KR100398420B1 - A Removal Method of Organics in Zn-Cr Eletroplating Wastewater - Google Patents
A Removal Method of Organics in Zn-Cr Eletroplating Wastewater Download PDFInfo
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- KR100398420B1 KR100398420B1 KR10-1999-0060906A KR19990060906A KR100398420B1 KR 100398420 B1 KR100398420 B1 KR 100398420B1 KR 19990060906 A KR19990060906 A KR 19990060906A KR 100398420 B1 KR100398420 B1 KR 100398420B1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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Abstract
본 발명은 Zn-Cr도금폐수중 유기물 제거방법에 관한 것이며, 그 목적하는 바는 Zn-Cr도금 폐수 중의 유기물성분인 EDTA 성분을 역세가능형 정밀 여과막과 역삼투법을 이용하여 분리제거하고 농축수는 도금용액으로 재활용할 수 있도록함으로써, 슬러지 발생을 최소화하면서 Zn-Cr 도금폐수 중의 유기물 성분을 효과적으로 제거할 수 있는 방법을 제공하고자 하는데 있다.The present invention relates to a method for removing organic matter in Zn-Cr plating wastewater, and an object thereof is to separate and remove the EDTA component, which is an organic component in Zn-Cr plating wastewater, using a backwashable microfiltration membrane and a reverse osmosis method, and the concentrated water is plated. The present invention aims to provide a method for effectively removing organic components from Zn-Cr plating wastewater while minimizing sludge generation by recycling them into a solution.
상기 목적을 달성하기 위한 본 발명은 Zn-Cr도금폐수를 처리하는 방법에 있어서, 세공경이 0.01-0.2μm인 역세가능형 정밀여과막을 이용하여 2-4kg/cm2의 운전압력으로 상기 폐수를 처리한 다음, 세공경이 10Å이하인 역삼투막을 이용하여 16-18kg/cm2의 운전압력으로 상기 역세가능형 정밀여과막을 통과한 폐수를 처리하는 것을 특징으로 하는 Zn-Cr도금폐수중 유기물 제거방법에 관한 것을 그 요지로 한다.In order to achieve the above object, the present invention provides a method for treating Zn-Cr plated wastewater, by using a backwashable precision filtration membrane having a pore diameter of 0.01-0.2 μm, the wastewater at an operating pressure of 2-4 kg / cm 2 . After the treatment, using the reverse osmosis membrane having a pore diameter of 10Å or less, the method for removing organic matter from Zn-Cr-plated wastewater, characterized in that the wastewater passing through the backwashable microfiltration membrane at an operating pressure of 16-18kg / cm 2 . Let that point be about that.
Description
본 발명은 Zn-Cr 도금폐수 처리방법에 관한 것이며, 보다 상세하게는 역세가능형 정밀여과막과 역삼투막을 이용한 Zn-Cr 도금폐수 중의 유기물 제거방법에 관한 것이다.The present invention relates to a Zn-Cr plating wastewater treatment method, and more particularly to a method for removing organic matter in Zn-Cr plating wastewater using a backwashable microfiltration membrane and a reverse osmosis membrane.
일반적으로 도금공장에서는 열연코일을 소재로 하여 산세, 냉간압연, 전기청정, 소둔 및 도금공정을 통하여 미려한 냉연 및 도금제품을 생산한다. 이때, 도금폐수 중의 유기물 성분을 제거하기 위해 종래의 화학적 산화법 및 응집 침전법이 사용되어 왔다.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. At this time, conventional chemical oxidation and coagulation precipitation methods have been used to remove organic components in the plating wastewater.
