KR101467476B1 - Method for biological processing of water containing organic material - Google Patents

Method for biological processing of water containing organic material Download PDF

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KR101467476B1
KR101467476B1 KR1020080013164A KR20080013164A KR101467476B1 KR 101467476 B1 KR101467476 B1 KR 101467476B1 KR 1020080013164 A KR1020080013164 A KR 1020080013164A KR 20080013164 A KR20080013164 A KR 20080013164A KR 101467476 B1 KR101467476 B1 KR 101467476B1
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biological treatment
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water
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KR20080078550A (en
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테츠로 후카세
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쿠리타 고교 가부시키가이샤
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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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1268—Membrane bioreactor systems
    • C02F3/1273—Submerged membrane bioreactors
    • 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
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Microbiology (AREA)
  • Activated Sludge Processes (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

본 발명은 생물처리 되어 미생물을 포함하는 혼합액을 막 분리할 경우의 막의 막힘을 방지하는 유기물 함유수의 생물처리 방법에 관한 것으로서, 생물 처리조(10) 내에 보유된 활성 슬러지에 대하여, 철로서의 농도가 MLSS의 10 ~ 40 질량％가 되도록 철염을 공존시킨다. 또한, 생물 처리조(10) 내의 혼합액의 pH를 5 ~ 6.5 범위 내로 하여 생물처리를 수행한다. 소정 범위의 철염을 포함하고, pH 값을 제어함으로써, 활성 슬러지를 구성하는 미생물의 응집을 단단하게 함과 동시에 미생물에 의한 점질물 등의 생산을 억제할 수 있다. 따라서, 침지막(11) 등의 막 분리장치의 막힘을 방지할 수 있다.The present invention relates to a method for biological treatment of an organic substance-containing water for preventing clogging of a membrane when a mixed solution containing a microorganism is subjected to biological treatment. The activated sludge contained in the biological treatment tank (10) Is 10 to 40% by mass of the MLSS. Further, the pH of the mixed solution in the biological treatment tank 10 is adjusted within the range of 5 to 6.5 to perform biological treatment. By controlling the pH value by including a predetermined range of iron salts, aggregation of microorganisms constituting activated sludge can be strengthened and production of viscous substances and the like caused by microorganisms can be suppressed. Therefore, clogging of the membrane separation device such as the immersion membrane 11 can be prevented.

유기물 함유수, 생물 처리, 활성 슬러지, 응집제, 막 분리 Organic matter-containing water, biological treatment, activated sludge, flocculant, membrane separation

Description

유기물 함유수의 생물처리방법{METHOD FOR BIOLOGICAL PROCESSING OF WATER CONTAINING ORGANIC MATERIAL}METHOD FOR BIOLOGICAL PROCESSING OF WATER CONTAINING ORGANIC MATERIAL BACKGROUND OF THE INVENTION [0001]

본 발명은 유기물 함유수를 활성 슬러지법으로 처리하는 유기물 함유수의 생물처리방법에 관한 것으로, 특히 생물 처리조 내의 혼합액을 막 분리하여 처리수를 얻는 생물처리방법에 관한 것이다.TECHNICAL FIELD The present invention relates to a biological treatment method of an organic substance-containing water in which an organic substance-containing water is treated by an activated sludge method, and more particularly, to a biological treatment method in which a mixed solution in a biological treatment tank is separated to obtain treated water.

유기물 함유수로부터 유기물을 제거하는 처리방법으로서 생물처리가 알려져 있다. 생물처리법 중에서도, 활성 슬러지라 불리는 미생물군집을 이용하는 활성 슬러지법은 여러가지 성상의 유기물 함유수에 적용할 수 있고, 양호한 수질의 처리수를 얻을 수 있기 때문에 널리 이용되고 있다. 활성 슬러지법에 의해 유기물 함유수를 처리하여 얻을 수 있는 활성 슬러지 처리수는 순수(초순수 포함. 이하 동일)를 제조하기 위한 원료수(原料水, 원수라고도 함)로서도 이용되고 있다(예를 들면 특허문헌 1).Biological treatment is known as a treatment method for removing organic matter from organic substance-containing water. Among the biological treatment methods, the activated sludge method using a microbial community called activated sludge is widely used because it can be applied to water containing various organic matters and can obtain treated water with good water quality. Activated sludge treated water obtained by treating organic-matter-containing water by the activated sludge method is also used as raw water (raw water, raw water) for producing pure water (including ultrapure water, hereinafter the same) (for example, patent Document 1).

