KR20040078776A - A method for treatment of sewage and wastewater - Google Patents

A method for treatment of sewage and wastewater Download PDF

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KR20040078776A
KR20040078776A KR1020030013632A KR20030013632A KR20040078776A KR 20040078776 A KR20040078776 A KR 20040078776A KR 1020030013632 A KR1020030013632 A KR 1020030013632A KR 20030013632 A KR20030013632 A KR 20030013632A KR 20040078776 A KR20040078776 A KR 20040078776A
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wastewater
sewage
chemical
treatment
electrolysis
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KR1020030013632A
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KR100461913B1 (en
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김상용
김탁현
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한국생산기술연구원
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/06Contaminated groundwater or leachate
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/20Nature of the water, waste water, sewage or sludge to be treated from animal husbandry

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

PURPOSE: To exclude additional injection of electrolyte during electrolysis of wastewater by feeding Cl-based coagulant in wastewater for chemical coagulation before electrolysis, thereby improving wastewater treatment efficiency with less chemical cost. CONSTITUTION: The method comprises steps of (a) feeding Cl-based coagulant into wastewater to bond colloid particles and then flash mixing; (b) agitating the wastewater slow to flocculate colloid particles; (c) settling flocculated colloid particle included in wastewater; and (d) treating supernatant by electrolysis.

Description

하수 및 폐수 처리 방법{A method for treatment of sewage and wastewater}A method for treatment of sewage and wastewater

본 발명은 하수는 물론 고농도의 유기성 산업폐수, 침출수 및 농축산폐수의 처리 등에 활용될 수 있는 하수 및 폐수 처리 방법에 관한 것이다.The present invention relates to sewage and wastewater treatment methods that can be utilized for the treatment of organic industrial wastewater, leachate and concentrated wastewater, as well as sewage.

특히, 염소계 화학 응집과 전기분해 반응을 결합한 고도 수처리 방법으로서, 염소 이온을 함유하는 화학 응집제를 이용한 응집단계와 전기화학적인 산화처리단계를 수처리 공정에 순차적으로 부여함으로써, 수처리 효율은 향상시키고 전해질 용액 등 화학 약품비는 경감시킨 하수 및 폐수 처리 방법에 관한 것이다.In particular, as a high water treatment method combining chlorine-based chemical coagulation and electrolysis reaction, by sequentially giving the coagulation step and electrochemical oxidation step using a chemical coagulant containing chlorine ions to the water treatment process, the water treatment efficiency is improved and the electrolyte solution Such chemical costs relate to reduced sewage and wastewater treatment methods.

하수 및 폐수 처리단계에서 이용되는 화학 응집은 부유물질(Suspended Solids) 혹은 콜로이드(Colloid)성 물질을 제거 하는데 수십년 동안 사용되어 왔고 용해성 금속물질과 유기물을 침전시키는데 효과적이다. 화학 응집 처리는 수중의 오염 물질을 불용성 또는 부유성 입자의 물리적 상태를 바꾸어 중력 침전에 의해 제거하기 위하여 화학약품을 사용한다.Chemical flocculation used in sewage and wastewater treatment steps has been used for decades to remove suspended solids or colloidal materials and is effective in the precipitation of soluble metals and organics. Chemical flocculation uses chemicals to remove contaminants in water by gravitational precipitation by changing the physical state of insoluble or suspended particles.

상기와 같은 화학적 응집을 위한 화학응집제로는 결합되는 금속성분에 따라 크게 황산알루미늄(Alum), 황산제1철, 황산제2철 등의 알루미늄염계 화학 응집제, 염화 제2철 등의 철염계 화학응집제, 그리고 PAC(Poly Aluminium Chloride),PASS(Poly Aluminium Silicate Sulfate), PACS(Poly Aluminium Chloride Silicate) 등의 고분자 응집제 등이 널리 사용된다.As the chemical coagulant for chemical coagulation as described above, aluminum salt-based chemical coagulants, such as aluminum sulfate, ferrous sulfate, and ferric sulfate, and iron salt-based chemical coagulants, such as ferric chloride, may be large depending on the metal component to be bonded. In addition, polymer flocculants such as poly aluminum chloride (PAC), poly aluminum silicate sulfate (PASS), and poly aluminum chloride silicate (PACS) are widely used.

전기화학(Electrochemistry)적인 산화는 전기분해(Electrolysis) 결과 생성되는 반응성이 큰 라디칼(Radical) 및 산화제에 의한 산화반응을 말하는데, 전기분해 과정중 생성되는 OHㆍ, Oㆍ, HOCl 등은 산화력이 크고 빠르게 반응하여 유기물을 직접적으로 산화시키거나, Cl2, ClO2, O3, H2O2, O2등의 다른 산화제로 분해되게 된다.Electrochemistry oxidation refers to oxidation by highly reactive radicals and oxidants produced by electrolysis. OH, O, HOCl, etc. generated during the electrolysis process are highly oxidizing. It reacts rapidly to directly oxidize the organics, or to decompose into other oxidants such as Cl 2 , ClO 2 , O 3 , H 2 O 2 , O 2 .

