KR100225693B1 - Nonbiodegradable organic material treatment process - Google Patents

Nonbiodegradable organic material treatment process Download PDF

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KR100225693B1
KR100225693B1 KR1019960061358A KR19960061358A KR100225693B1 KR 100225693 B1 KR100225693 B1 KR 100225693B1 KR 1019960061358 A KR1019960061358 A KR 1019960061358A KR 19960061358 A KR19960061358 A KR 19960061358A KR 100225693 B1 KR100225693 B1 KR 100225693B1
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tank
organic material
iron
particles
hardly decomposable
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KR1019960061358A
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KR19980043481A (en
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박칠림
유희찬
조순행
최영수
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장병주
주식회사대우
이일쇄
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F2001/007—Processes including a sedimentation step
    • 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
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

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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)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

본 발명은 생물학적으로 제거되지 않는 고령화된 매립지의 침출수 및 산업폐수를 정화처리하는 난분해성 유기물질 처리공법에 관한 것으로, 응집제를 투여하는 화학적 응집침전조, 펜튼산화조, 펜튼산화시 발생되는 철염의 응집침전조가 순차로 연결되어 난분해성 유기물질을 제거하여, 분자량 10,000 이상의 유기물질을 다량 포함하는 고령화된 매립지 침출수나 난분해성 산업폐수는 화학적 응집.침전 공정을 적용하여 우선적으로 분자량 10,000 이상의 유기물질을 제거하고 후단의 펜톤산화공정에서 분자량 10,000 이하의 유기물질을 제거하므로써 펜톤산화공정에 투입되는 화학약품의 양을 감소시키고 전체적인 처리 시스템의 비용을 절감하며, 난분해성 유기물질이 높은 효율로 제거되어 최종 유출수가 양질의 수질을 나타내게 된다.The present invention relates to a hardly degradable organic material treatment method for purifying leachate and industrial wastewater of aging landfills that are not biologically removed. A sedimentation tank is connected in sequence to remove hardly decomposable organic substances, and aging landfill leachate or hardly decomposable industrial wastewater containing a large amount of organic substances with a molecular weight of 10,000 or more is preferentially removed by applying a chemical flocculation and precipitation process. In order to reduce the amount of chemicals put into the Fenton oxidation process and reduce the cost of the entire treatment system by removing the organic material with molecular weight of 10,000 or less in the later Fenton oxidation process, the final effluent is removed with high efficiency Will give good quality water.

Description

난분해성 유기물질 처리공법Hardly degradable organic material treatment method

본 발명은 난분해성 유기물 제거방법에 관한 것으로서, 특히 생물학적으로 제거되지 않는 고령화된 매립지의 침출수 및 산업폐수를 정화처리하는 난분해성 유기물질 처리공법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing hardly degradable organic matters, and more particularly, to a hardly degradable organic material treatment method for purifying leachate and industrial wastewater of an aged landfill which is not biologically removed.

생물학적으로 분해가 어려운 유기물질은 일반적으로 분자량이 500 이상으로 성분을 파악하기 어려운 분자량 10,000 이상의 유기물질을 다량 포함하고 있다.Biologically difficult to decompose organic materials generally have a molecular weight of 500 or more, and contains a large amount of organic materials with a molecular weight of 10,000 or more that are difficult to identify.