그런데, 활성 슬러지법에 의한 처리를 행하는 생물 처리조 내에는, 처리조에 도입된 유기물 함유수와 조내에 보유되던 미생물이 혼합된 액(혼합액)이 보유된다. 이 때문에, 생물 처리조에서 처리된 맑은 처리액을 얻으려면 혼합액을 고액 분리할 필요가 있다. 생물 처리조의 혼합액 속에 포함되는 미생물 등은 미세하기 때문에, 고액 분리에 앞서 응집제를 혼합액에 첨가하여 미세한 고형분을 응집시킨다.Incidentally, in the biological treatment tank for performing the treatment by the activated sludge method, a liquid (mixed liquid) in which the organic-matter-containing water introduced into the treatment tank and the microorganisms retained in the tank are mixed is held. For this reason, in order to obtain a clear treatment liquid treated in the biological treatment tank, it is necessary to separate the liquid mixture into solid and liquid. Since the microorganisms contained in the mixed solution of the biological treatment tank are fine, the coagulant is added to the mixed solution before the solid-liquid separation, and the fine solid matters are agglomerated.

혼합액을 맑게 하는 고액 분리장치로는, 침전지, 막 분리장치 및 부상 분리장치 등이 있다. 특히, 막 분리장치는 다른 고액 분리장치에 비해서도 고형분의 분리능력이 높아 막 분리장치를 이용하면 맑은 처리수를 얻을 수 있다. 고액 분리장치로서 막 분리장치를 이용할 경우, 혼합액 중의 고형분을 응집시키는 응집제를 생물 처리조에 첨가할 수 있다(예를 들면 특허문헌 2).Examples of the solid-liquid separator for purifying the mixed liquid include a settling paper, a membrane separator, a float separator, and the like. Particularly, since the membrane separator has a higher ability to separate solids than other solid-liquid separators, clear water can be obtained by using a membrane separator. When a membrane separation device is used as the solid-liquid separation device, a flocculant for flocculating the solid content in the mixed liquid can be added to the biological treatment tank (for example, Patent Document 2).

(특허문헌 1) 일본 특허 공개 평성 5-329477호 공보(Patent Document 1) JP-A-5-329477

(특허문헌 2) 일본 특허 공개 평성 11-347587호 공보(Patent Document 2) Japanese Patent Laid-open No. Hei 11-347587

막 분리장치에는 분리막이 막히는 문제가 있다. 특히 혼합액을 막 분리하면, 혼합액에 포함되는 미생물 자체 및 미생물이 생산한 점질물 등이 막면에 부착하여 막히게 되는 경향이 있다.There is a problem that the membrane separator is clogged with the membrane. Particularly, when the mixed solution is separated by filtration, the microorganisms themselves contained in the mixed solution and the viscous products produced by the microorganisms tend to adhere to the membrane surface and become clogged.

이 때문에, 생물 처리조의 활성 슬러지 농도(Mixed Liquor Suspended Solid)를 낮게 (예를 들면 10,000 mg/L 이하로) 유지하거나, 생물 처리조에 보유되는 슬러지에 대한 BOD(생물화학적 산소소비량으로 나타내는 유기물) 슬러지 부하를 0.1 kg-BOD/kg-MLVSS/day 정도로 억제하는 등의 조치가 강구되고 있다.Therefore, it is possible to maintain the concentration of the activated sludge (Mixed Liquor Suspended Solid) of the biological treatment tank at a low level (for example, 10,000 mg / L or less), or to measure the BOD (biochemical oxygen consumption amount) sludge Measures are being taken to suppress the load to about 0.1 kg-BOD / kg-MLVSS / day.

그러나, 이들 조치에 의한 막힘 방지는 반드시 완전한 것은 아니며, 막의 투과 유속은 침지막의 경우 0.5 m/day 정도, 높은 경우에도 0.7 m/day 정도이다. 이 때문에, 고액 분리에 많은 막 분리장치가 필요하다.However, the prevention of clogging by these measures is not necessarily perfect, and the permeation flux of the membrane is about 0.5 m / day for the immersion membrane and about 0.7 m / day for the high membrane. Therefore, many membrane separation devices are required for solid-liquid separation.

본 발명은 이러한 과제에 대하여 응집제 첨가에 의한 막의 막힘 방지효과를 향상시키고, 막 분리장치의 투과 유속을 높일 수 있는 유기물 함유수의 처리방법을 제공하는 것을 목적으로 한다.The object of the present invention is to provide a method for treating an organic-material-containing water capable of enhancing the effect of preventing the clogging of the membrane by adding an aggregating agent and increasing the permeation flux of the membrane separation apparatus.

