KR20100060260A - Method for treating waste water contained heavy metal - Google Patents

Method for treating waste water contained heavy metal Download PDF

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KR20100060260A
KR20100060260A KR1020080118790A KR20080118790A KR20100060260A KR 20100060260 A KR20100060260 A KR 20100060260A KR 1020080118790 A KR1020080118790 A KR 1020080118790A KR 20080118790 A KR20080118790 A KR 20080118790A KR 20100060260 A KR20100060260 A KR 20100060260A
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wastewater
heavy metal
slag
heavy metals
reducing slag
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KR1020080118790A
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KR100997325B1 (en
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김상빈
손석규
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현대제철 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
    • C02F1/58—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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • 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
    • 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
    • C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)
  • Water Treatment By Sorption (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

PURPOSE: A processing method of wastewater containing heavy metal is provided to reduce processing costs by using reducing slag which is a by-product produced in an electric furnace steel making process and to stably process heavy metal in wastewater. CONSTITUTION: A processing method of wastewater containing heavy metal comprises the following steps: transferring the wastewater to a reaction tank(10); agitating granule sized reducing slag 1mm or less toward the reaction tank; precipitating a heavy metal through adsorption and substitution; precipitating sludge in the slag by discharging the wastewater to a settling tank(20); and discharging supernatant through a filtering machine.

Description

중금속 함유 폐수의 처리방법{Method for treating waste water contained heavy metal}Method for treating waste water contained heavy metal}

본 발명은 중금속 함유 폐수의 처리방법에 관한 것으로, 더욱 상세하게는 전기로 제강공정에서 발생하는 부산물인 환원슬래그를 이용하여 폐수 중 함유된 중금속을 제거하는 중금속 함유 폐수의 처리방법에 관한 것이다. The present invention relates to a method for treating heavy metal-containing wastewater, and more particularly, to a method for treating heavy metal-containing wastewater, which removes heavy metals contained in wastewater by using a reducing slag which is a by-product generated in an electric furnace steelmaking process.

제철공장에서 발생되는 산업폐수에는 다양한 오염물질이 포함되며, 폐수 중에 함유되어 있는 중금속은 산업발전의 영향으로 그 발생량이 증가하고 있다. Industrial wastewater generated in steel mills contains various pollutants, and heavy metals contained in the wastewater are increasing due to industrial development.

중금속은 구리(Cu), 카드뮴(Cd), 납(Pb), 수은(Ag) 등 비중이 4.0 이상의 무거운 금속원소를 말한다. 이러한 중금속은 미량이라도 토양이나 하천 및 지하수로 유입되면 수중 생태계 및 인간의 건강과 생활환경에 악영향을 미치게 된다. 따라서 폐수 중에 함유된 중금속을 효율적으로 제거하기 위한 다양한 방법의 연구가 진행되고 있다. Heavy metals refer to heavy metal elements having a specific gravity of at least 4.0 such as copper (Cu), cadmium (Cd), lead (Pb), and mercury (Ag). Even if a trace amount of heavy metals is introduced into soil, rivers, and groundwater, it adversely affects the aquatic ecosystem and human health and living environment. Therefore, studies of various methods for efficiently removing heavy metals contained in wastewater have been conducted.

폐수 중에 함유된 중금속의 제거방법에는 철염, 알루미늄 등의 화학약품을 첨가하는 방법과, 소석회 등을 이용하는 방법이 주로 활용된다. As a method for removing heavy metals contained in wastewater, a method of adding chemicals such as iron salt and aluminum, and a method using slaked lime or the like are mainly used.

소석회를 이용하는 방법은 폐수에 함유된 중금속을 수산화물 형태로 바꾸어 침전 분리시키는 방법이다. 하지만 이 방법은 비용면에서 저렴한 장점이 있지만 석회슬러지와 같은 폐기물이 다량 발생함으로 인하여 2차적인 환경오염을 유발하는 문제점이 있다. The method using slaked lime converts heavy metals contained in the waste water into hydroxide form and precipitates them. However, this method is inexpensive in terms of cost but has a problem of causing secondary environmental pollution due to the generation of large amounts of waste such as lime sludge.

