KR100804245B1 - Method for removing heavy metal and color from landfill leachates using steelmaking slag - Google Patents

Method for removing heavy metal and color from landfill leachates using steelmaking slag Download PDF

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KR100804245B1
KR100804245B1 KR1020060086784A KR20060086784A KR100804245B1 KR 100804245 B1 KR100804245 B1 KR 100804245B1 KR 1020060086784 A KR1020060086784 A KR 1020060086784A KR 20060086784 A KR20060086784 A KR 20060086784A KR 100804245 B1 KR100804245 B1 KR 100804245B1
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leachate
heavy metal
steelmaking slag
metal ions
landfill leachate
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KR1020060086784A
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Korean (ko)
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고광섭
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재단법인 포항산업과학연구원
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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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/62—Heavy metal 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06—Contaminated groundwater or leachate
    • 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

Abstract

A method for removing heavy metal ions and chromaticity components from leachate is provided to treat the leachate generated from a landfill efficiently, by using steelmaking slag, byproduct generated from a steelmaking process of an iron foundry. Leachate of a landfill is homogenized. The homogenized leachate is passed through a column filled with steelmaking slag containing CaO to have a pH value of 8 or more, thereby precipitating heavy metal ions with metal hydroxide. The heavy metal ions remaining in the leachate after precipitation are adsorbed on fine pores of the steelmaking slag. The leachate passed by the column is pH-regulated to have a pH value of 6-8. The pH-regulated leachate is passed through a column filled with granular activated carbon, thereby removing chromaticity components therefrom.

Description

제강슬래그를 이용한 침출수 중 중금속이온 및 색도 제거방법{Method for removing heavy metal and color from landfill leachates using steelmaking slag}Method for removing heavy metal and color from landfill leachates using steelmaking slag}

도 1은 본 발명의 방법이 적용된 침츨수의 처리 공정도, 및1 is a process chart of treatment of sediment water to which the method of the present invention is applied, and

도 2는 본 발명에 의한 시간변화에 따른 중금속이온 제거효율을 나타낸 그래프이다.Figure 2 is a graph showing the removal efficiency of heavy metal ions with time changes according to the present invention.

본 발명은 침출수 중의 중금속이온 및 색도 성분을 제거하는 방법에 관한 것으로, 더욱 자세하게는 매립장에서 발생하는 침출수를 제철소 제강공정에서 발생하는 부산물인 제강슬래그를 이용하여 효과적으로 침출수 중의 중금속이온 및 색도성분을 제거하는 방법에 관한 것이다. The present invention relates to a method for removing heavy metal ions and chromatic components in leachate, and more specifically, the leachate generated in the landfill site is effectively removed by using steelmaking slag which is a by-product of the steelmaking process. It is about how to.

매립장에서 발생되는 침출수는 유기물질,중금속이온 및 기타 무기물질이 다양하게 포함되어 있는 악성폐수로서 그 처리에 어려움이 많다.Leachate from landfill is a malignant wastewater containing a variety of organic materials, heavy metal ions and other inorganic materials, which is difficult to treat.

현재까지 가장 잘 알려진 매립장 침출수 처리방법은 다공층을 통하여 집수된 후 생물학적 방법으로 처리되고 있으나, 중금속이온 제거는 화학적침전법이 주로 이용되고 있다.The best known landfill leachate treatment to date is collected through the porous layer and then treated by biological methods, but heavy metal ion removal is mainly used for chemical precipitation.

그러나 최근에는 매립장에서 발생되는 침출수 중의 오염물질을 매립장 구조물질로 이용되는 점토질이나 복토용 토양에 흡착 처리함으로써 환경에 대한 위해를 근원적으로 줄이는 방법과 침출수의 재순환에 의한 매립장 안정화 방법이 활발하게 연구되고 있다. 상기와 같이 종래의 방법들은 기술적인 측면에서 많은 문제점을 내포하고 있고, 약품에 의한 화학침전법은 약품비용이 많이 들고 슬러지 발생량이 많을 뿐만 아니라 발생되는 슬러지 처리에 어려운 점이 많아 문제시 되고 있다. Recently, however, studies have been actively conducted to reduce the environmental hazards by adsorbing contaminants in leachate from landfills into clay or cover soils used as landfill structures and stabilizing landfills by recycling leachate. have. As described above, the conventional methods have many problems in technical aspects, and the chemical precipitation method using chemicals is a problem due to the high cost of chemicals and a large amount of sludge generation, as well as difficult sludge treatment.