본 발명자는 폭기조에 보유되는 활성 슬러지에 소정 범위의 농도가 되도록 철염을 포함시킴으로써 상기 과제를 달성할 수 있음을 발견하고 본 발명을 완성했다. 구체적으로는, 본 발명은 이하를 제공한다.The present inventors have found that the above problems can be achieved by including an iron salt in the activated sludge held in the aeration tank so as to have a concentration within a predetermined range, and have completed the present invention. Specifically, the present invention provides the following.

(1) 유기물을 포함하는 유기물 함유수를 생물 처리조에 도입해서 활성 슬러지와 혼합하여 생물처리하고, 상기 유기물 함유수와 상기 활성 슬러지가 혼합된 혼합액을 막 분리하는 유기물 함유수의 생물처리방법에 있어서, 철염을 철로서의 농도가 상기 활성 슬러지 농도의 10 질량％ 이상 45 질량％ 이하의 비율이 되도록 상기 생물 처리조 내에 존재시키고, 동시에 상기 혼합액의 pH를 5 이상 6.5 이하로 하는 유기물 함유수의 생물처리방법.(1) A biological treatment method for an organic substance-containing water for introducing an organic substance-containing water containing an organic substance into a biological treatment tank, mixing the same with an activated sludge for biological treatment, and separating a mixed solution obtained by mixing the organic substance-containing water and the activated sludge , The iron salt is present in the biological treatment tank so that the concentration as iron is 10% by mass or more and 45% by mass or less of the activated sludge concentration, and the pH of the mixed solution is 5 to 6.5 Way.

(2) 상기 활성 슬러지 농도에 대한 활성 슬러지 유기성 부유물질의 비인 MLVSS/MLSS를 0.05 이상 0.75 이하로 하는 (1)에 기재된 유기물 함유수의 생물처리방법.(2) The biological treatment method for organic matter-containing water according to (1), wherein MLVSS / MLSS, which is the ratio of the activated sludge organic suspended solids to the activated sludge concentration, is 0.05 to 0.75.

(3) 상기 생물 처리조 내에 침지시킨 침지막 모듈에 의해, 상기 혼합액을 막 분리하는 (1) 또는 (2)에 기재된 유기물 함유수의 생물처리방법.(3) The biological treatment method for organic matter-containing water according to (1) or (2), wherein the mixed solution is separated by an immersion membrane module immersed in the biological treatment tank.

(4) 상기 유기물 함유수는 자연수, 수도물 또는 회수수인 (1）내지 (3) 중 어느 하나에 기재된 유기물 함유수의 생물처리방법.(4) The method for biological treatment of an organic substance-containing water according to any one of (1) to (3), wherein the organic substance-containing water is natural water, tap water or recovered water.

본 명세서에서, 생물 처리조에는 BOD 제거를 수행하는 폭기조, 질화를 주체로 하는 질화조, 및 탈질(脫窒)을 주체로 하는 탈질조가 포함되는 것으로 한다. 생물 처리조는 활성 슬러지라 불리는 미생물군집을 보유한다. 본 명세서에서 활성 슬러지라 할 경우, BOD를 분해하는 호기성 세균을 주체로 하는 슬러지(이하, BOD 슬러지라 함) 뿐만 아니라, 암모니아를 산화하는 질화 세균을 주체로 하는 슬러지(이하, 질화 슬러지라 함) 및 질산 또는 아질산을 환원하는 탈질균을 주체로 하는 슬러지(이하, 탈질 슬러지라 함)가 포함되는 것으로 한다.In the present specification, the biological treatment tank is assumed to include an aeration tank that performs BOD removal, a nitrification tank that is mainly made of nitrification, and a denitrification tank that is mainly made of denitrification. The biological treatment tank holds a microbial community called activated sludge. In the present specification, when activated sludge is used, not only sludge (hereinafter referred to as BOD sludge) mainly containing aerobic bacteria decomposing BOD but also sludge composed mainly of nitrifying bacteria that oxidize ammonia (hereinafter referred to as nitrification sludge) (Hereinafter referred to as denitrification sludge) containing denitrifying bacteria as a main component for reducing nitric acid or nitrite.

