폐수 pH를 7.0으로 조절하고 80rpm으로 5분간 교반한 뒤 응집제(Polymer)를 소량 가하고 다시 80rpm 으로 5분간 교반하여 불소이온이 15ppm 이하가 되도록 처리하고 상등액에 조제한 황산구리용액과 아황산수소나트륨을 [표 5]와 같이 단계적으로 가하여 pH를 측정하고 pH가 6이상이면 황산을 이용하여 폐수의 pH를 6.0이하로 조절하고, pH6이하, pH4이상이면 그 pH조건에서 80rpm으로 5분간 교반한다. 여기에 고분자응집제(Polymer)를 소량 투입하고 다시 80rpm 으로 5분간 교반하여 시안이온을 제거하였다.Introduce 3,000ppm of 7% aluminum chloride into 1,000mℓ of steel blast furnace wastewater containing fluorine ion and cyan ion to adjust the wastewater pH to 7.0 and stir at 80rpm for 5 minutes Treat the fluorine ion to 15ppm or less and measure the pH by adding copper sulfate solution and sodium hydrogen sulfite prepared in the supernatant stepwise as shown in [Table 5], and adjust the pH of the wastewater to 6.0 or less by using sulfuric acid if the pH is 6 or more. If the pH is 6 or less and pH 4 or more, the mixture is stirred for 5 minutes at 80 rpm under the pH conditions. A small amount of a polymer coagulant (Polymer) was added thereto, followed by stirring at 80 rpm for 5 minutes to remove cyan ions.

시안이온 제거제 투입 후 폐수 중 시안이온의 농도는 수질오염 공정시험 방법에 따라 측정하여 하기 [표 5]에 나타내었다. 한편, 시안이온제거제 첨가 전 폐수의 시안이온 농도는 25.0rpm 이였다.After adding the cyanide remover, the concentration of cyanide in the wastewater was measured according to the water pollution process test method and is shown in the following [Table 5]. Meanwhile, the cyan ion concentration of the wastewater before adding the cyanide remover was 25.0 rpm.

[표 5]TABLE 5

구분division 황산구리Copper sulfate 아황산수소나트륨Sodium bisulfite 시안농도
(ppm)Cyan concentration
(ppm) 처리효율
(%)Processing efficiency
(%) 첨가량(mℓ)Addition amount (mℓ) 중량 %weight % 첨가량(mℓ)Addition amount (mℓ) 중량 %weight % 비교예 1Comparative Example 1 0.10.1 0.010.01 00 00 25.025.0 00 비교예 2Comparative Example 2 0.20.2 0.020.02 00 00 24.824.8 0.20.2 비교예 3Comparative Example 3 0.30.3 0.030.03 00 00 24.824.8 0.20.2 비교예 4Comparative Example 4 0.40.4 0.040.04 00 00 24.724.7 0.30.3 비교예 5Comparative Example 5 0.50.5 0.050.05 00 00 24.724.7 0.30.3 비교예 6Comparative Example 6 0.60.6 0.060.06 00 00 24.724.7 0.30.3 비교예 7Comparative Example 7 0.70.7 0.070.07 00 00 24.624.6 0.40.4 비교예 8Comparative Example 8 0.80.8 0.080.08 00 00 24.724.7 0.30.3 비교예 9Comparative Example 9 0.90.9 0.090.09 00 00 25.025.0 00 비교예 10Comparative Example 10 1.01.0 0.10.1 00 00 25.225.2 00 비교예 11Comparative Example 11 2.02.0 0.20.2 00 00 24.824.8 0.20.2 비교예 12Comparative Example 12 3.03.0 0.30.3 00 00 25.025.0 00 비교예 13Comparative Example 13 4.04.0 0.40.4 00 00 24.924.9 0.10.1 비교예 14Comparative Example 14 5.05.0 0.50.5 00 00 25.125.1 00 비교예 15Comparative Example 15 6.06.0 0.60.6 00 00 25.225.2 00 비교예 16Comparative Example 16 7.07.0 0.70.7 00 00 25.125.1 00 비교예 17Comparative Example 17 00 00 0.10.1 0.01310.0131 25.025.0 00 비교예 18Comparative Example 18 00 00 0.20.2 0.02620.0262 25.025.0 00 비교예 19Comparative Example 19 00 00 0.30.3 0.03930.0393 25.125.1 00 비교예 20Comparative Example 20 00 00 0.40.4 0.05240.0524 24.924.9 0.10.1 비교예 21Comparative Example 21 00 00 0.50.5 0.06550.0655 25.025.0 00 비교예 22Comparative Example 22 00 00 0.60.6 0.07860.0786 24.924.9 0.10.1 비교예 23Comparative Example 23 00 00 0.70.7 0.09170.0917 25.025.0 00 비교예 24Comparative Example 24 00 00 0.80.8 0.10480.1048 25.125.1 00 비교예 25Comparative Example 25 00 00 0.90.9 0.11790.1179 25.025.0 00 비교예 26Comparative Example 26 00 00 1.01.0 0.1310.131 25.025.0 00 비교예 27Comparative Example 27 00 00 2.02.0 0.2620.262 25.025.0 00 비교예 28Comparative Example 28 00 00 3.03.0 0.3930.393 24.924.9 0.10.1 비교예 29Comparative Example 29 00 00 4.04.0 0.5240.524 25.025.0 00 비교예 30Comparative Example 30 00 00 5.05.0 0.6550.655 25.125.1 00 비교예 31Comparative Example 31 00 00 6.06.0 0.7860.786 25.025.0 00 비교예 32Comparative Example 32 00 00 7.07.0 0.9170.917 25.025.0 00