이에, 본 발명자들은 상기의 문제점을 해결하기 위해 연구와 실험을 거듭하고 그 결과에 근거하여 본 발명을 제안하게 된 것으로, 본 발명은 제강슬래그 충전제를 이용하여 매립장 침출수 중의 중금속이온 및 색도를 제거하기 위한 방법을 제공하고자 하는데, 그 목적이 있다.Accordingly, the present inventors have repeatedly conducted research and experiments to solve the above problems and propose the present invention based on the results. The present invention uses steelmaking slag filler to remove heavy metal ions and chromaticity in landfill leachate. It is intended to provide a method for this purpose.

상기 목적을 달성하기 위한 본 발명의 매립장 침출수 중의 중금속이온 및 색도를 제거하는 방법은, 상기 매립장 침출수를 균질화하는 단계; 상기 균질화된 매립장 침출수를 CaO가 함유된 제강슬래그가 충전된 칼럼에 통과시켜 pH 8 이상으로 중화시켜 상기 중금속이온을 금속수산화물로 침전 제거하고, 상기 침전 제거 후 상기 매립장 침출수에 잔존하는 상기 중금속이온을 상기 제강슬래그 자체 미세 기공에 의해 흡착 제거하는 단계; 상기 제강슬래그가 충전된 칼럼에 통과되어 pH 8 이상으로 중화된 상기 매립장 침출수를 pH 6 내지 8로 pH를 조정하는 단계; 및 상기 pH가 조정된 매립장 침출수를 활성탄으로 단독 충전된 입상활성탄 충전 칼럼에 통과시켜 상기 pH 조정된 매립장 침출수로부터 상기 색도를 제거하는 단계를 포함하는 것을 특징으로 한다.Method for removing heavy metal ions and chromaticity in the landfill leachate of the present invention for achieving the above object, homogenizing the landfill leachate; The homogenized landfill leachate is passed through a steel-filled slag containing CaO to neutralize to pH 8 or above to precipitate and remove the heavy metal ions with metal hydroxide, and after the precipitation is removed, the heavy metal ions remaining in the landfill leachate are removed. Adsorption removal by the steelmaking slag itself micropores; Adjusting the pH of the landfill leachate to a pH of 6 to 8 which is passed through the column filled with the steelmaking slag and neutralized to pH 8 or higher; And removing the chromaticity from the pH-adjusted landfill leachate by passing the pH-adjusted landfill leachate through a granular activated carbon packed column alone filled with activated carbon.

또한, 바람직하게는, 상기 제강슬래그가 충전된 칼럼을 통과하는 침출수의 체류시간은 유속 4 내지 6 S.V(Space Velocity(1/hr))로 유지하는 것이 바람직하다. 이를 시간으로 환산하면, 4 S.V는 60분/4S.V가 되어 15분이되고, 6S.V는 60분/6S.V가 되어 10분이된다. 즉, 본 실시예에서 침출수의 체류시간은 10분 내지 15분으로 유지하는 것이 바람직하다. 본 실시예에서 침출수의 체류시간을 유속 4 내지 6 S.V로 한정하는 이유는, 유속이 4 S.V 미만이 되면 채널링 효과로 인해 접촉효율이 저하되고, 6 S.V 초과가 되면 처리유량이 많아져 제강슬래그 흡착력의 저하를 야기시키기 때문이다. 이때 침출수의 체류시간이 10분 내지 15분인 경우, 운전 시간은 4 내지 6시간을 유지하는 것이 바람직하다. Preferably, the residence time of the leachate passing through the column filled with the steelmaking slag is preferably maintained at a flow velocity of 4 to 6 S.V (Space Velocity (1 / hr)). In terms of time, 4 S.V becomes 60 minutes / 4 S.V, which is 15 minutes, and 6 S.V becomes 60 minutes / 6 S.V, which is 10 minutes. That is, in this embodiment, the residence time of the leachate is preferably maintained at 10 to 15 minutes. The reason for limiting the residence time of the leachate to the flow rate of 4 to 6 SV in this embodiment is that the contact efficiency is lowered due to the channeling effect when the flow rate is less than 4 SV, and the treatment flow rate increases when the flow rate is greater than 6 SV, so that the steel slag adsorption force is increased. This is because it causes a decrease. At this time, if the residence time of the leachate is 10 minutes to 15 minutes, the operating time is preferably maintained for 4 to 6 hours.