전기분해 과정중 양극에서의 산화반응에 의해 유기물, 알칼리도, 색도, COD(Chemical Oxygen Demand) 등을 처리하고 음극에서의 환원반응에 의해 산도, 중금속 등을 처리하기 때문에 유해 물질이 양극 및 음극에서 동시에 처리된다.During the electrolysis process, organic materials, alkalinity, color, chemical oxygen demand (COD) are processed by oxidation reaction at the anode, and acidity and heavy metals are processed by reduction reaction at the cathode. Is processed.

또한, 충분히 많은 고에너지를 가하면 반응 후 생성되는 물질은 주성분이 SOx, NOx, COx등과 H2O 그리고 저분자 물질로 완전히 산화분해될 수 있으므로 슬러지(Sludge)가 전혀 생성되지 않거나 극미량이 생성되기 때문에 부가적인 2차 처리가 요구되지 않는 장점이 있다.In addition, if a sufficient amount of high energy is applied, the material produced after the reaction may be completely oxidized to SO x , NO x , CO x, and H 2 O and low molecular weight material, so that no sludge is produced or a very small amount is produced. There is an advantage that no additional secondary processing is required.

전기분해방법에 의한 폐수처리는 기존의 방법들에 비해 싼 비용이 들며, 그 장점으로는 처리전에 pH(수소이온농도)를 조정할 필요가 없으며, 많은 양의 화학약품을 투입할 필요도 없고, 수처리 후에는 기존처리방법에서 문제가 되는 슬러지의 양도 현저히 줄일수 있으며 또한, 색도의 제거는 전기화학적 방법만으로도 높은 제거율을 얻을수 있는 장점이 있다.Wastewater treatment by electrolysis method is cheaper than conventional methods, and its advantages do not need to adjust pH (hydrogen ion concentration) before treatment, and do not need to add a large amount of chemical, Afterwards, the amount of sludge that is a problem in the existing treatment method can be significantly reduced, and the removal of chromaticity has the advantage of obtaining a high removal rate by the electrochemical method alone.

또한, 전기분해방법에 의한 수처리시 이용되는 화학약품의 소비가 화학적 침전법에 비하여 극미하고, 폐수처리시의 조건과 반응 온도 등의 조건은 전압 전류에 따라 조정하기 쉽고 운전이 용이한 장점이 있다.In addition, the consumption of chemicals used in the water treatment by the electrolysis method is less than the chemical precipitation method, and the conditions such as wastewater treatment conditions and reaction temperature can be easily adjusted according to the voltage current and easy to operate. .

그러나, 전기화학적 산화반응은 크게 직접산화반응과 간접산화반응으로 나누어 이루어지는데, 직접산화반응은 주로 양극의 활성 및 전류밀도에 의해 좌우되지만 간접산화반응에 의한 전기분해 반응은 전극반응에 의해 생성되는 이차적인 산화제들의 영향을 받게되는 문제가 있다.However, the electrochemical oxidation reaction is largely divided into direct oxidation and indirect oxidation reaction. The direct oxidation reaction mainly depends on the activity and current density of the anode, but the electrolysis reaction by the indirect oxidation reaction is generated by the electrode reaction. There is a problem of being affected by secondary oxidants.

따라서, 일반적으로는 전기화학반응시 전류의 흐름을 원활하게 하기 위하여 인위적으로 전해질 용액을 첨가시켜주는데, 일반적으로는 NaCl(염화나트륨) 이나 KCl(염화칼륨) 등이 가장 널리 사용된다.Therefore, in general, an electrolyte solution is artificially added to smooth the flow of electric current during an electrochemical reaction, and in general, NaCl (sodium chloride) or KCl (potassium chloride) is most widely used.

직접산화에 의한 전기분해시에는 O2, OHㆍ 등의 산화제 물질이 생성되며, 간접산화시에는 이외에도 Cl2, HOCl, OCl-등도 생성된다. 전기화학적 산화시 직접산화반응만에 의한 전기분해되는 정도는 그다지 많지 않으며, 주로 간접산화에 의해 생생되는 산화제가 함께 기여하는 정도가 높다.In the electrolysis by direct oxidation, oxidant substances such as O 2 and OH. Are generated, and in addition to indirect oxidation, Cl 2 , HOCl, OCl −, and the like are produced. In electrochemical oxidation, the degree of electrolysis by direct oxidation alone is not very high, and the degree of contribution of oxidants generated by indirect oxidation is mainly contributed.

