KR100325329B1 - METHOD FOR REMOVING COLOR FROM Pb-Sn PLATING WASTEWATER - Google Patents

METHOD FOR REMOVING COLOR FROM Pb-Sn PLATING WASTEWATER Download PDF

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KR100325329B1
KR100325329B1 KR1019970074247A KR19970074247A KR100325329B1 KR 100325329 B1 KR100325329 B1 KR 100325329B1 KR 1019970074247 A KR1019970074247 A KR 1019970074247A KR 19970074247 A KR19970074247 A KR 19970074247A KR 100325329 B1 KR100325329 B1 KR 100325329B1
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wastewater
lead
tin plating
activated carbon
color
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KR19990054433A (en
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고광섭
강신경
김해룡
유윤기
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이구택
포항종합제철 주식회사
신현준
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
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • 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
    • 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)
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  • Analytical Chemistry (AREA)
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Abstract

PURPOSE: To remove color of Pb-Sn plating wastewater generated from steelmaking facilities by using activated carbon column with reduced amount of sludge. CONSTITUTION: The method comprises the steps of homogenizing Pb-Sn plating wastewater; bubbling air into the wastewater upwardly to remove oil; adjusting pH of the wastewater to pH 9 in order to convert heavy metal ion into metal oxides, thereby precipitating the metal oxides; removing residual impurities from the wastewater after heavy metal precipitation; and introducing the wastewater into an activated carbon column to adsorb color.

Description

납-주석도금폐수의 색도제거방법How to remove color of lead-tin plating wastewater

본 발명은 납-주석도금폐수의 색도제거방법에 관한 것으로, 보다 상세하게는 입상활성탄을 충진한 흡착탑을 이용하여 납-주석도금폐수의 색도를 제거하는 방법에 관한 것이다.The present invention relates to a method for removing color of lead-tin plating wastewater, and more particularly, to a method for removing color of lead-tin plating wastewater by using an adsorption tower filled with granular activated carbon.

일반적으로 도금공장에서는 열연코일을 소재로 하여 산세, 냉간압연, 전기청정, 소둔 및 도금공정을 통하여 미려한 냉연 및 도금제품을 생산한다.In general, plating factories produce beautiful cold rolled and plated products using hot rolled coils through pickling, cold rolling, electric cleaning, annealing, and plating processes.

이러한 도금과정에서 오일, 산, 알칼리, 탈유폐액, 유기물함유폐수, 크롬함유폐수 등 다양한 폐수가 발생하게 된다.In this plating process, various wastewaters such as oil, acid, alkali, de-waste, organic matter-containing wastewater and chromium-containing wastewater are generated.

특히 납-주석을 이용하여 도금할 때 발생하는 도금폐수의 경우에는 폐수의 색도가 높다는 문제점이 있다.In particular, in the case of plating wastewater generated when plating with lead-tin, the chromaticity of the wastewater is high.

도금공장에서 납-주석을 이용하여 도금할 때 발생되는 납-주석도금폐수중의 색도를 제거하기 위하여 종래에는 화학적 산화법과 응집침전법 등을 주로 사용하여 왔다.In order to remove chromaticity in the lead-tin plating wastewater generated when plating using lead-tin in a plating factory, chemical oxidation and coagulation sedimentation have been mainly used.

화학적 산화법은 과산화수소, 과망간산칼륨 등과 같은 산화제를 사용하여 색도성분을 화학적으로 산화시켜 제거하는 방법이고, 응집침전법은 알루미늄염과 철염을 사용하여 색도성분을 응집시켜 침전시키는 방법이다[J of KSEE, 제18권 제1번 p43-54(1996)].The chemical oxidation method is a method of chemically oxidizing and removing chromatic components using an oxidizing agent such as hydrogen peroxide and potassium permanganate, and the coagulation precipitation method is a method of agglomeration and precipitation of chromatic components using aluminum salts and iron salts [J of KSEE, Vol. 18, No. 1, p43-54 (1996).

도 1은 상기와 같은 종래의 방법에 의한 도금공장 폐수의 처리공정을 도시한 것이다.Figure 1 shows the treatment process of the plating plant wastewater by the conventional method as described above.

납-주석도금폐수는 조정조(1)에서 균질화되고, 오일분리조(2)에서 부상오일이 제거된다.The lead-tin plating wastewater is homogenized in the adjusting tank 1, and the floating oil is removed in the oil separation tank 2.