이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

본 발명에 사용되는 제강슬래그는 통상의 제강슬래그를 사용할 수 있으며, 그 대표적인 예로서 하기 표 1과 같은 화학조성을 갖는 제강슬래그를 사용할 수 있다.The steelmaking slag used in the present invention may use a conventional steelmaking slag, and a steelmaking slag having a chemical composition as shown in Table 1 may be used as a representative example thereof.

성분ingredient CaOCaO SiO2 SiO 2 Al2O3 Al 2 O 3 T-FeT-Fe MnOMnO 조성Furtherance 44.8 -52.344.8 -52.3 13.2-18.813.2-18.8 0.9-2.80.9-2.8 14.8-19.214.8-19.2 2.8-9.62.8-9.6

(단위 : wt%)(Unit: wt%)

상기 표 1과 같이 제강슬래그는 통상 50wt% 정도의 CaO를 함유하고 있는데,상기 CaO가 알칼리성을 나타내므로 중화제로서의 역할을 하게 된다. 따라서 본 실시예에서는 중화제 특성을 갖는 CaO가 함유된 제강슬래그를 충전재로 이용하여 제강슬래그 충전층을 형성하고, 침출수를 수계로 유출하기 전에 상기 형성된 제강슬래그 충전층을 통과시켜 pH 8 이상으로 중화처리한다. 이에 의해, 중금속이온 및 색도가 함유된 매립장 침출수로부터 중금속이온을 수산화물로 침전 제거할 수 있다. As shown in Table 1, the steelmaking slag usually contains about 50 wt% of CaO. Since CaO exhibits alkalinity, it serves as a neutralizing agent. Therefore, in the present embodiment, using the steelmaking slag containing CaO having a neutralizing agent as a filler to form a steelmaking slag packed layer, and neutralized to pH 8 or more by passing the formed steelmaking slag packed layer before flowing out the leachate into the water system do. Thereby, heavy metal ions can be precipitated and removed by hydroxide from landfill leachate containing heavy metal ions and chromaticity.

본 발명에서 사용한 제강슬래그의 입자 size별 비표면적을 분석하였다. 그 결과를 하기 표 2에 나타내었다. 흡착력에 가장 큰 영향을 미치는 인자로는 비표면적을 들 수 있는데, 제강슬래그의 입자가 작을수록 표면적은 증가하고 따라서 흡착사이트(site)도 증가하여 흡착능력이 좋아짐을 알 수 있다.
본 실시예에서는 제강슬래그 충전층을 통과시키는 것에 의해 매립장 침출수로부터 중금속 이온을 수산화물로 침전 제거함과 동시에, 제강슬래그의 자체 미세 기공에 의한 중금속이온에 대한 흡착능력을 이용하여 제강슬래그 충전층을 통과하는 침출수로부터 크롬,아연,납 등의 중금속이온을 흡착 제거한다. The specific surface area of each steel size of steelmaking slag used in the present invention was analyzed. The results are shown in Table 2 below. The most influential factor on the adsorption capacity is the specific surface area. As the particles of steelmaking slag are smaller, the surface area increases, and thus the adsorption site (site) also increases, so that the adsorption capacity is improved.
In this embodiment, the heavy metal ions are precipitated and removed from the landfill leachate by passing the steelmaking slag packed layer, and the adsorption capacity of heavy metal ions by the fine pores of the steelmaking slag is passed through the steelmaking slag packed layer. Heavy metal ions such as chromium, zinc and lead are adsorbed and removed from the leachate.