참고로, 간접산화시에 발생되는 산화제 중 수산화 라디칼(OHㆍ)의 산화력은 오존(O3) 산화력의 1.4배이며, 염소(Cl2)는 오존의 약 66% 수준의 산화력을 발휘한다.For reference, the oxidation power of the hydroxyl radical (OH ·) in the oxidizing agent generated during indirect oxidation is 1.4 times the ozone (O 3 ) oxidation power, and chlorine (Cl 2 ) exhibits about 66% of the oxidation power of ozone.

염소는 산화력이 강하고, 살균력이 있어 정수처리시에는 전처리 후에 최종적으로 수도관으로 급수하기 이전에 잔류 유기물질이나 세균의 번식을 막기 위하여염소살균을 하기도 한다.Chlorine has strong oxidizing power and sterilizing power, so during water treatment, chlorine sterilization may be performed to prevent the regeneration of residual organic substances or bacteria before preliminary water supply to the water pipe.

종래기술에 따른 하수 및 폐수의 전기화학적 산화반응시 전류흐름을 향상시키고, 간접산화반응에 참여하게 되는 산화제를 생성해내고자 인위적인 전해질용액을 첨가해 준다.In the electrochemical oxidation of sewage and wastewater according to the prior art, an artificial electrolyte solution is added to improve current flow and to generate an oxidant that participates in an indirect oxidation reaction.

일반적으로 첨가되는 전해질용액은 염소이온을 함유하면서, 저렴하고 주변에 흔한 염화나트륨(NaCl) 용액을 전해질 용액으로 사용하게 된다.In general, the added electrolyte solution contains chlorine ions, and inexpensive and common sodium chloride (NaCl) solution is used as the electrolyte solution.

그러나, 전기화학적 산화반응에서는 처리대상 하수나 폐수중에 부유물질(Suspended Solids)이나 콜로이드(Colloid)성 물질이 공존하는 경우, 부유물질이나 콜로이드성 물질이 전기분해시 전류의 흐름을 방해할 뿐만 아니라, 전극 표면에 달라붙어 스케일(Scale)을 형성하는 문제를 야기시켜 수처리 효율을 저감시키는 단점이 있었다.However, in the electrochemical oxidation reaction, when suspended solids or colloidal materials coexist in the sewage or wastewater to be treated, the suspended solids or colloidal materials not only disturb the flow of current during electrolysis. There is a disadvantage in that the water treatment efficiency is reduced by causing a problem of forming a scale by sticking to the electrode surface.

따라서, 이를 위하여 필수적으로 전기화학적인 산화반응 이전단계에서 이들 부유물질이나 콜로이드성 물질의 사전적인 처리가 수행되어야 하는 문제가 있었다.Therefore, for this purpose, there is a problem that pretreatment of these suspended substances or colloidal substances must be performed before the electrochemical oxidation step.

본 발명은 상기와 같은 종래 기술의 단점을 극복하고자 창안된 것으로서, 전기화학적 산화 반응시에 필요한 염소 이온을 함유하는 전해질 용액의 첨가를 배제하고, 전체 수처리 효율은 증가시킬수 있는 하수 및 폐수 처리 방법을 제공함에 그 목적이 있다.The present invention was devised to overcome the disadvantages of the prior art as described above. The present invention provides a method for treating sewage and wastewater, which eliminates the addition of an electrolyte solution containing chlorine ions necessary for an electrochemical oxidation reaction and increases the overall water treatment efficiency. The purpose is to provide.

상기와 같은 목적을 달성하기 위해 본 발명은 하수 또는 폐수에 포함된 콜로이드의 하전을 중화시키고, 상기 콜로이드 입자를 상호결합시키기 위한 화학 응집제를 투여하여 혼화하는 혼화단계; 상기 혼화단계 후 교반기를 이용하여 콜로이드 입자간의 충돌을 촉진시킴으로써 콜로이드 입자를 응집시키는 응집단계; 상기 응집단계 후, 하수 또는 폐수에 포함된 응집 상태의 콜로이드 입자를 침전시키기 위한 침전단계; 상기 침전단계 후의 침전조 상등액을 전기화학적으로 산화처리하는 산화처리단계; 로 이행되는 것을 특징으로 하는 하수 및 폐수 처리 방법을 제공한다.In order to achieve the above object, the present invention provides a compounding step of neutralizing the charging of colloids contained in sewage or wastewater, and mixing and administering a chemical flocculant to crosslink the colloidal particles; An agglomeration step of agglomerating the colloidal particles by promoting collision between the colloidal particles using the stirrer after the mixing step; A precipitation step for precipitating colloidal particles in the aggregated state contained in the sewage or wastewater after the aggregation step; An oxidation treatment step of electrochemically oxidizing the sedimentation tank supernatant after the precipitation step; It provides a sewage and wastewater treatment method characterized in that the transition to.