그리고, 철염, 알루미늄 등의 화학약품을 첨가하는 방법은 중금속 제거 효과는 우수하나 고가의 약품비용을 요구하므로 폐수처리의 운전비용을 상승시키는 문제점이 있다. In addition, the method of adding a chemical such as iron salt, aluminum, etc. is excellent in removing heavy metals, but it requires a high cost of chemicals, thereby increasing the operating cost of wastewater treatment.

본 발명은 상기한 바와 같은 종래의 문제점을 해결하기 위한 것으로, 본 발명의 목적은 중금속이 함유된 폐수를 처리함에 있어 화학약품과 소석회를 대체하면서도 저비용으로 폐수의 중금속 처리효율을 높일 수 있도록 한 중금속 함유 폐수의 처리방법을 제공하는 것이다. The present invention is to solve the conventional problems as described above, an object of the present invention is to replace the chemicals and hydrated lime in the treatment of wastewater containing heavy metals and to improve the heavy metal treatment efficiency of the wastewater at low cost It is to provide a method for treating wastewater containing.

상기한 바와 같은 목적을 달성하기 위한 본 발명의 특징에 따르면, 본 발명은 중금속이 함유된 폐수를 반응조로 유입하고, 상기 반응조 내로 입도 1mm 이하의 환원슬래그를 투입하고 교반하여 중금속을 흡착과 치환을 통해 침전시키는 제 1단계와, 상기 제 1단계를 거친 폐수를 침전조로 배출하여 슬래그를 포함한 슬러지는 침전시키고 상등수만 여과기를 통해 배출시키는 제 2단계를 포함한다.According to the characteristics of the present invention for achieving the above object, the present invention is to introduce the waste water containing heavy metals into the reaction tank, and to reduce the adsorption and substitution of heavy metals by introducing and stirring a reducing slag having a particle size of 1mm or less into the reactor. And a second step of discharging the wastewater passed through the first step into the sedimentation tank to precipitate the sludge including the slag and discharge only the supernatant water through the filter.

상기 환원슬래그는 구리(Cu)와 카드뮴(Cd)의 중금속이 함유된 폐수 1L 당 5~25g을 투입한다.The reducing slag is charged 5 ~ 25g per 1L of wastewater containing heavy metals of copper (Cu) and cadmium (Cd).

본 발명은 중금속이 함유된 폐수를 처리함에 있어 전기로 제강공정에서 발생되는 부산물인 환원슬래그를 재활용한다. 따라서 종래의 화학약품과 소석회를 사용하여 중금속 함유 폐수를 처리하는 방법보다 원가절감 측면에서 경제적인 효과가 있다. The present invention recycles the reducing slag which is a by-product generated in the steelmaking process of electricity in treating wastewater containing heavy metals. Therefore, it is more economical in terms of cost reduction than the conventional method of treating heavy metal-containing wastewater using chemicals and slaked lime.

또한, 환원슬래그는 적정량을 투입할 경우 현재 많이 배출되어 문제가 되는 중금속인 구리와 카드뮴의 제거율이 100%에 근접한다. 따라서 종래의 소석회를 사용하는 방법보다 폐수 중의 중금속을 안정적으로 처리할 수 있는 효과가 있다.In addition, the reduction slag is discharged a lot when the appropriate amount is injected, the removal rate of copper and cadmium, which is a problem, close to 100%. Therefore, there is an effect that can treat the heavy metal in the waste water stably than the method using the conventional slaked lime.

이하 본 발명에 의한 중금속 함유 폐수의 처리방법의 바람직한 실시예를 상세하게 설명한다.Hereinafter, a preferred embodiment of the method for treating heavy metal-containing wastewater according to the present invention will be described in detail.

도 1은 본 발명에 따른 중금속 함유 폐수의 처리방법을 실현하기 위한 공정의 개략적인 구성도이다. 1 is a schematic configuration diagram of a process for realizing a method for treating heavy metal-containing wastewater according to the present invention.