실시예 53Example 53 0.20.2 0.020.02 0.20.2 0.02620.0262 24.124.1 3.603.60 실시예 54Example 54 0.40.4 0.040.04 0.40.4 0.05240.0524 23.623.6 5.605.60 실시예 55Example 55 0.60.6 0.060.06 0.60.6 0.07860.0786 22.022.0 12.0012.00 실시예 56Example 56 0.80.8 0.080.08 0.80.8 0.10480.1048 20.720.7 17.2017.20 실시예 57Example 57 1.01.0 0.100.10 1.01.0 0.13100.1310 18.918.9 24.4024.40 실시예 58Example 58 1.21.2 0.120.12 1.21.2 0.15720.1572 16.216.2 35.2035.20 실시예 59Example 59 1.41.4 0.140.14 1.41.4 0.18340.1834 14.714.7 41.2041.20 실시예 60Example 60 1.61.6 0.160.16 1.61.6 0.20960.2096 11.811.8 52.8052.80 실시예 61Example 61 1.81.8 0.180.18 1.81.8 0.23580.2358 11.0311.03 55.8855.88 실시예 62Example 62 2.02.0 0.200.20 2.02.0 0.26200.2620 8.878.87 64.5264.52 실시예 63Example 63 4.04.0 0.400.40 4.04.0 0.52400.5240 7.677.67 69.3269.32 실시예 64Example 64 6.06.0 0.600.60 6.06.0 0.78600.7860 4.554.55 81.8081.80 실시예 65Example 65 8.08.0 0.800.80 8.08.0 1.0481.048 3.153.15 87.4087.40 실시예 66Example 66 10.010.0 1.01.0 10.010.0 1.3101.310 1.511.51 93.9693.96 실시예 67Example 67 12.012.0 1.21.2 12.012.0 1.5721.572 0.950.95 96.2096.20 실시예 68Example 68 14.014.0 1.41.4 14.014.0 1.8341.834 0.410.41 98.3698.36 실시예 69Example 69 16.016.0 1.61.6 16.016.0 2.0962.096 0.280.28 98.8898.88 실시예 70Example 70 18.018.0 1.81.8 18.018.0 2.3582.358 0.240.24 99.0499.04 실시예 71Example 71 20.020.0 2.02.0 20.020.0 2.6202.620 0.240.24 99.0499.04

상기 [표 5]에서 나타난 바와 같이 시안이 함유된 폐수에 시안제거제 중 하나인 황산구리만을 단계적으로 첨가한 결과는 시안이온이 제거되지 않았고, 또한 아황산수소나트륨만을 단계적으로 첨가한 결과에서도 시안이온이 제거되지 않았음을 알 수 있었다.As shown in [Table 5], the result of stepwise addition of copper sulfate, one of the cyanide removers, to the wastewater containing cyan was not removed. It was not known.

따라서 시안이온 제거를 위해서는 황산구리 및 아황산수소나트륨을 동시에 첨가하고 그 비율을 1:1.31을 유지해야 시안이온제거의 최대 효율의 폐수를 처리할 수 있음을 알 수 있었다.Therefore, it was found that copper cyanide and sodium bisulfite were added at the same time and the ratio was maintained at 1: 1.31 to treat wastewater with the maximum efficiency of cyanide removal.