상기와 같은 난분해성 유기물질을 제거하는 기존의 처리방법으로는 화학적 산화방법을 들 수 있다. 기존에 이용되는 화학적 산화 방법으로는 오존, 자외선(UV) 또는 과산화수소 등을 산화제로 이용하는 방법들을 들 수 있다. 이중에서 오존을 산화제로 이용하는 경우에는 오존 생성시 다량의 거품이 발생하여 운영상의 어려움이 있으며, 자외선(UV)을 이용하는 방법은 처리대상 폐수의 색도나 탁도가 높을 경우 처리효율이 현저하게 감소한다는 단점이 있어, 일반적으로 철염을 촉매로 하여 과산화수소를 산화제로 이용하는 펜튼산화 방법이 이용되고 있다. 그러나 펜튼산화 방법도 난분해성 유기물질의 농도가 높을 경우 약품비가 과다하게 소요되고 저농도 폐수에 비하여 처리효율이 감소된다는 문제점이 있다.Conventional treatment methods for removing such hardly decomposable organic substances include chemical oxidation. Conventional chemical oxidation methods include ozone, ultraviolet (UV) or hydrogen peroxide as a oxidant. In the case of using ozone as an oxidizing agent, a large amount of foam is generated when ozone is generated, and there is a difficulty in operating. The method of using ultraviolet light (UV) significantly reduces the treatment efficiency when the color or turbidity of the wastewater to be treated is high. In general, a fenton oxidation method using hydrogen peroxide as a catalyst and hydrogen peroxide as an oxidizing agent is used. However, the Fenton oxidation method also has a problem in that when the concentration of the hardly decomposable organic substance is high, the chemical cost is excessively consumed and the treatment efficiency is reduced as compared with the low concentration wastewater.

상기한 문제점을 해결하기 위한 안출된 본 발명은 분자량 10,000 이상의 유기물질을 다량 포함하는 고령화된 매립지 침출수나 난분해성 산업폐수는 화학적 응집, 침전 공정을 적용하여 우선적으로 분자량 10,000 이상의 유기물질을 제거하고 후단의 펜튼산화공정에서 분자량 10,000 이하의 유기물질을 제거하므로써, 난분해성 유기물질이 높은 효율로 제거할 수 있는 난분해성 유기물질 처리공법을 제공하고자 하는 것이다.The present invention devised to solve the above problems is the aged landfill leachate or hardly decomposable industrial wastewater containing a large amount of molecular weight of 10,000 or more by applying a chemical flocculation, precipitation process preferentially remove the organic material of molecular weight of 10,000 or more after By removing the organic material having a molecular weight of 10,000 or less in the fenton oxidation process of the present invention, it is to provide a hardly degradable organic material processing method that can be removed with high efficiency.

제1도는 본 발명의 난분해성 유기물질 처리 공정을 도시하는 개략도.1 is a schematic diagram showing a process for treating hardly degradable organic materials of the present invention.

* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings

1 : 급속 교반조 2 : 제1pH 조정조1: Rapid stirring tank 2: 1st pH adjustment tank

3 : 제1완속교반조 4 : 제1약품친전조3: first slow stirring 4: first chemical friendly

5 : 펜튼산화조 6 : 제2pH 조정조5: Fenton oxidation tank 6: 2nd pH adjustment tank

7 : 제2완속교반조 8 : 제2약품침전조7: 2nd slow stirring 8: 2nd drug settling

9 : 방류관9: discharge pipe

도면을 참조하여 본 발명의 구성과 작용을 상세히 설명하면 다음과 같다.Referring to the drawings the configuration and operation of the present invention in detail as follows.

제1도는 본 발명의 난분해성 유기물질 처리 공법의 개략도이다.1 is a schematic view of a hardly degradable organic material treatment method of the present invention.

화학적 응집, 침전 공정은 4개의 반응조로 구성되어 있다.Chemical flocculation and precipitation processes consist of four reactors.

우선 급속교반조(1)에서 응집제로 FeCl₃를 투입하여 450rpm 의 속도로 15분간 급속히 교반하면서 폐수내의 유기물질과 응집제와의 접촉을 높인후, 제1 pH 조정조(2)로 유입시킨다. 제1 pH 조정조(2)에서는 NaOH 와 H2SO4를 이용하여 유입된 폐수의 산도를 가장 효율이 높은 조건인 pH5 로 조절하여 준다. 이때 교반속도는 300rpm 이며, 체류시간은 30분으로 한다.First, FeCl 3 is added to the coagulant in the rapid agitation tank 1, and while stirring rapidly at a speed of 450 rpm for 15 minutes, the contact between the organic material and the coagulant in the wastewater is increased, and then introduced into the first pH adjusting tank 2. In the first pH adjusting tank 2, the acidity of the wastewater introduced using NaOH and H 2 SO 4 is adjusted to pH 5, which is the most efficient condition. At this time, the stirring speed is 300rpm, and the residence time is 30 minutes.