본 발명은 중금속이 함유된 폐수를 반응조로 유입하고 반응조 내로 환원슬래그를 투입하여 폐수 중의 중금속을 흡착 및 치환하여 제거하는 제 1단계와, 제 1단계에서의 폐수를 침전조로 배출하여 상등수만 배출시키는 제 2단계를 포함한다.In the present invention, a wastewater containing heavy metals is introduced into a reactor and a reducing slag is introduced into the reactor to absorb and replace heavy metals in the wastewater, and the wastewater in the first stage is discharged to the settling tank to discharge only the supernatant. It includes a second step.

더 상세히 설명하면, 본 발명은 중금속 함유 폐수를 처리함에 있어 전기로 제강공정에서 발생되는 부산물인 환원슬래그를 재활용하는데 그 특징이 있다. In more detail, the present invention is characterized in recycling the reducing slag which is a by-product generated in the steel making process in the treatment of heavy metal-containing wastewater.

전기로 제강공정에서는 제강톤당 13~17%의 양으로 부산물인 슬래그가 발생된다. 슬래그는 산화슬래그와 환원슬래그로 구분된다. 그 중 환원슬래그는 제강공정에서 산소(O2)와 황(S)을 제거하기 위해 투입되는 생석회와 용강과의 반응에 의해 발생되며, 슬래그 총량의 약 10%를 차지한다. In the furnace steelmaking process, slag is generated as a by-product in an amount of 13 to 17% per ton of steelmaking. Slag is divided into oxidized slag and reduced slag. Among them, reducing slag is generated by the reaction between quicklime and molten steel, which are added to remove oxygen (O 2 ) and sulfur (S) in the steelmaking process, and account for about 10% of the total amount of slag.

전기로 환원슬래그의 성분비는 아래의 표 1과 같다. The component ratio of the furnace slag is shown in Table 1 below.

성분ingredient FeFe SiO2 SiO 2 Al2O5Al 2 O5 MgOMgO CaOCaO Free CaOFree CaO FF NiNi ZnZn PbPb CuCu 함량(%)content(%) 22.0922.09 3.913.91 19.4119.41 11.5211.52 38.0338.03 1.621.62 0.520.52 N.DN.D. N.DN.D. N.DN.D. N.DN.D.

이와 같은 성분의 환원슬래그는 Free CaO를 포함한 산화칼슘(CaO)의 함량이 39.65%로 높아 소석회를 대체하기에 적합하다. 상술한 점에 착안하여 폐수 내 고농도로 함유되어 있는 중금속을 환원슬래그를 이용하여 제거하는 것이다. The reduced slag of such a component is suitable for replacing slaked lime with a high content of calcium oxide (CaO) including Free CaO (39.65%). In view of the foregoing, heavy metals contained in high concentrations in the wastewater are removed using reducing slag.

환원슬래그를 이용한 중금속의 제거는 흡착과 치환에 의해 이루어진다. Removal of heavy metals using reducing slag is accomplished by adsorption and substitution.

흡착은 환원슬래그의 기공이나 입자표면에 중금속이 흡착되는 것이다. 환원슬래그는 입도 1mm이하로 미세 분말화하여 투입할수록 폐수와 접촉되는 반응표면적이 넓어져 흡착처리 효율이 높아진다. 이에 따라 환원슬래그는 볼(ball), 분쇄기(mill), 체(sieve)가름 등을 이용하여 1mm이하의 입도를 가지도록 제조하여 사용한다.Adsorption is the adsorption of heavy metals to the pores or particle surface of the reducing slag. As the reduced slag is finely powdered to a particle size of 1 mm or less, the reaction surface area in contact with the waste water becomes wider, thereby increasing the efficiency of adsorption treatment. Accordingly, the reducing slag is manufactured and used to have a particle size of 1 mm or less using a ball, a mill, a sieve cut, and the like.

치환은 화학적 침전법에 의한 방법이다. 환원슬래그 성분 중 CaO는 폐수와 작용하면 Ca(OH)2로 되고, 여기서, 이온화된 CaOH-는 폐수 중의 중금속인 Cu와 Cd를 Cu(OH)2와 Cd(OH)2로 형성시켜 침전시키게 된다. Substitution is by chemical precipitation. CaO in the reducing slag component becomes Ca (OH) 2 when it interacts with the wastewater, where ionized CaOH − is precipitated by forming Cu and Cd, Cu (OH) 2 and Cd (OH) 2 , heavy metals in the wastewater. .