<실시 예 6>Example 6

본 실시 예는 본 발명에 의한 시안이온제거제에 있어 황산구리에 황산제1철 또는 황산구리에 염화제2철을 혼합하여 시안이온제거제로 사용하기 위한 실험으로황산구리 10중량%수용액에 10중량% 황산제1철 수용액을 단계적으로 가하여 시안이온제거제를 조제하여 13.1중량%가 되도록 조제한 아황산수소나트륨과 함께 폐수에 주입하여 시안제거 효율을 조사하였다.This example is a test for mixing cyanide remover according to the present invention using ferric sulfate or copper sulfate in ferric sulfate, and using it as a cyanide remover. An aqueous solution of iron was added stepwise to prepare a cyanide remover, and injected into the wastewater with sodium bisulfite prepared to be 13.1% by weight to investigate the cyanide removal efficiency.

또한, 황산구리 10중량% 수용액에 10중량% 염화제2철 수용액을 단계적으로 주입하여 시안이온제거제를 조제하여 13.1중량%가 되도록 조제한 아황산수소나트륨과 함께 폐수에 주입하여 시안제거 효율을 조사하였다.In addition, a 10% by weight aqueous solution of ferric chloride was injected stepwise into a 10% by weight aqueous solution of copper sulfate to prepare a cyanide remover and injected into the wastewater with sodium bisulfite prepared to be 13.1% by weight to investigate the cyanide removal efficiency.

본 발명에 있어 황산제1철 및 염화제2철로 명명하고 있으나 동일한 효과를 갖는 황산철화합물, 황산철혼합물, 염화철화합물, 염화철혼합물은 모두 적용할 수 있다.Although ferrous sulfate and ferric chloride are named in the present invention, all of the ferrous sulfate compounds, ferrous sulfate mixtures, ferric chloride compounds, and ferric chloride mixtures having the same effect can be used.

불소이온과 시안이온이 함유된 제철 고로 폐수 1,000mℓ에 7% 염화알루미늄3,000ppm 을 주입하여 폐수 pH를 7.0으로 조절하고 80rpm으로 5분간 교반한 뒤 응집제(Polymer)를 소량 가하고 다시 80rpm 으로 5분간 교반하여 불소이온이 15ppm 이하가 되도록 처리하고 조제한 황산구리용액과 황산제1철을 혼합한 수용액과 13.1 중량%가 되도록 조제한 아황산수소나트륨을 [표 6]와 같이 단계적으로 가하여 pH를 측정하고 pH가 6이상이면 황산을 이용하여 폐수의 pH를 6.0 이하로 조절하고, pH가 6이하, 4이상이면 그 pH조건에서 80rpm으로 5분간 교반한다. 여기에 고분자응집제(Polymer)를 소량 투입하고 다시 80rpm으로 5분간 교반하여 시안이온을 제거하였다.Introduce 3,000ppm of 7% aluminum chloride into 1,000mℓ of steel blast furnace wastewater containing fluorine and cyan ions to adjust the wastewater pH to 7.0, stir at 80rpm for 5 minutes, add a small amount of polymer and then stir at 80rpm for 5 minutes. Treated so that the fluorine ion is 15ppm or less, and the aqueous solution of the mixed copper sulfate solution and ferrous sulfate solution and sodium hydrogen sulfite prepared so as to be 13.1% by weight are added stepwise as shown in [Table 6] to measure the pH and the pH is 6 or more. If sulfuric acid is used to adjust the pH of the wastewater to 6.0 or less, and if the pH is 6 or less, 4 or more, the solution is stirred at 80 rpm for 5 minutes at the pH condition. A small amount of a polymer coagulant (Polymer) was added thereto and stirred at 80 rpm for 5 minutes to remove cyan ions.

시안이온 제거제 투입 후 폐수 중 시안이온의 농도는 수질오염 공정시험 방법에 따라 측정하여 하기 표 6에 나타내었다. 한편, 시안이온제거제 첨가 전 폐수의 시안이온 농도는 25.0ppm 이였다.The concentration of cyan ions in the wastewater after adding the cyan ion remover was measured according to the water pollution process test method and is shown in Table 6 below. On the other hand, the cyan ion concentration of the wastewater before adding the cyanide remover was 25.0 ppm.