상기 화학 응집제는 염소계 화학 응집제인 것을 특징으로 한다.The chemical flocculant is characterized in that the chlorine-based chemical flocculant.

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

본 발명의 기술적 사상은 전기화학적 산화 처리를 이용하여 하수 및 폐수를 처리함에 있어서, 염소이온을 함유하는 전해질의 첨가를 배제하고, 수처리 효율을 높일수 있도록 화학응집반응과 전기분해반응을 결합한 하수 및 폐수 처리 방법에 있다.The technical idea of the present invention is to treat sewage and wastewater by using an electrochemical oxidation treatment, to eliminate the addition of electrolytes containing chlorine ions, and to sewage and wastewater combined with a chemical aggregation reaction and an electrolysis reaction to improve water treatment efficiency. It is in the processing method.

상기와 같은 기술적 사상을 구현하기 위한 본 발명에 따른 하수 및 폐수 처리 방법은, 처리 대상수에 화학 응집제를 투여하여 혼화하는 혼화단계, 상기 혼화단계 후의 하수 및 폐수에 포함된 콜로이드 입자를 응집시키는 응집단계, 상기 응집단계 후의 하수 또는 폐수에 포함된 응집 콜로이드 입자를 침전조에서 침전시키는 침전단계, 상기 침전단계 후의 침전조 상등액을 산화처리하는 산화처리 단계로 이행된다.The sewage and wastewater treatment method according to the present invention for implementing the technical idea as described above, the mixing step of admixing by administering a chemical flocculant to the water to be treated, agglomeration to aggregate the colloid particles contained in the sewage and wastewater after the mixing step Step, the precipitation step of precipitating the colloidal colloid particles contained in the sewage or waste water after the flocculation step in the precipitation tank, and the oxidation treatment step of oxidizing the precipitation tank supernatant after the precipitation step.

이하, 본 발명의 하수 및 폐수 처리 방법을 구성하는 각 단계별 공정을 보다 상세히 설명한다.Hereinafter, each step process constituting the sewage and wastewater treatment method of the present invention will be described in more detail.

혼화단계Admixture Stage

혼화단계란 급속교반이라고도 하며, 처리 대상수에 투입한 화학 응집제를 완전혼화시키기 위한 단계로서, 콜로이드 입자상에 다가의 알루미늄 수화물이 흡착하여 하전중화(Charge Neutralization)를 일으키거나(i), 수산화물이 침전물을 형성하면서 콜로이드 입자를 그 사이에 두고 침전물을 형성하는 면상 침전물(Floc) 형성의 과정(ii)에 의해 응집이 일어나는 단계이다.The miscation step, also known as rapid stirring, is a step for completely mismixing the chemical flocculant introduced into the water to be treated. The polyvalent aluminum hydrate is adsorbed onto the colloidal particles to cause charge neutralization (i), or the hydroxide precipitates. Aggregation is a step in which a floc is formed by forming a precipitate while colloidal particles are formed therebetween.

참고로, 상기 (i), (ii)의 두가지 반응은 서로 경쟁적으로 일어나므로 하전중화를 위해서는 화학 응집제를 가능한한 빨리 골고루 처리 대상수에 첨가하여 수백분의 1초 사이에 만들어지는 수화물이 콜로이드에 흡착되어 중화시키도록 하는 것이 필요하다.For reference, since the two reactions of (i) and (ii) occur competitively with each other, hydrates formed between several hundredths of a second by adding a chemical flocculant to the treated water as soon as possible for charge neutralization are collided with colloid. It is necessary to allow it to be adsorbed and neutralized.

이와는 반대로 면상 침전물 형성에서는 수산화물의 형성이 1~7 초 사이에 일어나므로 고강도의 짧은 시간 내의 교반이 하전중화에서 처럼 결정적으로 필요하지 않기 때문에 혼화시에는 강력한 교반이 짧은 시간내에 이루어져야 한다.On the contrary, in the formation of planar precipitates, hydroxide formation takes place between 1 and 7 seconds, and therefore, strong mixing should be performed within a short time when mixing, since stirring within a short time of high strength is not critically necessary as in charge neutralization.

응집단계Coagulation stage

응집단계는 완속교반이라고도 하며, 본 발명에 의한 응집단계의 근본 목적은 입자간의 충돌을 촉진시킴으로써, 면상 침전물(Floc) 형성을 돕는 단계이다.The coagulation step is also referred to as slow stirring, and the primary purpose of the coagulation step according to the present invention is to assist in the formation of planar precipitates by promoting collision between particles.