이외에도, 환원슬래그 성분 중 SiO2는 각종의 유기폐수(불순물질)를 흡착, 흡수시켜 많은 유기물질을 제거시키며, MgO는 폐수와 작용하여 슬러지의 침강성을 촉진시키게 된다. In addition, SiO 2 in the reducing slag component adsorbs and absorbs various organic wastewater (impurity) to remove many organic substances, and MgO acts with the wastewater to promote sludge settling.

환원슬래그는 구리(Cu) 10ppm과 카드뮴(Cd) 5ppm의 중금속이 함유된 폐수 1L 당 5 ~ 25g 범위로 투입되는 것이 바람직하다. 환원슬래그는 투입량이 폐수 1L 당 5g미만으로 투입되면 중금속 제거율이 미비하고, 25g을 초과한 투입은 그 효과가 포화될 뿐 아니라 침전조에서 슬러지양을 늘려 슬러지 재처리를 위한 추가비용의 문제를 발생시킨다. 따라서 폐수 1L 당 25g 이상의 투입은 무의미하다. The reducing slag is preferably added in the range of 5-25 g per liter of wastewater containing 10 ppm of copper (Cu) and 5 ppm of cadmium (Cd). Reducing slag has a heavy metal removal rate when the input amount is less than 5g per 1L of wastewater, and the input exceeding 25g not only saturates the effect but also increases the amount of sludge in the sedimentation tank, causing additional cost for sludge reprocessing. . Therefore, input of more than 25g per 1L of wastewater is meaningless.

이하, 각 단계 공정에 대해 상세히 설명하기로 한다.Hereinafter, each step process will be described in detail.

1. 제 1 단계(환원슬래그 투입)1. First step (Reduction slag input)

중금속이 함유된 폐수를 반응조(10)로 유입하고, 이 반응조(10)에 입도 1mm이하의 환원슬래그를 투입하고 교반을 실시한다. 환원슬래그는 구리(Cu) 10ppm과 카드뮴(Cd) 5ppm의 중금속이 함유된 폐수 1L 당 5 ~ 25g 범위로 투입하고, 교반은 충분한 반응을 위해 2시간 이상으로 한다. 단, 3시간을 초과하면 그 효과가 포화되므로 원가 및 에너지 절감차원에서 3시간 이내로 유지한다. 그리고 반응은 실온(25℃)에서 수행한다.        Wastewater containing heavy metals is introduced into the reaction tank 10, and a reducing slag having a particle size of 1 mm or less is introduced into the reaction tank 10 and stirred. The reducing slag is charged in the range of 5 to 25 g per 1 L of wastewater containing 10 ppm of copper (Cu) and 5 ppm of cadmium (Cd), and stirring is performed for 2 hours or more for a sufficient reaction. However, if it exceeds 3 hours, the effect is saturated, so it should be kept within 3 hours in terms of cost and energy saving. And the reaction is carried out at room temperature (25 ° C.).

2. 제 2 단계(침전 및 배출)2. Second stage (sedimentation and discharge)

반응조(10)의 폐수를 침전조(20)로 배출하여 슬래그를 포함한 슬러지와 상등수를 분리하고 상등수의 맑은 용액은 여과기를 통과하여 배출시킨다. 침전조(20)는 최종적으로 잔류하는 오염물질(예컨데, 비중이 가벼운 중금속인 MnO2 등)을 배출기준 이내로 관리하기 위해 설치된다. 여과기로는 활성탄 여과기 또는 모래를 이용한 여과기 등이 사용된다. The wastewater of the reactor 10 is discharged to the settling tank 20 to separate the sludge and the supernatant containing the slag, and the clear solution of the supernatant is discharged through the filter. The sedimentation tank 20 is installed to finally manage the remaining pollutants (eg, MnO 2 , a heavy metal with a specific gravity) within emission standards. As the filter, an activated carbon filter or a filter using sand is used.