상기 화학적 산화법은 과산화수소, 과망간삼칼륨 등과 같은 산화제를 사용하여 폐수 중의 유기물을 화학적으로 산화시켜 제거하는 방법이고, 응집 침전법은 알루미늄염이나 철염을 사용하여 폐수 중의 유기물을 응집, 침전시켜 제거하는 방법이다.〔Journal of KSEE, Vol. 18. p43-54(1996)〕The chemical oxidation method is a method of chemically oxidizing and removing organic substances in wastewater using an oxidizing agent such as hydrogen peroxide, tripotassium permanganate, etc., and the coagulation precipitation method is a method of flocculating and precipitation of organic substances in wastewater using aluminum salt or iron salt. [Journal of KSEE, Vol. 18. p43-54 (1996)]
그러나, 이와 같은 종래의 방법은 응집제와 같은 화학약품을 사용함으로써 약품 비용으로 인한 비용이 발생되어 폐수처리 비용이 상승하게 되고, 슬러지가 다량 발생할 뿐만 아니라 별도로 발생하는 슬러지를 처리해야 하는 문제가 있는 것이다.However, such a conventional method has a problem in that the costs of chemicals are generated by using a chemical such as a flocculant, thereby increasing the cost of wastewater treatment, and a large amount of sludge is generated, as well as a problem of treating sludge generated separately. .
이에, 본 발명자들은 상기 문제를 해결하기 위해 연구와 실험을 거듭하고 그 결과에 근거하여 본 발명을 제안하게 된 것으로, 본 발명은 Zn-Cr도금 폐수 중의 유기물성분인 EDTA(Ethylene Diamine Tetraacetic Acid)성분을 역세가능형 정밀 여과막과 역삼투법을 이용하여 분리제거하고 농축수는 도금용액으로 재활용할 수 있도록함으로써, 슬러지 발생을 최소화하면서 Zn-Cr 도금폐수 중의 유기물 성분을 효과적으로 제거할 수 있는 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 is an EDTA (Ethylene Diamine Tetraacetic Acid) component which is an organic component in Zn-Cr plating wastewater. By separating and removing by using a backwashable microfiltration membrane and reverse osmosis method, the concentrated water can be recycled to the plating solution, thereby providing a method for effectively removing organic components in Zn-Cr plating wastewater while minimizing sludge generation. , Its purpose is.
도 1은 본 발명에 의한 역세가능형 정밀여과막과 역삼투막에 의한 폐수 중의 유기물 제거효과를 COD 농도로 나타낸 그래프.1 is a graph showing the COD concentration of the organic matter removal effect in the wastewater by the backwashable microfiltration membrane and the reverse osmosis membrane according to the present invention.
도 2는 종래 방법에 의한 폐수 중의 유기물 제거효과를 COD 농도로 나타낸 그래프.Figure 2 is a graph showing the COD concentration of the organic matter removal effect in the waste water by the conventional method.
상기 목적을 달성하기 위한 본 발명은 Zn-Cr도금폐수를 처리하는 방법에 있어서, 세공경이 0.01-0.2μm인 역세가능형 정밀여과막을 이용하여 2-4kg/cm2의 운전압력으로 상기 폐수를 처리한 다음, 세공경이 10Å이하인 역삼투막을 이용하여 16-18kg/cm2의 운전압력으로 상기 역세가능형 정밀여과막을 통과한 폐수를 처리하는 것을 특징으로 하는 Zn-Cr도금폐수중 유기물 제거방법에 관한 것이다.In order to achieve the above object, the present invention provides a method for treating Zn-Cr plated wastewater, by using a backwashable precision filtration membrane having a pore diameter of 0.01-0.2 μm, the wastewater at an operating pressure of 2-4 kg / cm 2 . After the treatment, using the reverse osmosis membrane having a pore diameter of 10Å or less, the method for removing organic matter from Zn-Cr-plated wastewater, characterized in that the wastewater passing through the backwashable microfiltration membrane at an operating pressure of 16-18kg / cm 2 . It is about.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서는 Zn-Cr도금폐수를 세공경이 0.01-0.2μm인 역세가능형 정밀여과막을 이용하여 2-4kg/cm2의 운전압력으로 처리한다.In the present invention, the Zn-Cr plating wastewater is treated at an operating pressure of 2-4 kg / cm 2 using a backwashable microfiltration membrane having a pore diameter of 0.01-0.2 μm.
상기 역세가능형 정밀여과막은 SS성분(부유물질)을 제거하기 위한 것이다.The backwashable microfiltration membrane is for removing the SS component (floating material).