pH 가 조정된 폐수는 최적의 pH상태에서 침전성이 좋아지도록 응집입자간의 결합을 유도하여 서서히 입자의 크기를 키워주기 위해 제1완속교반조(3)로 유입시킨다. 제1완속교반조(3)에서 교반속도 20 rpm 으로 체류시간 20분 동안 침전성이 높아지도록 입자크기를 증가시킨 후, 침전성이 높아진 입자를 침전시켜 폐수로부터 응집된 난분해성 유기물질을 분리하는 역할을 하는 제1약품침전조(4)에서 응집된 입자를 침전시킨다.The pH-adjusted wastewater is introduced into the first slow stirring tank (3) to induce the binding between the aggregated particles so that the sedimentability is improved at the optimum pH state and gradually increase the size of the particles. In the first slow stirring tank (3), the particle size was increased to increase the precipitation for 20 minutes at the stirring speed of 20 rpm, and then the precipitated particles were precipitated to separate the aggregated hardly decomposable organic material from the wastewater. Agglomerated particles are precipitated in the first chemical precipitation tank (4) serving to serve.

화학적 응집, 침전 반응을 여러 운전조건으로 실험한 결과, 상기 운전조건에서 분자량 500 이상의 유기물질이 95% 이상 제거되었다.As a result of experiments on chemical flocculation and precipitation reaction under various operating conditions, 95% or more of organic substances having a molecular weight of 500 or more were removed.

화학적 응집, 침전에서 처리된 폐수는 과산화수소수(H2O2)와 황산철염(FeSO4)을 이용하여 폐수중의 난분해성 유기물질을 산화시키는 펜튼 산화조(5)로 유입시킨다. 펜튼 산화조(5)에 약품 투입시 여러 조건 실험을 통하여 과산화수소수(H2O2)와 황산철염(FeSO4)의 최적비는 1 : 1.25(무게비)임을 얻었다.The wastewater treated in the chemical flocculation and precipitation is introduced into the Fenton oxidation tank (5) which oxidizes the hardly decomposable organic substances in the wastewater using hydrogen peroxide (H 2 O 2 ) and ferrous sulfate (FeSO 4 ). When the chemicals were introduced into the Fenton oxidation tank (5), the optimum ratio of hydrogen peroxide (H 2 O 2 ) and ferric sulfate (FeSO 4 ) was 1: 1.25 (weight ratio).

펜튼 산화조(5)는 200 rpm, 체류시간 60 분, pH2 내지 3 정도로 운전된다. 펜튼 산화조(5)를 거친 폐수는 제2 pH 조정조(6)로 유입되어 최적 pH 는 수산화 나트륨을 이용하여 pH8로 조정되고 제2완속교반조(7)측으로 유입시킨다. 제2완속교반조(7)에서는 철입자 크기를 증가시켜 침전성을 향상시키고, 제2약품침전조(8)를 거쳐 촉매로 이용한 FeSO4를 침전제거 시킨다. 최종 처리된 폐수는 방류관(9)으로 배출된다.The Fenton oxidizing tank 5 is operated at 200 rpm, a residence time of 60 minutes, and a pH of 2-3. Wastewater passing through the Fenton oxidizing tank (5) flows into the second pH adjusting tank (6) so that the optimum pH is adjusted to pH8 using sodium hydroxide and introduced into the second slow stirring tank (7). In the second slow stirring tank (7), the iron particle size is increased to improve the sedimentation property, and the FeSO 4 used as a catalyst is precipitated through the second chemical precipitation tank (8). The finally treated wastewater is discharged to the discharge pipe 9.

재침전 공정에서는 화학적 응집, 침전과는 달리 응집제를 투여하지 않으며, 이때 제2완속교반조와 제2약품침전조의 조건은 화학적 응집, 침전시 제1완속교반조와 제1약품침전조의 경우와 동일하다.In the reprecipitation process, unlike chemical flocculation and precipitation, no flocculant is administered, and the conditions of the second slow stirring tank and the second chemical precipitation tank are the same as those of the first slow stirring tank and the first chemical precipitation tank during chemical flocculation and precipitation.