참고로, 입자간의 충돌은 브라운 운동(Brownian movement), 유체 운동입자간의 침강속도의 차이에 의해 일어나며, 입자간 접촉빈도와 그에 따른 입자의 성장은 물의 성분(수온, 점도, 밀도 등), 입자의 성분(입자농도, 크기, 밀도 등)과 교반설비의 특성(체류시간, 흐름의 형태, 교반강도) 등에 의해 영향을 받는다.For reference, collisions between particles are caused by Brownian movement, difference in sedimentation speed between fluid particles, and the contact frequency between particles and the growth of particles are related to the composition of water (water temperature, viscosity, density, etc.) It is influenced by the components (particle concentration, size, density, etc.) and the characteristics of the stirring equipment (retention time, flow type, stirring strength).

직경 1㎛ 이하인 두 입자간의 충돌은 기본적으로 브라운 운동에 의해 일어나며, 크기가 서로다른 입자들 사이의 충돌은 특히 밀도가 다른 경우 침강속도의 차이에 의해 일어난다.Collision between two particles of diameter 1 µm or less is basically caused by Brownian motion, and collisions between particles of different sizes are caused by differences in sedimentation velocity, especially at different densities.

이러한 두 과정에 의한 충돌은 교반강도에 의해 직접적으로 영향을 받지 않으며 이 경우의 교반은 단지 충돌이 일어날수 있도록 입자들을 현탁시켜 주는 역할만 한다.The collisions by these two processes are not directly affected by the agitation strength, in which case the agitation only serves to suspend the particles so that a collision can occur.

유체운동에 의한 충돌은 입자크기와는 상관없이 모든 입자에 작용하며 브라운 운동이나 침강속도 차이에 의한 영향은 받지 않고 입자의 크기 성분(크기, 밀도 등) 영역에서 지배적으로 작용한다.Collision caused by fluid motion acts on all particles irrespective of particle size and is dominant in the area of particle size (size, density, etc.) without being affected by Brownian motion or sedimentation speed difference.

본 발명의 응집단계는 상기와 같은 기본 이론이 적용되며, 처리 대상 하수 또는 폐수의 오염부하에 따라, 교반흐름 및 교반강도를 적절히 제어할 수 있음은 당업자에게 있어 자명할 것이다.The coagulation step of the present invention is applied to the basic theory as described above, it will be apparent to those skilled in the art that it is possible to properly control the stirring flow and the stirring strength, depending on the pollution load of the sewage or waste water to be treated.

침전단계Precipitation step

본 발명에 따른 침전단계는 상기 혼화단계와 응집단계를 거친 후의 하수 및 폐수를 일시 침전시키는 단계이다. 즉, 하수 또는 폐수에 포함된 응집 콜로이드 입자를 침전조에서 침전시키는 단계이다.Precipitation step according to the present invention is a step of temporarily settling sewage and waste water after the mixing step and the flocculation step. That is, the step of precipitating the aggregated colloidal particles contained in the sewage or waste water in the sedimentation tank.

본 발명에서는 염소계 화학 응집제를 투여함으로 인해 화학 응집제를 이용한 처리 상등수 중에는 염소이온이 포함되어 있다.In the present invention, chlorine ions are included in the treated supernatant using the chemical flocculant by administering the chlorine-based chemical flocculant.

따라서, 침전단계 후에 진행되는 산화처리단계에서는 전해질 용액의 첨가없이 바로 전류를 흘려주어 산화처리단계를 진행할 수 있다.Therefore, in the oxidation treatment step performed after the precipitation step, the oxidation treatment step may be performed by flowing a current immediately without adding the electrolyte solution.

산화처리단계Oxidation step

본 단계는 상기 침전단계에서 응집침전이 일어나고, 상등수중에 잔류하게 되는 염소이온(Cl-)에 의해 인위적인 전해질 용액의 첨가없이 바로 처리 대상수에 전류를 흘려주어 전기화학(Electrochemistry)적으로 산화처리를 하는 단계이다.In this step, agglomeration sedimentation occurs in the precipitation step, and chlorine ions (Cl ) remaining in the supernatant water immediately flow current to the water to be treated without the addition of an artificial electrolyte solution to perform oxidation treatment electrochemically. It's a step.

본 발명에 따른 하수 및 폐수 처리 방법은 상기에 언급한 혼화단계, 응집단계, 침전단계, 산화처리단계를 순차적으로 이행하며 진행된다.Sewage and wastewater treatment method according to the present invention proceeds by sequentially performing the above-mentioned mixing step, flocculation step, precipitation step, oxidation treatment step.

또한, 종래기술과 비교해 부각되어야 할 점은 전기화학적인 산화처리 전에 염소를 함유하는 화학 응집제에 의한 화학응집이 이루어지기 때문에 전기분해시 인위적인 전해질 용액의 첨가를 배제할 수 있는 점이다.In addition, it should be noted that compared with the prior art, since the chemical agglomeration with chlorine-containing chemical coagulant is performed before the electrochemical oxidation treatment, it is possible to exclude the addition of an artificial electrolyte solution during electrolysis.