균질화되고 오일이 제거된 폐수는 중화조(3)로 이송되어 중화반응이 일어나침전조(4)에서 중금속이온이 침전된다.The waste water homogenized and the oil is removed is transferred to the neutralization tank (3), whereby a neutralization reaction occurs, and heavy metal ions are precipitated in the precipitation tank (4).

색도를 제거하기 위한 과산화수소나 염화철(II)는 중화조(3)에서 첨가되어 폐수와 화학적 산화반응 또는 응집침전반응을 하게 된다.Hydrogen peroxide or iron (II) chloride to remove chromaticity is added in the neutralization tank (3) to undergo chemical oxidation or flocculation settling with the wastewater.

침전조(4)에서 침전물들은 슬러지저장조(5)로 이송되고 상등액은 상등수조(6)로 이송된다.In the sedimentation tank (4), sediment is transferred to the sludge storage tank (5) and the supernatant is transferred to the supernatant tank (6).

상등수조(6)를 거친 상등액은 자갈필터(7)에서 미세 불순물성분이 제거됨으로써 처리수로 된다.The supernatant liquid having passed through the supernatant tank 6 is treated water by removing fine impurity components from the gravel filter 7.

그러나 상기와 같은 종래의 방법들은 산화제 및 응집제와 같은 화학약품을 사용하므로 약품비용이 많이 들어 폐수처리비용이 상승하게 되고 슬러지가 많이 발생하게 될 뿐 아니라 발생하는 슬러지의 처리가 어려운 문제점이 있다.However, since the conventional methods use chemicals such as oxidizing agents and flocculants, the cost of chemicals increases and wastewater treatment costs increase and sludge is generated a lot.

상기의 문제점을 해결하기 위한 본 발명은 제철소의 도금공장에서 납-주석 도금모드시 발생하는 납-주석도금폐수의 색도를 제거하기 위하여 입상활성탄을 충진한 흡착탑을 이용하여 색도성분을 흡착하여 제거함으로써 슬러지발생을 최소화하면서 납-주석도금폐수중 색도성분을 효과적으로 제거할 수 있는 방법을 제공함을 그 목적으로 한다.The present invention for solving the above problems by adsorbing and removing the chromatic components by using an adsorption tower filled with granular activated carbon to remove the chromaticity of the lead-tin plating wastewater generated during the lead-tin plating mode in the plating factory of steel mill Its purpose is to provide a method to effectively remove chromatic components from lead-tin plating wastewater while minimizing sludge generation.

도 1은 종래의 도금공장폐수의 처리공정도,1 is a process chart of the conventional plating plant wastewater,

도 2는 본 발명에 의한 도금공장폐수의 처리공정도,Figure 2 is a process chart of the plating plant wastewater according to the present invention,

도 3은 본 발명에 의한 방법의 색도제거효과를 도시한 그래프,3 is a graph showing the chromaticity removing effect of the method according to the present invention;

도 4는 종래의 방법중 화학적 산화법에 의한 색도제거효과를 도시한 그래프,4 is a graph showing the color removal effect by the chemical oxidation method of the conventional method,

도 5는 종래의 방법중 응집침전법에 의한 색도제거효과를 도시한 그래프.Figure 5 is a graph showing the color removal effect by the coagulation sedimentation method of the conventional method.

본 발명은 납-주석 도금폐수중 색도를 제거하는 방법에 있어서, 상기 폐수를 균질화하는 단계; 균질화된 폐수중 공기를 공급해서 부상오일성분을 제거하는 단계; pH 9로 조정하여 중금속이온을 금속산화물로 침전시키는 단계; 미제거된 불순물을 제거하는 단계; 활성탄 흡착탑을 이용하여 색도성분을 흡착하여 제거하는 단계를 포함하여 이루어지는 것을 특징으로 하는 납-주석도금폐수의 색도제거방법에 관한 것이다.The present invention provides a method for removing chromaticity in lead-tin plating wastewater, comprising: homogenizing the wastewater; Supplying air in the homogenized wastewater to remove floating oil components; adjusting the pH to 9 to precipitate heavy metal ions as metal oxides; Removing unremoved impurities; The present invention relates to a method for removing color of lead-tin plating wastewater, comprising: adsorbing and removing chromaticity components using an activated carbon adsorption tower.