상기 역세가능형 정밀여과막은 세공경이 0.01-0.2μm와 같은 범위의 것을 사용하는데, 이는 전처리 효과를 나타내는 지표인 SDI(Silt Density Index)가 5이하를 만족시키기 위한 것이다. 즉, 역세가능형 정밀여과막을 이용한 전처리후에 행하는 역삼투막에 문제가 없도록 하기 위해서는 SDI가 5이하를 만족시켜야 하는 것이다.The backwashable microfiltration membrane has a pore diameter in the range of 0.01-0.2 μm, which is intended to satisfy the SDI (Silt Density Index), which is an index indicating the pretreatment effect. In other words, in order to prevent problems with the reverse osmosis membrane after pretreatment using the backwashable microfiltration membrane, the SDI must satisfy 5 or less.
상기 운전압력은 2-4kg/cm2의 범위로 행하는 것이 바람직한데, 운전압력이 2kg/cm2미만이면 처리시간이 너무 길어지는 문제점이 있고, 4kg/cm2을 초과하면 막에 부하가 너무 걸리며, 특히 막이 오염되어 있을 때 더욱 심해진다.The operating pressure is preferably carried out in the range of 2-4kg / cm 2 , there is a problem that the processing time is too long if the operating pressure is less than 2kg / cm 2, if the load exceeds 4kg / cm 2 is too much load on the membrane This is especially true when the membrane is contaminated.
또한, 본 발명에서는 상기 역세가능형 정밀여과막을 통과한 폐수를 세공경이 10Å이하인 역삼투막을 이용하여 16-18kg/cm2의 운전압력으로 처리한다.In the present invention, the wastewater passing through the backwashable microfiltration membrane is treated at an operating pressure of 16-18 kg / cm 2 using a reverse osmosis membrane having a pore diameter of 10 kPa or less.
상기 역삼투막은 EDTA의 제거에 효과적이며, 특히 금속-EDTA를 제거하기 위한 것이다.The reverse osmosis membrane is effective for removing EDTA, particularly for removing metal-EDTA.
상기 역삼투막은 세공경이 10Å이하인 것을 사용하는 것이 바람직한데, 세경공이 10Å을 초과하는 경우에는 금속-EDTA의 제거효과를 충분히 얻을 수 없기 때문이다.The reverse osmosis membrane is preferably used having a pore diameter of 10 kPa or less, because when the fine pore exceeds 10 kPa, the effect of removing the metal-EDTA cannot be sufficiently obtained.
상기 운전압력은 16-18kg/cm2의 범위로 행하는 것이 바람직한데, 운전압력이 16kg/cm2미만이면 처리시간이 너무 길어지는 문제점이 있고, 18kg/cm2을 초과하면 막에 부하가 너무 걸리며, 특히 막이 오염되어 있을 때 더욱 심해진다.The operating pressure is preferably carried out in the range of 16-18kg / cm 2 , but if the operating pressure is less than 16kg / cm 2, there is a problem that the processing time is too long, and if the operating pressure exceeds 18kg / cm 2 , the membrane is too overloaded. This is especially true when the membrane is contaminated.
상기 역삼투막으로 유입되는 폐수의 양은 장치조건에 따라 설정할 수 있으나, 본 발명과 같은 장치구성 및 운전조건하에서는 16-18ℓ/min의 범위로 유입되는 것이 바람직하다.The amount of wastewater introduced into the reverse osmosis membrane may be set according to the device conditions, but it is preferable to be introduced in the range of 16-18 l / min under the device configuration and operating conditions as the present invention.