입자크기(mesh)Particle size (mesh) 7 - 12 7-12 12 - 2012-20 20 - 7020-70 비교분석(㎡/g)Comparative analysis (㎡ / g) 20.2720.27 23.6123.61 41.4341.43 Pore Volume(cc/g)Pore Volume (cc / g) 0.00720.0072 0.00840.0084 0.01470.0147

제강슬래그에 의한 2차 오염 유무를 판단하기 위해 제강슬래그 용출실험에 의한 투과수 중 오염물 농도를 분석한 결과를 표 3에 나타내었다.Table 3 shows the results of analyzing the concentration of contaminants in the permeated water by steelmaking slag dissolution test to determine the secondary contamination caused by steelmaking slag.

성분ingredient FF CdCD PbPb MnMn CrCr 함량content 0.1mg/L이하0.1mg / L or less 00 0-0.01mg/L0-0.01mg / L 00 0-0.020-0.02

상기 표 3에서 볼 수 있듯이 제강슬래그에서 용출되는 각각의 오염물질 농도는 매우 낮아 매립장 침출수를 처리하는 중화제로 이용하는데 문제가 야기되지 않는다는 것을 보여준다.As can be seen in Table 3, the concentration of each pollutant eluted from the steelmaking slag is very low, indicating that there is no problem in using the landfill leachate as a neutralizing agent.

이하에서는 실시예를 통하여 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.

(실시예)(Example)

제1도에 표시된 바와 같이 매립장 침출수를 대신해서 합성한 중금속이온 함유 침출수 시료를 내경 26mm, 높이 600mm 인 칼럼에 30-70mesh 제강슬래그를 322g, 470mm 충전한 칼럼에서 유속 4 내지 6 S.V(Space Velocity) 바람직하게는 5 S.V로, 4 내지 6시간 바람직하게는 5시간 동안 상향류로 접촉시키면 크롬, 아연, 납이온을 포함한 중금속이온을 금속수산화물로 침전 제거되고. 동시에 제강슬래그 자체 미세 기공의 흡착능력에 의해서 중금속이온이 흡착 제거된다. pH 조정조에서 pH 조정제로 pH를 6 내지 8, 바람직하게는 pH7 근처로 조정한 후 침출수가 입상활성탄 충전 칼럼을 통과하면 pH가 조정된 침출수 중 색도가 제거된 투명한 색상을 띄게 되는 최종 처리수를 얻을 수 있다.
본 실시예에서 입상활성탄은 모래나 자갈과 같은 기타 불순물이 포함되어 있지 않은 활성탄만으로 단독 충전된 칼럼이다. 입상활성탄 충전 칼럼의 통과 조건은 단지 침출수로부터 색도를 제거하기 위한 목적이므로 제강슬래그 충전 칼럼에서와 같은 유속으로 통과시킨다. 제2도에서 나타난 바와 같이 시간변화에 대한 중금속이온 제거효율이 2시간 이후 그 제거효율이 90%이상으로 거의 완전히 제거됨을 알 수 있었다. As shown in FIG. 1, 4 to 6 SV (Space Velocity) flows in a column filled with 322 g of 30-70mesh steelmaking slag in a column having a diameter of 26 mm and a height of 600 mm for a leachate containing heavy metal ions synthesized in place of the landfill leachate. Preferably, at 5 SV, 4 to 6 hours, preferably 5 hours of upstream contact, heavy metal ions including chromium, zinc and lead ions are precipitated and removed with metal hydroxides. At the same time, heavy metal ions are adsorbed and removed by the adsorption capacity of the fine pores of steelmaking slag itself. After adjusting the pH to 6 to 8, preferably near pH 7, in the pH adjusting tank, the leachate is passed through the granular activated carbon packed column to obtain the final treated water, which has a clear color without the color of the adjusted leachate. Can be.
In this embodiment, the granular activated carbon is a column filled solely with activated carbon that does not contain other impurities such as sand or gravel. The passing conditions of the granular activated carbon packed column are only for removing the color from the leachate, so they are passed at the same flow rate as in the steelmaking slag packed column. As shown in FIG. 2, it was found that the removal efficiency of heavy metal ions with respect to time was almost completely removed after 90 hours.