또한 상기의 흡착탑을 만들기 위한 활성탄은 입상활성탄을 사용하고, 활성탄의 충진높이는 1-1.5m범위로 하며, 흡착탑내로의 폐수의 유입속도는 10-15m/hr로 하는 것을 특징으로 하는 납-주석도금폐수의 색도제거방법에 관한 것이다.In addition, the activated carbon used to make the adsorption tower uses granular activated carbon, and the filling height of the activated carbon is in the range of 1-1.5 m, and the inflow rate of wastewater into the adsorption tower is 10-15 m / hr. The present invention relates to a method for removing color of wastewater.

이하 본 발명에 대하여 상세하게 설명한다.Hereinafter, the present invention will be described in detail.

본 발명은 납-주석 도금폐수중 색도를 제거하는 방법에 있어서, 상기 폐수를 균질화하는 단계; 균질화된 폐수중 공기를 공급해서 부상오일성분을 제거하는 단계; pH 9로 조정하여 중금속이온을 금속산화물로 침전시키는 단계; 미제거된 불순물을 제거하는 단계; 활성탄 흡착탑을 이용하여 색도성분을 흡착하여 제거하는 단계를 포함하여 이루어지는 것을 특징으로 하는 납-주석도금폐수의 색도제거방법에 관한 것이다.The present invention provides a method for removing chromaticity in lead-tin plating wastewater, comprising: homogenizing the wastewater; Supplying air in the homogenized wastewater to remove floating oil components; adjusting the pH to 9 to precipitate heavy metal ions as metal oxides; Removing unremoved impurities; The present invention relates to a method for removing color of lead-tin plating wastewater, comprising: adsorbing and removing chromaticity components using an activated carbon adsorption tower.

이하 도면을 참조하여 본 발명은 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

도 2는 본 발명에 의한 납-주석도금폐수의 색도제거공정을 도시한 공정도이다.2 is a process chart showing a color removal process of lead-tin plating wastewater according to the present invention.

본 발명을 납-주석도금폐수의 색도제거공정의 장치는 납-주석 도금폐수를 균질화시키는 조정조(1), 부상오일을 제거시키는 오일분리조(2), 중금속이온을 침전시켜 제거시키는 중화조(3) 및 침전조(4), 미세 불순물성분을 제거하는 자갈필터(7), 색도성분을 제거하는 카본필터(8)로 구성된다.The apparatus of the present invention for removing the color of lead-tin plating waste water is a control tank (1) for homogenizing lead-tin plating waste water, an oil separation tank (2) for removing floating oil, and a neutralization tank for precipitating and removing heavy metal ions ( 3) and a precipitation tank 4, a gravel filter 7 for removing fine impurity components, and a carbon filter 8 for removing chromatic components.

납-주석도금폐수는 먼저 조정조(1)에서 균질화되고, 균질화된 납-주석도금폐수오일분리조(2)로 이송된다.The lead-tin plating wastewater is first homogenized in the adjusting tank 1 and then transferred to the homogenized lead-tin plating wastewater oil separation tank 2.

오일분리조(2)에서는 납-주석도금폐수에 공기를 공급하여 부상오일성분을 제거한다.In the oil separation tank 2, air is supplied to the lead-tin plating wastewater to remove the floating oil component.

오일이 제거된 납-주석도금폐수는 중화조(3)로 이송되고, 중화조(3)와 침전조(4)에서는 폐수의 pH를 9로 조정함으로써 중금속이온을 금속산화물형태로 침전시켜 제거한다.Oil-free lead-tin plating wastewater is transferred to the neutralization tank (3), and in the neutralization tank (3) and the settling tank (4) by adjusting the pH of the wastewater to 9 to remove the heavy metal ions in the form of metal oxides.

침전조(4)에서 중금속이온의 침전물은 슬러지저장조(5)로 이송되고 상등액은 상등수조(6)로 이송된다.In the settling tank (4), the precipitate of heavy metal ions is transferred to the sludge storage tank (5) and the supernatant is transferred to the supernatant tank (6).

상등수조(6)로 이송된 납-주석도금폐수는 자갈필터(7)를 통과하게 되는데, 자갈필터(7)를 통과하면서 납-주석도금폐수의 미세 불순물성분이 제거된다.The lead-tin plating wastewater transferred to the upper tank 6 passes through the gravel filter 7, and fine impurities of the lead-tin plating wastewater are removed while passing through the gravel filter 7.