즉, 전기분해시 전류의 흐름을 방해하고, 전극표면에 달라붙어 스케일을 형성하는 부유물질 및 콜로이드를 본 발명에 따른 하수 및 폐수 처리 방법에서는 산화처리단계 전에 화학적 응집제를 이용하여 상기 부유물질 및 콜로이드를 화학 응집시켜, 전기화학적인 산화처리단계 전에 침전시킴으로써 오염부하를 경감시켜 준 것이다.That is, in the sewage and wastewater treatment method according to the present invention, suspended substances and colloids, which hinder the flow of current during electrolysis and adhere to the surface of the electrode, are formed using a chemical flocculant before the oxidation treatment step. Was chemically aggregated and precipitated before the electrochemical oxidation step to reduce the contamination load.

이하, 본 발명에 따른 실시예를 예시함으로써 본 발명을 보다 구체화하여 설명하고자 한다.Hereinafter, the present invention will be described in more detail by illustrating examples according to the present invention.

하기에 예시하는 실시예는 본 발명의 기술적 사상에 따른 일예를 보여주는 것일뿐, 본 발명의 특허청구범위를 제한하는 것으로 해석되어서는 아니될 것이다.The examples illustrated below are merely examples of the technical idea of the present invention, and should not be construed as limiting the claims of the present invention.

하기 실시예는 섬유 전처리(Preparation) 공정에서 발생된 염색 폐수를 대상 처리수로 하여 본 발명에 따라 화학 응집제를 이용하여 사전처리한 후 전기화학적인 산화처리를 하였다.The following examples were subjected to electrochemical oxidation after pretreatment using a chemical flocculant according to the present invention using the dye wastewater generated in the fiber preparation process as the treated water.

또한, 상기 화학 응집제는 염소를 포함하는 염소계 화학 응집제와 염소를 포함하지 않는 화학 응집제를 사용하고, 이에 따른 염색 폐수 처리 결과를 비교, 예시하였다.In addition, the chemical flocculant uses a chlorine-based chemical flocculant containing chlorine and a chemical flocculant containing no chlorine, and compared and exemplified the dye wastewater treatment results.

염색 폐수의 COD 처리를 예시하는 하기 실시예도 본 발명에 따른 기술적 사상인 염소이온을 함유하는 전해질의 첨가를 배제하고, 수처리 효율을 높일수 있도록 화학응집반응과 전기분해반응을 결합한 하수 및 폐수 처리 방법을 이용함은 물론이다.The following example illustrating the COD treatment of the dyeing wastewater also includes a method for treating sewage and wastewater combining a chemical coagulation reaction and an electrolysis reaction so as to exclude the addition of an electrolyte containing chlorine ion, which is a technical idea according to the present invention, and to improve water treatment efficiency. Of course it is.

[실시예]EXAMPLE

본 발명에 따른 염색 폐수의 COD 처리COD treatment of dyeing wastewater according to the invention

본 실시예에서는 일반적인 화학 응집제 즉, Al2(SO4)3ㆍ18H2O(Alum, 황산알루미늄), Fe2(SO4)3(황산제2철), FeCl3(염화철) 및 PAC(폴리염화알루미늄)를 적용하여초기 COD가 395mg/l인 염색 폐수의 응집교반시험(Jar-test)을 통해 상등액의 염소이온농도를 환경공정시험법을 통해 분석하였다.In this embodiment, general chemical flocculants such as Al 2 (SO 4 ) 3 18 H 2 O (Alum, aluminum sulfate), Fe 2 (SO 4 ) 3 (ferric sulfate), FeCl 3 (iron chloride) and PAC (poly Aluminum chloride) was used to analyze the chlorine ion concentration in the supernatant through the Jar-test of the dyeing wastewater with an initial COD of 395 mg / l.

참고로, 상기 응집교반시험은 효과적이고 경제적인 응집처리를 위해서, 최적 pH나 화학 응집제량을 알기 위해 실제로 폐수 시료를 갖고 시험하는 것이다.For reference, the flocculation stirring test is to actually test with wastewater samples to find the optimum pH or amount of chemical flocculant for effective and economical flocculation treatment.

이때의 최적 응집조건(pH, 응집제주입량)은 아래의 표 1과 같다.The optimum coagulation condition (pH, flocculant injection amount) is shown in Table 1 below.