여기서, 상등수는 침전조에서 슬러지를 가라앉힌 윗부분의 가장 맑은 물을 의미한다. 그리고, 침전조는 다수개가 구비되어, 반응조에서 중화처리한 폐수를 여러단계의 침전조를 통과시키면서 중화처리할 수도 있다. Here, the supernatant means the clearest water in the upper part where the sludge is settled in the sedimentation tank. In addition, a plurality of settling tanks are provided, and the wastewater neutralized in the reaction tank may be neutralized while passing through various stages of settling tanks.

이하, 본 발명의 이해를 돕고자 중금속 함유 폐수의 처리방법을 실시예를 통해 설명하기로 한다. Hereinafter, a method for treating heavy metal-containing wastewater to help understanding of the present invention will be described through examples.

[실시예 1]Example 1

표 1의 성분을 갖는 환원슬래그를 분쇄하고 체가름하여 입도 1mm이하로 제조하였다. 이와 같이 제조된 환원슬래그의 중금속 제거능력을 확인하기 위해 구리(10ppm)와 카드뮴(5ppm)을 포함한 중금속 함유 폐수를 제조하여 환원슬래그의 투입량을 변화시키면서 중금속 제거능력을 확인하였다. The reduced slag having the components shown in Table 1 was pulverized and sieved to prepare a particle size of 1 mm or less. In order to confirm the heavy metal removal capacity of the reduced slag prepared as described above, heavy metal-containing wastewater including copper (10ppm) and cadmium (5ppm) was prepared, and the heavy metal removal capacity was confirmed while changing the input amount of the reducing slag.

즉, 중금속 함유 폐수 1L에 환원슬래그를 무게비로 0.25%, 0.5%, 1%, 2.5% 투입하여 급속 교반시킨 후 방치하여 환원슬래그를 침전시키고 상등수를 채취하여 분석하였다. That is, 0.25%, 0.5%, 1%, and 2.5% of the reduced slag was added to 1 L of heavy metal-containing wastewater by rapid stirring, followed by rapid stirring to precipitate the reduced slag, and the supernatant was collected and analyzed.

표 2는 환원슬래그 투입량에 따른 구리와 카드뮴의 제거율 변화를 실험한 결과이다. Table 2 shows the results of experiments on the change of removal rate of copper and cadmium according to the input of reducing slag.

구분
division
환원슬래그 투입농도(중량비)Reduced slag injection concentration (weight ratio) 00 0.25%0.25% 0.5%0.5% 1%One% 2.5%2.5% Cu
Cu
농도(ppm)Concentration (ppm) 1010 7.76687.7668 0.0040.004 0.00120.0012 0.01010.0101 제거율(%)% Removal 00 22.322.3 99.9699.96 99.9999.99 99.999.9 Cd
CD
농도(ppm)Concentration (ppm) 55 55 00 00 00 제거율(%)% Removal 00 00 100100 100100 100100

표 2의 구리와 카드뮴의 제거효율을 살펴보면, 환원슬래그를 5%이상으로 투입하였을 경우 폐수에 함유된 구리와 카드뮴의 제거율이 100%에 근접함이 확인된다. 이는 폐수 1L를 기준으로 할때 5g에 해당되는 투입량이다. Looking at the removal efficiency of copper and cadmium in Table 2, it is confirmed that the removal rate of copper and cadmium in the wastewater is close to 100% when the reducing slag is added at 5% or more. This is an input equivalent to 5g based on 1L of wastewater.

여기서, 구리와 카드뮴을 실험데이터로서 제시한 것은 구리와 카드뮴이 일반적으로 많이 배출되고 문제가 되는 중금속이기 때문이다. The reason why copper and cadmium are presented as experimental data is that copper and cadmium are heavy metals that are generally emitted and problematic.