자갈필터(7)를 통과한 납-주석도금폐수는 마지막으로 흡착탑인 카본필터(8)를 통과하게 된다. 활성탄, 모래, 자갈이 위에서부터 충진된 카본필터(8)는 납-주석도금폐수를 하향류로 통과하면서 납-주석도금폐수의 색도성분을 흡착하여 제거한다.The lead-tin plating wastewater passing through the gravel filter 7 finally passes through the carbon filter 8 which is an adsorption tower. The carbon filter 8 filled with activated carbon, sand, and gravel from above is adsorbed and removed the chromatic components of the lead-tin plating wastewater while flowing downwardly through the lead-tin plating wastewater.

흡착탑을 만들기 위한 활성탄으로는 입상활성탄을 사용하고, 흡착탑에 활성탄을 충진하는 높이는 1-1.5m범위로 하며, 흡착탑내로의 폐수의 유입속도는 10-15m/hr로 하는 것이 바람직하다.Granular activated carbon is used as the activated carbon for making the adsorption tower, and the height of filling activated carbon in the adsorption tower is in the range of 1-1.5 m, and the inflow rate of wastewater into the adsorption tower is preferably 10-15 m / hr.

이하 실시예를 통하여 상세하게 설명한다.It will be described in detail through the following examples.

(실시예)(Example)

먼저 상등수조의 납-주석 도금폐수를 종래의 방법중 과산화수소를 이용한 화학적 산화법으로 처리한 후, 그 결과를 하기 표 1에 나타내었다.First, the lead-tin plating wastewater of the upper tank was treated by a chemical oxidation method using hydrogen peroxide in a conventional method, and the results are shown in Table 1 below.

과산화수소주입농도(mg/ℓ)Hydrogen peroxide injection concentration (mg / ℓ) 00 500500 800800 10001000 15001500 20002000 색도(도)Chromaticity (degrees) 105105 3030 2424 2222 2222 2222

상기 표 1의 결과에서 초기 색도가 105도였던 납-주석 도금폐수는 과산화수소로 산화처리한 후에도 색도가 20도이상으로 나타나 과산화수소의 색도제거효율이 그다지 높지 않음을 알 수 있다.In the result of Table 1, the lead-tin plating wastewater having an initial color of 105 degrees is shown to have a color of 20 degrees or more even after oxidation with hydrogen peroxide, so that the color removal efficiency of hydrogen peroxide is not very high.

다음으로 상등수조의 납-주석 도금폐수를 종래의 방법중 염화철(II)을 이용한 응집침전법으로 처리하여, 그 결과를 하기 표 2에 나타내었다.Next, the lead-tin plating wastewater of the upper tank was treated by a coagulation sedimentation method using iron (II) chloride in the conventional method, and the results are shown in Table 2 below.

염화철(II)주입농도(mg/ℓ)Iron (II) chloride injection concentration (mg / ℓ) 00 500500 800800 10001000 15001500 20002000 색도(도)Chromaticity (degrees) 105105 3535 2525 2323 2424 2424

상기 표 2의 결과에서 초기 색도가 105도였던 납-주석 도금폐수는 염화철로 응집처리한 후에도 색도가 20도이상으로 나타나 염화철(II)의 색도제거효율이 그다지 높지 않음을 알 수 있다.In the result of Table 2, the lead-tin plating wastewater having an initial color of 105 ° was shown to have a color of 20 ° C. or more after agglomeration with iron chloride, so that the color removal efficiency of iron (II) chloride was not very high.

염화철(II)의 색도제거효율은 과산화수소를 이용한 방법에 비해서도 색도제거효과가 낮았다.The color removal efficiency of iron (II) chloride was lower than that of hydrogen peroxide.

마지막으로 본 발명의 방법을 이용하여 납-주석도금폐수를 처리하여 색도를 제거한 후 색도를 측정하였다.Finally, the chromaticity was measured after removing the chromaticity by treating lead-tin plating wastewater using the method of the present invention.