이와 같이 본 발명은 CaO가 함유된 제강슬래그를 충전재로 이용하여 충전층을 형성하여 수계로 유출 전에 제강슬래그 층을 통과시켜 pH 8 이상으로 중화처리하여 금속수산화물로 침전 제거함과 동시에 제강슬래그의 중금속이온 흡착능력에 의해서 크롬,아연,납 등의 중금속이온을 제거하고, 입상활성탄 충전층을 통과시켜 색도를 제거하여 매립장 침출수를 효과적으로 처리할 수 있다.As described above, the present invention forms a packed layer using the CaO-containing steel slag as a filler, passes through the steel slag layer before flowing out into the water, neutralizes it to pH 8 or more, and removes precipitates with metal hydroxide, and at the same time, heavy metal ions of the steelmaking slag. The adsorption ability can remove heavy metal ions such as chromium, zinc and lead, and remove chromaticity through the granular activated carbon packed bed to effectively treat the landfill leachate.

Claims (2)

매립장 침출수 중의 중금속이온 및 색도를 제거하는 방법에 있어서, In the method for removing heavy metal ions and chromaticity in landfill leachate, 상기 매립장 침출수를 균질화하는 단계; Homogenizing the landfill leachate; 상기 균질화된 매립장 침출수를 CaO가 함유된 제강슬래그가 충전된 칼럼에 통과시켜 pH 8 이상으로 중화시켜 상기 중금속이온을 금속수산화물로 침전 제거하고, 상기 침전 제거 후 상기 매립장 침출수에 잔존하는 상기 중금속이온을 상기 제강슬래그 자체 미세 기공에 의해 흡착 제거하는 단계;The homogenized landfill leachate is passed through a column filled with CaO containing steelmaking slag to neutralize to pH 8 or above to precipitate and remove the heavy metal ions with metal hydroxide, and after the precipitation is removed, the heavy metal ions remaining in the landfill leachate are removed. Adsorption removal by the steelmaking slag itself micropores; 상기 제강슬래그가 충전된 칼럼에 통과되어 pH 8 이상으로 중화된 상기 매립장 침출수를 pH 6 내지 8로 pH를 조정하는 단계; 및Adjusting the pH of the landfill leachate to a pH of 6 to 8 which is passed through the column filled with the steelmaking slag and neutralized to pH 8 or higher; And 상기 pH가 조정된 매립장 침출수를 활성탄으로 단독 충전된 입상활성탄 충전 칼럼에 통과시켜 상기 pH 조정된 매립장 침출수로부터 상기 색도를 제거하는 단계를 포함하는 것을 특징으로 하는 매립장 침출수 중 중금속이온 및 색도 제거방법.And removing the chromaticity from the pH-adjusted landfill leachate by passing the pH-adjusted landfill leachate through a granular activated carbon packed column filled solely with activated charcoal. 제 1 항에 있어서,The method of claim 1, 상기 제강슬래그가 충전된 칼럼을 통과하는 매립장 침출수는 유속 4 내지 6 S.V(Space Velocity)으로 10 내지 15분 동안 체류하는 것을 특징으로 하는 매립장 침출수 중 중금속이온 및 색도 제거방법.Landfill leachate passing through the column filled with steelmaking slag is heavy metal ions and chromaticity removal method in the landfill leachate, characterized in that the residence for 10 to 15 minutes at a flow rate of 4 to 6 S.V (Space Velocity).
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