[표 1] 화학응집제별 최적 응집조건[Table 1] Optimum Coagulation Conditions by Chemical Coagulant

화학응집제Chemical coagulant AlumAlum Fe2(SO4)3 Fe 2 (SO 4 ) 3 FeCl3 FeCl 3 PACPAC 수소이온농도Hydrogen ion concentration 88 66 66 55 응집제주입량Coagulant Injection 1946mg/l1946 mg / l 700mg/l700 mg / l 878mg/l878 mg / l 12ml/l12ml / l

응집교반시험 후 응집처리 상등액 중의 각 화학 응집제별 염소이온농도는 표 2에 나타낸 바와 같다.After the coagulation stirring test, the chlorine ion concentration of each chemical coagulant in the coagulation supernatant is shown in Table 2.

[표 2] 화학 응집제별 염소이온농도 및 COD 처리효율[Table 2] Chlorine Ion Concentration and COD Treatment Efficiency by Chemical Coagulant

화학응집제Chemical coagulant AlumAlum Fe2(SO4)3 Fe 2 (SO 4 ) 3 FeCl3 FeCl 3 PACPAC 염소이온농도(mg/l)Chlorine Ion Concentration (mg / l) 121121 121121 531531 26552655 COD 처리효율(%)COD treatment efficiency (%) 55.855.8 51.951.9 99.099.0 100100

상기 표 2에서 보는 바와 같이, FeCl3및 PAC에서 염소이온농도가 상대적으로 높게 나타남을 알 수 있다. FeCl3및 PAC를 적용한 응집교반시험에서의 염소이온농도를 종래기술에 따라 많이 사용되는 전해질 용액인 염화나트륨(NaCl)의 양으로 환산하면 각각 875mg/l, 4,377mg/l에 해당하는 이온농도 수치이다.As shown in Table 2, it can be seen that the chlorine ion concentration in FeCl 3 and PAC is relatively high. The chlorine ion concentration in the coagulation stirring test using FeCl 3 and PAC is equivalent to 875 mg / l and 4,377 mg / l, respectively. .

참고로, Alum과 Fe2(SO4)3의 화학 응집제의 경우는 염소 이온을 포함하지 않는 화학 응집제이기 때문에 염소이온농도 수치는 원래 염색 폐수 내의 염소이온 농도 값과 동일하다.For reference, since the chemical coagulant of Alum and Fe 2 (SO 4 ) 3 is a chemical coagulant that does not contain chlorine ions, the chlorine ion concentration value is the same as the original chlorine ion concentration value in the dyeing wastewater.

따라서, 상기와 같은 결과는 염소를 포함하는 염소계 화학 응집제의 경우가 전기화학적인 산화처리시 중요한 역할을 하는 염소이온의 농도가 높음을 고찰할 수 있었다.Therefore, the above results could be considered that the chlorine-based chemical flocculant containing chlorine has a high concentration of chlorine ions that play an important role in the electrochemical oxidation treatment.

또한, 본 실시예에서는 폐수의 처리 성능을 살펴보기 위하여 염색 공단에서 발생되는 염색 폐수를 대상으로 하여 수처리 실험을 수행하였다.In addition, in the present embodiment, to examine the treatment performance of the wastewater, a water treatment experiment was performed on the dye wastewater generated in the dyeing complex.

먼저, 응집교반시험을 이용하여 화학 응집을 수행한 후, 다음과 같은 조건에서 전기화학적인 산화처리를 수행하였고, 산화처리 조건은 하기와 같다.First, after performing the chemical coagulation by using the coagulation stirring test, the electrochemical oxidation treatment was performed under the following conditions, the oxidation treatment conditions are as follows.

※ 전기화학적인 산화처리 조건※ Electrochemical Oxidation Condition

반응기 체적 : 1.6 LiterReactor Volume: 1.6 Liter

양극재료 : RuO2/TiAnode Material: RuO 2 / Ti

음극재료 : STS 재질Cathode Material: STS Material

전극개수 : 4개(양극 2, 음극2), 양극과 음극 교차 설치Number of electrodes: 4 (positive 2, negative 2), cross installation between anode and cathode

전극판 면적: 11cm ×8cmElectrode plate area: 11 cm × 8 cm

전류: 5A의 직류 전류 공급Current: 5A DC Current Supply

상기와 같은 전기화학적인 산화처리 조건하에서 120분 후의 처리 유출수 성분에 대하여 CODcr(크롬법에 의한 화학적 산소 요구량) 처리효율을 조사하여 본 결과는 표 2에 나타낸 바와 같다.The COD cr (chemical oxygen demand by chromium method) treatment efficiency of the treated effluent after 120 minutes under the electrochemical oxidation treatment conditions as described above is shown in Table 2.