[표 6]TABLE 6

구분division 황산구리
첨가량(mℓ)Copper sulfate
Addition amount (mℓ) 황산제1철
첨가량(mℓ)Ferrous sulfate
Addition amount (mℓ) 아황산수소나트륨
첨가량(mℓ)Sodium bisulfite
Addition amount (mℓ) 시안농도
(ppm)Cyan concentration
(ppm) 처리효율
(%)Processing efficiency
(%) 비교예 33Comparative Example 33 2020 00 00 25.025.0 00 비교예 34Comparative Example 34 2020 22 00 24.924.9 0.40.4 비교예 35Comparative Example 35 2020 44 00 24.724.7 1.21.2 비교예 36Comparative Example 36 2020 66 00 25.025.0 00 비교예 37Comparative Example 37 2020 88 00 24.724.7 1.21.2 비교예 38Comparative Example 38 2020 1010 00 24.624.6 1.61.6 비교예 39Comparative Example 39 2020 1212 00 24.624.6 1.61.6 비교예 40Comparative Example 40 2020 1414 00 24.624.6 1.61.6 비교예 41Comparative Example 41 2020 1616 00 25.225.2 00 비교예 42Comparative Example 42 2020 1818 00 24.724.7 1.21.2 비교예 43Comparative Example 43 2020 2020 00 24.924.9 0.40.4

실시예 72Example 72 2020 00 2020 0.240.24 99.0499.04 실시예 73Example 73 2020 22 2020 0.210.21 99.1699.16 실시예 74Example 74 2020 44 2020 0.190.19 99.2499.24 실시예 75Example 75 2020 66 2020 0.170.17 99.3299.32 실시예 76Example 76 2020 88 2020 0.180.18 99.2899.28 실시예 77Example 77 2020 1010 2020 0.160.16 99.3699.36 실시예 78Example 78 2020 1212 2020 0.150.15 99.4099.40 실시예 79Example 79 2020 1414 2020 0.140.14 99.4499.44 실시예 80Example 80 2020 1616 2020 0.130.13 99.4899.48 실시예 81Example 81 2020 1818 2020 0.140.14 99.4499.44 실시예 82Example 82 2020 2020 2020 0.150.15 99.4099.40

상기 [표 6]에서 나타난 바와 같이 불소이온과 시안이 함유된 폐수에 불소를 제거한 뒤 시안제거제 중 하나인 황산구리와 황산제1철의 혼합물을 단계적으로 첨가한 결과는 시안이온의 제거효율이 미미하고, 아황산수소나트륨을 황산구리 중량% 1.31배 첨가한 결과에서 황산구리만을 사용할 때보다 최대 0~0.4% 범위에서 시안이온의 제거효율이 증가함을 알 수 있었다.As shown in [Table 6], after removing fluorine from wastewater containing fluorine ions and cyanide, a stepwise addition of a mixture of copper sulfate and ferrous sulfate, one of the cyanide removers, shows that the removal efficiency of cyanide is insignificant. As a result of the addition of 1.31 times the weight of copper sulfate, sodium hydrogen sulfite, it was found that the removal efficiency of cyan ions increased in the range of 0 to 0.4% at maximum compared to using only copper sulfate.

또한, 불소이온을 15ppm이하로 처리한 폐수에 조제한 황산구리용액과 염화제2철을 혼합한 수용액과 아황산수소나트륨을 [표 6]와 같이 단계적으로 가하여 pH를 측정하고 pH가 6이상이면 황산을 이용하여 폐수의 pH를 6.0이하로 조절하고, pH가 6이하, 4이상이면 그 pH조건에서 80rpm으로 5분간 교반한다. 여기에 고분자응집제(Polymer)를 소량 투입하고 다시 80rpm으로 5분간 교반하여 시안이온을 제거하였다.In addition, the pH was measured by stepwise addition of an aqueous solution of copper sulfate and ferric chloride prepared in wastewater treated with fluorine ions less than 15ppm as shown in [Table 6] and sulfuric acid if the pH was 6 or more. The pH of the wastewater is adjusted to 6.0 or less, and if the pH is 6 or less and 4 or more, the solution is stirred for 5 minutes at 80 rpm under the pH conditions. A small amount of a polymer coagulant (Polymer) was added thereto and stirred at 80 rpm for 5 minutes to remove cyan ions.