상술한 실험결과에 의해, 폐수 1L 당 입도 1mm이하의 환원슬래그를 5~25g 범위로 투입하고, 침전조를 통해 상등수만 배출하는 방법이 폐수에 함유된 중금속을 효율적으로 제거할 수 있는 방법임을 알 수 있다. According to the above experimental results, reducing slag having a particle size of 1mm or less per 1L of wastewater was introduced in the range of 5-25g, and only the supernatant water was discharged through the sedimentation tank to efficiently remove heavy metals contained in the wastewater. have.

이와 같은 본 발명의 기본적인 기술적 사상의 범주 내에서, 당업계의 통상의 지식을 가진 자에게 있어서는 다른 많은 변형이 가능함은 물론이고, 본 발명의 권리범위는 첨부한 특허청구 범위에 기초하여 해석되어야 할 것이다. Within the scope of the basic technical idea of the present invention, many other modifications are possible to those skilled in the art, and the scope of the present invention should be interpreted based on the appended claims. will be.

도 1은 본 발명에 따른 중금속 함유 폐수의 처리방법을 실현하기 위한 공정의 개략적인 구성도. 1 is a schematic configuration diagram of a process for realizing a method for treating heavy metal-containing wastewater according to the present invention.

* 도면의 주요 부분에 대한 부호의 설명 *Explanation of symbols on the main parts of the drawings

10:반응조 20:침전조10: reactor 20: sedimentation tank

Claims (2)

중금속이 함유된 폐수를 반응조로 유입하고, 상기 반응조 내로 입도 1mm 이하의 환원슬래그를 투입하고 교반하여 중금속을 흡착과 치환을 통해 침전시키는 제 1단계와, A first step of introducing heavy metal-containing wastewater into the reaction tank, and introducing a reducing slag having a particle size of 1 mm or less into the reactor and stirring the precipitate to precipitate the heavy metal by adsorption and substitution; 상기 제 1단계를 거친 폐수를 침전조로 배출하여 슬래그를 포함한 슬러지는 침전시키고 상등수만 여과기를 통해 배출시키는 제 2단계를 포함하는 것을 특징으로 하는 중금속 함유 폐수의 처리방법.Discharging the wastewater passed through the first step to the sedimentation tank, the sludge including the slag is settled, and the wastewater containing heavy metals, characterized in that it comprises a second step of discharge through the filter. 청구항 1에 있어서, The method according to claim 1, 상기 환원슬래그는 구리(Cu)와 카드뮴(Cd)의 중금속이 함유된 폐수 1L 당 5~25g을 투입하는 것을 특징으로 하는 산성폐수의 처리방법.The reducing slag is 5 to 25g per 1L waste water containing heavy metals of copper (Cu) and cadmium (Cd) treatment method of acidic wastewater.
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CN104086030A (en) * 2014-07-24 2014-10-08 江苏贝斯特水处理科技有限公司 Method for treating pickling wastewater in iron and steel industry
CN108558083A (en) * 2018-05-07 2018-09-21 程佩芳 A kind of heavy metal wastewater thereby integrated approach device
CN108773929A (en) * 2018-06-13 2018-11-09 岳西县创奇电器有限责任公司 A kind of electroplating wastewater preprocess method
CN111252875A (en) * 2020-02-20 2020-06-09 广西埃索凯生物科技有限公司 Treatment process of heavy metal-containing wastewater
CN114524553A (en) * 2022-03-16 2022-05-24 赣州八0一钨业有限公司 Process for treating heavy metal wastewater by using alkaline-boiling tungsten slag

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CN104086030A (en) * 2014-07-24 2014-10-08 江苏贝斯特水处理科技有限公司 Method for treating pickling wastewater in iron and steel industry
CN108558083A (en) * 2018-05-07 2018-09-21 程佩芳 A kind of heavy metal wastewater thereby integrated approach device
CN108773929A (en) * 2018-06-13 2018-11-09 岳西县创奇电器有限责任公司 A kind of electroplating wastewater preprocess method
CN111252875A (en) * 2020-02-20 2020-06-09 广西埃索凯生物科技有限公司 Treatment process of heavy metal-containing wastewater
CN114524553A (en) * 2022-03-16 2022-05-24 赣州八0一钨业有限公司 Process for treating heavy metal wastewater by using alkaline-boiling tungsten slag

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