즉, 염소 이온을 함유하는 화학 응집제로 화학 응집한 후 전기분해를 수행한 경우는 2시간 후에 거의 100%에 가까운 COD 처리율을 보이지만, 염소 이온이 아닌 다른 음이온을 함유하는 화학 응집제로 화학 응집 처리후 전기 분해한 경우는 2시간 전기분해로 50% 전후의 COD 처리 효율을 보여 염소계 화학 응집후 전기분해가 비염소계 화학응집 후 전기분해보다 훨씬 더 처리효율이 우수함을 나타내고 있다.In other words, when electrolysis is performed after chemical coagulation with a chemical coagulant containing chlorine ions, the COD treatment rate is almost 100% after 2 hours, but after chemical coagulation treatment with a chemical coagulant containing an anion other than chlorine ion. In case of electrolysis, COD treatment efficiency was about 50% by 2 hours electrolysis, indicating that electrolysis after chlorine-based chemical coagulation is much better than electrolysis after non-chlorine-based chemical coagulation.

상기와 같은 결과를 고찰해 보면, 처리 대상 하수나 폐수중에 존재하는 부유물질이나 콜로이드성 물질을 전처리함에 따라, 전류 흐름의 방해 현상 및 전극표면에 부착되어 스케일을 형성하는 문제점들을 해결할 수 있다.Considering the above results, as a pretreatment of suspended solids or colloidal substances present in the sewage or wastewater to be treated, problems such as disturbance of current flow and problems attached to the electrode surface to form scales can be solved.

따라서, 전기화학적 산화단계의 처리효율을 향상시켜주고, 근본적으로 기존에 인위적으로 첨가되던 전해질 용액의 첨가를 생략시켜 줌으로써, 약품비 등의 운전비용을 저감시켜 줄 수 있는 이득을 얻을수 있다.Therefore, by improving the treatment efficiency of the electrochemical oxidation step, and by essentially eliminating the addition of the conventionally added electrolyte solution, it is possible to obtain a benefit that can reduce the operating cost, such as chemical costs.

상기한 바와 같이 본 발명에 따르면, 하수 및 폐수를 처리함에 있어서 염소를 함유하는 화학응집제를 채택한 화학응집 처리를 수행하고, 그 상등수 중에 잔류하는 염소 이온을 이용하여 인위적인 전해질 용액의 첨가없이 바로 전류를 흘려주어 전기화학적으로 산화 처리함으로써, 수처리 효율을 향상시킬 수 있을 뿐만 아니라 약품비 등을 절약할 수 있는 경제적인 효과가 기대된다.As described above, according to the present invention, in the treatment of sewage and wastewater, a chemical agglomeration treatment employing a chemical coagulant containing chlorine is carried out, and current is immediately applied without adding an artificial electrolyte solution using chlorine ions remaining in the supernatant water. By flowing and oxidizing electrochemically, not only can the efficiency of water treatment be improved, but also the economic effect which can save chemical cost etc. is anticipated.

Claims (2)

하수 또는 폐수에 포함된 콜로이드의 하전을 중화시키고, 상기 콜로이드 입자를 상호결합시키기 위한 화학 응집제를 투여하여 혼화하는 혼화단계;A mixing step of neutralizing the charging of the colloids contained in the sewage or wastewater, and mixing and administering a chemical flocculant for mutually bonding the colloidal particles; 상기 혼화단계 후 교반기를 이용하여 콜로이드 입자간의 충돌을 촉진시킴으로써 콜로이드 입자를 응집시키는 응집단계;An agglomeration step of agglomerating the colloidal particles by promoting collision between the colloidal particles using the stirrer after the mixing step; 상기 응집단계 후, 하수 또는 폐수에 포함된 응집 상태의 콜로이드 입자를 침전시키기 위한 침전단계;A precipitation step for precipitating colloidal particles in the aggregated state contained in the sewage or wastewater after the aggregation step; 상기 침전단계 후의 침전조 상등액을 전기화학적으로 산화처리하는 산화처리단계;An oxidation treatment step of electrochemically oxidizing the sedimentation tank supernatant after the precipitation step; 로 이행되는 것을 특징으로 하는 하수 및 폐수 처리 방법.Sewage and wastewater treatment method characterized in that the transition to. 제 1 항에 있어서,The method of claim 1, 상기 화학 응집제는 염소계 화학 응집제인 것을 특징으로 하는 하수 및 폐수 처리 방법.The chemical flocculant is a chlorine-based chemical flocculant, characterized in that sewage and wastewater treatment method.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100943031B1 (en) * 2008-08-22 2010-02-18 남건용 An attachable input device on mobile unit
KR101528530B1 (en) * 2014-09-24 2015-06-15 (주) 테크윈 Apparatus and method for industrial wastewater treatment using oxidizing agent produced from the wastewater

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100943031B1 (en) * 2008-08-22 2010-02-18 남건용 An attachable input device on mobile unit
KR101528530B1 (en) * 2014-09-24 2015-06-15 (주) 테크윈 Apparatus and method for industrial wastewater treatment using oxidizing agent produced from the wastewater

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