직경 100mm, 높이 3000mm의 흡착칼럼실험장치에 활성탄을 2000mm 충진하여 카본칼럼을 제작한 후 상등수조의 납-주석 도금폐수를 일정한 유량으로 32시간동안 하향류로 통과시키면서 흡착실험을 하였다.Adsorption experiments were carried out by filling activated carbon 2000mm into an adsorption column tester with a diameter of 100mm and a height of 3000mm and passing the lead-tin plating wastewater of the upper tank at a constant flow rate for 32 hours.

흡착칼럼을 통과한 폐수의 색도를 측정하여 그 결과를 하기 표 3에 나타내었다.The chromaticity of the wastewater passing through the adsorption column was measured and the results are shown in Table 3 below.

반응시간(시간)Response time (hours) 00 1One 22 44 88 1818 3232 색도(도)Chromaticity (degrees) 105105 22 33 33 33 55 55

상기 표 3의 결과에서 초기 색도가 105도였던 납-주석 도금폐수는 카본칼럼을 통과한 후에는 색도가 5도이하로 낮아져 본 발명에 의한 방법의 색도제거효율이 종래의 방법에 비해 아주 우수하다는 것을 알 수 있다.In the result of Table 3, the lead-tin plating wastewater, which had an initial color of 105 degrees, was lowered to less than 5 degrees after passing through a carbon column, indicating that the chromaticity removal efficiency of the method according to the present invention is superior to the conventional method. Able to know.

상기와 같은 본 발명은 입상활성탄을 충진한 흡착탑을 이용하여 제철소의 도금공장에서 납-주석 도금모드시 발생하는 납-주석도금폐수의 색도성분을 흡착하여 제거함으로써 슬러지발생을 최소화하면서도 납-주석도금폐수중 색도성분을 효과적으로 제거할 수 있는 효과가 있다.The present invention as described above, by adsorbing and removing the chromatic components of lead-tin plating wastewater generated during the lead-tin plating mode in the steel mill plating adsorption tower packed with granular activated carbon, while minimizing sludge generation, lead-tin plating There is an effect that can effectively remove the chromatic components in the waste water.

Claims (2)

납-주석 도금폐수중 색도를 제거하는 방법에 있어서, 상기 폐수를 균질화하는 단계; 균질화된 폐수중 공기를 공급해서 부상오일성분을 제거하는 단계; pH 9로 조정하여 중금속이온을 금속산화물로 침전시키는 단계; 미제거된 불순물을 제거하는 단계; 활성탄 흡착탑을 이용하여 색도성분을 흡착하여 제거하는 단계를 포함하여 이루어지는 것을 특징으로 하는 납-주석도금폐수의 색도제거방법.CLAIMS 1. A method for removing chromaticity in lead-tin plating wastewater, the method comprising: homogenizing the wastewater; Supplying air in the homogenized wastewater to remove floating oil components; adjusting the pH to 9 to precipitate heavy metal ions as metal oxides; Removing unremoved impurities; Color removal method of lead-tin plating waste water, characterized in that it comprises the step of adsorbing and removing the chromatic component using the activated carbon adsorption column. 제1항에 있어서, 흡착탑을 만들기 위한 활성탄은 입상활성탄을 사용하고, 활성탄의 충진높이는 1-1.5m범위로 하며, 흡착탑내로의 폐수의 유입속도는 10-15m/hr로 하는 것을 특징으로 하는 납-주석도금폐수의 색도제거방법.The method of claim 1, wherein the activated carbon used to make the adsorption tower is granular activated carbon, the filling height of the activated carbon is in the range of 1-1.5m, and the inflow rate of wastewater into the adsorption tower is 10-15m / hr. -Color removal method of tin plating wastewater.
KR1019970074247A 1997-12-26 1997-12-26 METHOD FOR REMOVING COLOR FROM Pb-Sn PLATING WASTEWATER KR100325329B1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000040927A (en) * 1998-12-21 2000-07-15 신현준 Method for removing organic matters in coating wastewater
KR100804245B1 (en) * 2006-09-08 2008-02-18 재단법인 포항산업과학연구원 Method for removing heavy metal and color from landfill leachates using steelmaking slag

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000040927A (en) * 1998-12-21 2000-07-15 신현준 Method for removing organic matters in coating wastewater
KR100804245B1 (en) * 2006-09-08 2008-02-18 재단법인 포항산업과학연구원 Method for removing heavy metal and color from landfill leachates using steelmaking slag

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