시안이온 제거제 투입 후 폐수 중 시안이온의 농도는 수질오염 공정시험 방법에 따라 측정하여 하기 [표 7]에 나타내었다. 한편, 시안이온제거제 첨가 전 폐수의 시안이온 농도는 25.0ppm 이였다.After adding the cyanide remover, the concentration of cyanide in the wastewater was measured according to the water pollution process test method and is shown in the following [Table 7]. On the other hand, the cyan ion concentration of the wastewater before adding the cyanide remover was 25.0 ppm.

[표 7]TABLE 7

구분division 황산구리
첨가량(mℓ)Copper sulfate
Addition amount (mℓ) 염화제1철
첨가량(mℓ)Ferrous chloride
Addition amount (mℓ) 아황산수소나트륨
첨가량(mℓ)Sodium bisulfite
Addition amount (mℓ) 시안농도
(ppm)Cyan concentration
(ppm) 처리효율
(%)Processing efficiency
(%) 비교예 44Comparative Example 44 2020 00 00 2525 00 비교예 45Comparative Example 45 2020 22 00 24.724.7 1.21.2 비교예 46Comparative Example 46 2020 44 00 24.824.8 0.80.8 비교예 47Comparative Example 47 2020 66 00 24.824.8 0.80.8 비교예 48Comparative Example 48 2020 88 00 24.724.7 1.21.2 비교예 49Comparative Example 49 2020 1010 00 24.524.5 2.02.0 비교예 50Comparative Example 50 2020 1212 00 24.624.6 1.61.6 비교예 51Comparative Example 51 2020 1414 00 24.624.6 1.61.6 비교예 52Comparative Example 52 2020 1616 00 24.824.8 0.80.8 비교예 53Comparative Example 53 2020 118118 00 24.924.9 0.40.4 비교예 54Comparative Example 54 2020 2020 00 24.824.8 0.80.8

실시예 83Example 83 2020 00 2020 0.240.24 99.0499.04 실시예 84Example 84 2020 22 2020 0.220.22 99.1299.12 실시예 85Example 85 2020 44 2020 0.190.19 99.2499.24 실시예 86Example 86 2020 66 2020 0.180.18 99.2899.28 실시예 87Example 87 2020 88 2020 0.180.18 99.2899.28 실시예 88Example 88 2020 1010 2020 0.180.18 99.2899.28 실시예 89Example 89 2020 1212 2020 0.160.16 99.3699.36 실시예 90Example 90 2020 1414 2020 0.150.15 99.4099.40 실시예 91Example 91 2020 1616 2020 0.150.15 99.4099.40 실시예 92Example 92 2020 1818 2020 0.140.14 99.4499.44 실시예 93Example 93 2020 2020 2020 0.150.15 99.4099.40

상기 [표 7]에서 나타난 바와 같이 불소이온과 시안이 함유된 폐수에 불소를 제거한 뒤 시안제거제 중 하나인 황산구리와 염화제2철의 혼합물만을 단계적으로 첨가한 결과는 시안이온의 제거효율이 미미하고, 아황산수소나트륨을 황산구리 중량% 1.31배 첨가한 결과에서 황산구리만을 사용할 때보다 최대 0~0.4%범위에서 시안이온의 제거효율이 증가함을 알 수 있었다.As shown in [Table 7], after removing fluorine from the wastewater containing fluorine ions and cyanide, the stepwise addition of only a mixture of copper sulfate and ferric chloride, which is one of the cyanide removers, shows that the removal efficiency of cyan ions is insignificant. In the results of adding 1.31 times the weight of sodium hydrogen sulfite to 1.31 times the weight of copper sulfate, it was found that the removal efficiency of cyan ions increased in the range of 0 to 0.4% at maximum compared to using only copper sulfate.

도 1, 도 2는 종래의 불소, 시안이온 함유 폐수의 불소, 시안이온 처리공정도,1 and 2 are fluorine and cyan ion treatment process diagram of a conventional fluorine and cyan ion-containing wastewater,

도 3, 도 4는 본 발명의 불소, 시안이온 함유 폐수의 불소, 시안이온 처리 공정도.3 and 4 are fluorine and cyan ion treatment process diagram of the fluorine and cyan ion-containing wastewater of the present invention.