본 발명을 실시하는데 있어서 필요한 실험장치는 크게 유입폐수저장조(Feed Storage Tank), BMF(Backwashable Micro Filter, 역세가능형 정밀여과막), 역삼투블럭(R/O Block )으로 구성되어 있고, 원폐수의 온도가 높을 경우 분리막 시스템의 최고운전 온도인 45℃이하로 냉각시키기 위한 냉각기가 부착되어 있다. Zn-Cr도금폐수가 유입폐수저장조에서 공급펌프(Feed Pump)를 통해 BMF를 거쳐서 고압 펌프(Pump)에 의해 역삼투막(R/O Membrane)을 통과하여 투과수와 농축수로 분리된다. 막(Membrane)을 장시간 가동하면 막오염의 진행에 따라 투과 유량(Flux)이 감소하는데 이때에는 세정제를 사용하여 막을 세정해주어야 한다.The experimental apparatus required for carrying out the present invention is composed of a largely fed inlet storage tank (Feed Storage Tank), backwashable micro filter (backwashable microfiltration membrane), reverse osmosis block (R / O Block), If the temperature is high, a cooler is attached to cool below 45 ℃, the maximum operating temperature of the membrane system. Zn-Cr plating wastewater is separated into permeate and concentrated water through the reverse osmosis membrane (R / O membrane) by the high pressure pump through the BMF through the feed pump in the inflow wastewater storage tank. If the membrane is operated for a long time, the flux decreases as the membrane contamination progresses. In this case, the membrane should be cleaned using a cleaning agent.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
실시예 1Example 1
세공경이 0.01μm이고 중공사형(Hollow Fiber Type)인 역세가능형 정밀여과막(BMF)과, 직경 61mm, 길이 1016mm이고 세공경이 10Å인 역삼투막 모듈 장치로, Zn-Cr도금폐수를 16-18ℓ/min의 유속으로 연속운전을 수행하였다. 이때, BMF의 운전압력은 3kg/cm2이었고, 역삼튜막 모듈의 운전압력은 17kg/cm2이었다.Reverse osmosis membrane module device with a pore diameter of 0.01 μm and hollow fiber type (BMF), and a reverse osmosis membrane module device with a diameter of 61 mm, a length of 1016 mm, and a pore diameter of 10 μm. Continuous operation was performed at a flow rate of min. At this time, the operating pressure of the BMF was 3kg / cm 2 , the operating pressure of the reverse osmosis membrane module was 17kg / cm 2 .
상기 Zn-Cr도금폐수 원수의 pH, SS농도 및 COD는 하기 표1과 같았으며, BMF처리후 및 역삼투막 처리후의 pH, SS농도 및 COD를 각각 측정하여 하기 표1에 나타내었다. 또한, 제거효율을 계산하여 하기 표1에 나타내었다.The pH, SS concentration and COD of the Zn-Cr plated wastewater were as shown in Table 1 below, and the pH, SS concentration, and COD after BMF treatment and reverse osmosis membrane treatment were measured, respectively, and are shown in Table 1 below. In addition, the removal efficiency is calculated and shown in Table 1 below.
상기 표1에서 알 수 있는 바와 같이, BMF와 R/O처리한 경우의 SS성분은 제거효율이 100%이고, COD성분은 99.5%로 처리효과가 우수하였다. 또한, BMF처리수의 SS농도가 0.5ppm으로 전처리 효과를 나타내는 지표인 SDI가 5이하를 만족하였다.As can be seen in Table 1, the SS component in the case of BMF and R / O treatment is 100% removal efficiency, COD component was 99.5% was excellent treatment effect. In addition, the SS concentration of the BMF treated water was 0.5 ppm, and the SDI, an index indicating the pretreatment effect, satisfied 5 or less.
실시예 2Example 2
(발명예)(Invention example)
SDI가 5이하인 Zn-Cr 도금폐수를 역삼투막 모듈 실험장치에 16~18ℓ/min의 유속으로 78시간동안 연속운전을 수행하였고, 운전압력은 16~18㎏/㎠로 고정하여 폐수 중의 EDTA 성분을 분리제거하였다.The Zn-Cr plating wastewater with SDI of 5 or less was continuously operated for 78 hours at a reverse osmosis membrane module experimental apparatus at a flow rate of 16-18 l / min, and the operating pressure was fixed at 16-18 kg / cm 2 to separate EDTA components from the wastewater. Removed.
그때의 운전시간 변화에 다른 투과수의 COD 농도를 하기 표2 및 도 1에 나타내었다.The COD concentrations of the permeate water different from the operation time change at that time are shown in Table 2 and FIG. 1.
상기 표2 및 도 1의 그래프에서 알 수 있듯이, 초기 Zn-Cr 도금폐수의 COD 농도가 2000㎎/L 이었고 투과수와 리턴수를 다시 재이용(recycle)해서 78시간 연속 운전한 후 투과수의 COD농도가 10.9㎎/L로 낮아져, 역삼투막을 이용하여 Zn-Cr 도금폐수 중의 유기물이 효과적으로 제거됨을 알 수 있었다.As can be seen from the graph of Table 2 and FIG. 1, the COD concentration of the initial Zn-Cr plating wastewater was 2000 mg / L and the recycled permeate and return water were recycled for 78 hours, and then the COD of the permeate was It was found that the concentration was lowered to 10.9 mg / L, and the organic matter in the Zn-Cr plating wastewater was effectively removed using a reverse osmosis membrane.