상기와 같은 본 발명의 난분해성 유기물질 처리공법에 따르면 고령화된 매립지의 침출수나 산업폐수에 포함되어 있는 분자량 500 이상의 난분해성 유기물질이 총유기탄소(TOC)를 기준으로 98% 이상 처리되어 우수한 제거양상을 나타낸다.According to the hardly degradable organic material treatment method of the present invention as described above, the hardly degradable organic material having a molecular weight of 500 or more contained in the leachate or industrial wastewater of an aged landfill is treated more than 98% based on total organic carbon (TOC), thereby providing excellent removal. It shows an aspect.

Claims (2)

난분해성 유기물질에 응집제를 투여하여, 응집제와 폐수내 난분해성 유기물질과의 접촉기회를 높여주기 위하여 빠른 속도로 교반하는 급속 교반조(1); 최상의 응집효율이 나타날 수 있는 최적 pH 5로 조정하는 제1 pH 조정조(2); 최적의 pH 상태에서 침전성이 좋아지도록 응집입자간의 결합을 유도하여 서서히 입자의 크기를 키워주도록 완속교반하는 제1완속교반조(3); 충분히 입자크기가 증가하여 침전성이 높아진 입자를 침전시켜 폐수로부터 응집된 난분해성 유기물질을 분리하는 역할을 하는 제1약품침전조(4); 산화제로 과산화수소(H2O2), 촉매로 철(Fe++)을 투입하여 폐수중의 난분해성 유기물질을 산화시키는 공정인 펜튼 산화조(5); 별도의 응집제를 투여하지 않고 촉매로 투입한 철을 침전시키기 위한 공정으로 NaOH를 이용하여 최적 pH 8 로 조정하는 제2 pH 조정조(6); 침전성이 좋아지도록 철 입자 크기를 증가시키기 위한 제2완속교반조(7); 및 충분히 입자크기가 증가하여 침전성이 높아진 입자를 침전시켜 폐수로부터 촉매로 사용된 철입자를 분리하는 역할을 하는 약품침전조(8); 를 순차적으로 거쳐서 처리하는 난분해성 유기물질 처리공법.A rapid agitation tank (1) which is agitated at a high speed so as to administer a coagulant to the hardly decomposable organic material and to increase the contact opportunity between the coagulant and the hardly decomposable organic material in the wastewater; A first pH adjustment tank 2 adjusting to an optimum pH 5 at which the best aggregation efficiency can be seen; A first slow stirring tank (3) which stirs slowly to induce binding between the aggregated particles so as to increase precipitation at an optimum pH and gradually increase the size of the particles; A first chemical precipitation tank (4) which serves to separate the aggregated hardly decomposable organic material from the waste water by precipitating the particles having sufficiently increased particle size to increase the settability; Fenton's oxidation tank (5), which is a process of oxidizing hardly decomposable organic substances in waste water by introducing hydrogen peroxide (H 2 O 2 ) as an oxidizing agent and iron (Fe ++) as a catalyst; A second pH adjusting tank 6 for adjusting iron to an optimum pH 8 using NaOH as a step for precipitating iron added as a catalyst without administering a separate flocculant; A second slow stirring tank (7) for increasing the iron particle size to improve the settling property; And a chemical precipitation tank (8) which serves to separate the iron particles used as catalysts from the waste water by precipitating the particles having a sufficiently increased particle size to increase the settling property; Hardly degradable organic material treatment method to process sequentially through. 제1항에 있어서, 펜튼 산화조(5)에 유입되는 과산화수소수(H2O2)와 황상철염 (FeSO4)의 최적비는 1 : 1.25(무게비)인 난분해성 유기물질 처리공법.The method of claim 1, wherein the optimum ratio of hydrogen peroxide (H 2 O 2 ) and sulfuric iron salt (FeSO 4 ) flowing in the Fenton oxidizing tank (5) is 1: 1.25 (weight ratio).
KR1019960061358A 1996-12-03 1996-12-03 Nonbiodegradable organic material treatment process KR100225693B1 (en)

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