<도면의 주요부분에 대한 부호의 설명><Description of the symbols for the main parts of the drawings>

(1)--집수조 (2)--제 1반응조(1)-Sump Tank (2)-First Reactor

(3)--제 1응집조 (4)--제 2반응조(3)-First Aggregate (4)-Second Reactor

(5)--제 2반응조 (6)--방류조(5)-Second Reaction Tank (6)-Discharge Tank

(7)--응집조 (8)--폐수(7)-coagulation tank (8)-wastewater

Claims (10)

불소이온, 시안착화합물과 유리시안을 함유하고 있는 폐수 처리방법에 있어서,In the wastewater treatment method containing fluorine ion, cyanide complex and free cyanide, 불소이온의 제거는, 폐수에 0.5~20 중량%의 알루미늄화합물을 투입하고 산성도를 ph5내지 ph9로 조절하여 알루미늄화합물이 불소이온과 결합하여 침전을 형성하는 단계를 포함하고,The removal of fluorine ions includes the step of adding 0.5-20% by weight of the aluminum compound to the wastewater and adjusting the acidity to ph5 to ph9 to form a precipitate by combining the aluminum compound with the fluorine ion, 시안착화합물과 유리시안의 제거는, 폐수의 산성도를 ph4내지 ph6으로 조절하고, 황산에 5~10중량% 황산구리화합물 및 6.6~13.1중량% 아황산수소나트륨을 같이 혼합하고 교반하는 단계가 포함되어,The removal of the cyanide compound and the free cyanide includes adjusting the acidity of the wastewater to ph 4 to ph 6, and mixing and stirring 5 to 10 wt% copper sulfate compound and 6.6 to 13.1 wt% sodium hydrogen sulfite together with sulfuric acid. 고분자응집제를 투입하여 생성된 슬러지를 응집하여 침강시키고 액상의 폐수에 ph조절제를 투입하여 산성도는 pH6.5내지 pH7.5이고, 불소이온의 농도는 최대 허용치 15ppm이며 시안이온의 농도는 최대 허용치 1ppm으로 제거하는 것을 특징으로 하는 불소이온, 시안착화합물과 유리시안을 함유하고 있는 폐수의 처리방법.The sludge produced by adding the polymer coagulant is agglomerated and settled. The pH control agent is added to the liquid wastewater, and the acidity is pH 6.5 to pH7.5. The concentration of fluorine ion is 15 ppm maximum and the cyan ion concentration is 1 ppm maximum. A method for treating wastewater containing fluorine ions, cyanide compounds and free cyan, characterized in that the removal is carried out by 제 1항에 있어서,The method of claim 1, 시안착화합물과 유리시안을 제거하기 위하여 투입하는 황산과 혼합된 5~10 중량% 황산구리화합물에 0.5~10중량% 황산철화합물을 추가로 투입한 혼합물을 만들고, 여기에 6.6~13.1 중량% 아황산수소나트륨을 더 투입하는 단계가 포함되는 것을 특징으로 하는 불소이온, 시안착화합물과 유리시안을 함유하고 있는 폐수 처리방법.A mixture of 5-10 wt% copper sulfate compound added with sulfuric acid added to remove cyanide compound and free cyanide was added to 0.5-10 wt% ferrous sulfate compound, and 6.6-13.1 wt% sodium hydrogen sulfite Waste water treatment method containing a fluorine ion, a cyanide complex and free cyan, characterized in that it further comprises the step of adding. 제 1항에 있어서,The method of claim 1, 시안착화합물과 유리시안을 제거하기 위하여 투입하는 황산과 혼합된 5~10 중량% 황산구리화합물에 0.5~10중량% 염화철화합물을 추가로 투입한 혼합물을 만들고, 여기에 6.6~13.1 중량% 아황산수소나트륨을 더 투입하는 단계가 포함되는 것을 특징으로 하는 불소이온, 시안착화합물과 유리시안을 함유하고 있는 폐수 처리방법.A mixture of 0.5-10% by weight of ferric chloride was added to 5-10% by weight of copper sulfate compound mixed with sulfuric acid added to remove cyanide and free cyanide, and 6.6-13.1% by weight of sodium hydrogen sulfite was added thereto. Waste water treatment method containing a fluorine ion, a cyanide complex and free cyan, characterized in that further comprising the step of adding. 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete
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KR20180097263A (en) 2017-02-23 2018-08-31 한승케미칼 주식회사 Waste water treatment method of removing fluorine and cyanides
KR102116420B1 (en) * 2017-02-23 2020-05-28 한승케미칼 주식회사 Waste water treatment method of removing fluorine and cyanides
KR20180114325A (en) 2017-04-10 2018-10-18 김상수 Waste water treatment method of removing fluorine and cyanides using rare metal

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