(비교예)(Comparative Example)
Zn-Cr도금폐수를 종래의 방법인 과산화수소와 철염을 이용한 Fenton Oxidation 방법으로 처리하였으며, 그 결과를 하기 표3에 나타내었다. 또한, 도 2에 사용된 과산화수소의 주입농도에 따른 COD 농도로 나타내었다.Zn-Cr plating wastewater was treated by the conventional Fenton Oxidation method using hydrogen peroxide and iron salts, and the results are shown in Table 3 below. In addition, it is represented by the COD concentration according to the injection concentration of hydrogen peroxide used in FIG.
상기 표3 및 도 2의 그래프에서 알 수 있는 바와 같이, 초기 COD 농도가 2000㎎/L였던 Zn-Cr 도금폐수는 과산화수소와 철염으로 유기물을 산화분해한 후에도 과산화수소 주입농도 600㎎/L일 때 처리수의 COD 농도가 968㎎/L 이상으로 COD 제거율이 52% 정도로 폐수 중의 유기물 성분의 제거 효율이 상기 발명예에 비하여 그다지 높지 않음을 알 수 있었다.As can be seen in the graphs of Table 3 and Figure 2, the Zn-Cr plating wastewater, which had an initial COD concentration of 2000 mg / L, was treated at a hydrogen peroxide injection concentration of 600 mg / L even after oxidative decomposition of organic matter with hydrogen peroxide and iron salt. The COD concentration of the water was 968 mg / L or more and the COD removal rate was 52%, indicating that the removal efficiency of the organic component in the wastewater was not so high as compared with the above-described invention.
상술한 바와 같은 본 발명에 의하면, 역세가능형 정밀여과막과 역삼투막을 이용하여 Zn-Cr폐수중의 EDTA성분을 분리제거함으로서, 종래 화학적산화법 및 응집침전법에 비하여 슬러지 발생을 감소시킴과 동시에 폐수 중의 유기물 성분을 효과적으로 제거할 수 있다.According to the present invention as described above, by separating and removing the EDTA component in the Zn-Cr wastewater using a backwashable microfiltration membrane and a reverse osmosis membrane, the sludge generation is reduced compared to the conventional chemical oxidation method and flocculation sedimentation method, The organic component can be removed effectively.
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| KR100429763B1 (en) * | 2002-01-08 | 2004-05-03 | 정건용 | Method for Recycling the Valuable Components from Cleaning Wastewater of Printed Circuit Board |
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| JPH03242288A (en) * | 1990-02-17 | 1991-10-29 | Nitto Denko Corp | Treatment of raw water by reverse osmosis membrane module |
| KR19980078119A (en) * | 1997-04-25 | 1998-11-16 | 안덕기 | Wastewater Treatment and Reuse Method using Microfiltration and Reverse Osmosis Membrane and Its Apparatus |
| KR19990032736A (en) * | 1997-10-20 | 1999-05-15 | 한형수 | High efficiency water treatment system |
| KR19990050183A (en) * | 1997-12-16 | 1999-07-05 | 이구택 | Wastewater treatment using backwashable microfiltration membrane and reverse osmosis membrane system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH03242288A (en) * | 1990-02-17 | 1991-10-29 | Nitto Denko Corp | Treatment of raw water by reverse osmosis membrane module |
| KR19980078119A (en) * | 1997-04-25 | 1998-11-16 | 안덕기 | Wastewater Treatment and Reuse Method using Microfiltration and Reverse Osmosis Membrane and Its Apparatus |
| KR19990032736A (en) * | 1997-10-20 | 1999-05-15 | 한형수 | High efficiency water treatment system |
| KR19990050183A (en) * | 1997-12-16 | 1999-07-05 | 이구택 | Wastewater treatment using backwashable microfiltration membrane and reverse osmosis membrane system |
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| US8269127B2 (en) | 2008-12-04 | 2012-09-18 | Ls Industrial Systems Co., Ltd. | Tulip contacting device for vacuum circuit breaker |
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