생물 처리조는 MLSS 농도 1,000 ~ 30,000 mg/L 정도의 활성 슬러지를 유지하도록 운전하고, 활성 슬러지가 MLSS 농도의 10 질량％ 이상의 비율로 철을 포함하도록 철염을 첨가한다. 첨가하는 철염으로는, 염화제2철, 염화제1철, 및 폴리황산제2철 등을 들 수 있다. 철염을 과잉 첨가하면, 철에서 유래한 매우 미세한 입자가 생성되기 때문에, 철염의 첨가량은 MLSS 농도의 40 질량％를 상한으로 하며, 35 질량％를 상한으로 하는 것이 보다 바람직하다. 생물 처리조는 부유식, 스폰지 등의 담체가 첨가된 것, 및 고정바닥 등일 수 있고, 담체를 첨가한 경우 또는 고정바닥식인 경우에 부유 슬러지 중의 철염의 함유량이 철로서 10 질량％ 이상 40 질량％ 이하일 수 있다.The biological treatment tank is operated so as to maintain activated sludge with an MLSS concentration of about 1,000 to 30,000 mg / L, and an iron salt is added so that the activated sludge contains iron at a ratio of 10% by mass or more of the MLSS concentration. Examples of the iron salt to be added include ferric chloride, ferrous chloride, and ferric polysulfate. When the iron salt is excessively added, very fine particles derived from iron are produced. Therefore, the addition amount of the iron salt is preferably 40% by mass of the MLSS concentration, and more preferably 35% by mass. The biological treatment tank may be a floating tank, a sponge or the like, and a fixed bottom or the like. In the case of adding a carrier or a fixed bottom tank, the iron salt content in the floating sludge may be 10 mass% or more and 40 mass% or less .

철염의 첨가량은 생물 처리조에 도입되는 유기물 함유수의 유기물 농도를 기준으로 결정할 수 있는데, 이 경우 유기물 함유수에 포함되는 유기물(TOC)의 25 ~ 400 질량％ 정도를 첨가할 수 있다. 생물 처리조 내의 활성 슬러지에는 철염 이외 에 응집 작용이 있는 물질, 예를 들면 알루미늄염은 포함되지 않는 것이 좋지만, 다소(예를 들면, 철 10 질량％ 정도 이하)라면 혼입되어 있을 수 있다.The addition amount of the iron salt can be determined based on the organic substance concentration of the organic substance-containing water introduced into the biological treatment tank. In this case, about 25 to 400 mass% of the organic matter (TOC) contained in the organic substance-containing water can be added. The activated sludge in the biological treatment tank should not contain substances other than iron salts, such as aluminum salts, which have a cohesive action, but may be mixed if they are somewhat (for example, about 10 mass% or less iron).

여기서, MLSS 중의 유기물량의 비율, 구체적으로는 활성 슬러지 유기성 부유물질(Mixed Liquor Volatile Suspended Solids)/MLSS의 비는 0.05 ~ 0.75 정도, 특히 0.15 ~ 0.5 범위가 되도록 할 수 있다. 생물 처리조에 도입되는 유기물 함유수의 유기물 농도가 극단적으로 낮을 경우(예를 들면 생물분해 가능한 유기물인 Assimirable organic carbon, 이하 AOC 농도가 100 ng/L 정도 미만), 생물 처리조 내에서의 활성 슬러지의 증식이 적어져서 MLVSS/MLSS의 비가 상기 범위를 벗어날 경우도 있다. 이러한 경우에는, 생물 처리조에 미량의 유기물을 첨가하거나, 유기물 농도가 높은 다른 유기물 함유수를 혼합할 수 있다.Here, the ratio of the amount of organic matter in the MLSS, specifically, the ratio of the activated sludge organic suspended solids / MLSS, may be in the range of 0.05 to 0.75, particularly 0.15 to 0.5. When the concentration of organic matter in the organic substance-containing water introduced into the biological treatment tank is extremely low (for example, Assiminable organic carbon, hereinafter referred to as AOC concentration is less than about 100 ng / L), the amount of activated sludge in the biological treatment tank The MLVSS / MLSS ratio may deviate from the above range due to the reduced proliferation. In such a case, a small amount of organic matter may be added to the biological treatment tank or other organic matter-containing water having a high organic matter concentration may be mixed.

철염이 첨가된 활성 슬러지를 보유하는 생물 처리조의 조내액(즉 혼합액)은 pH를 5 ~ 6.5로 하고, 특히 5.5 ~ 6.0으로 하는 것이 바람직하다. pH조정에는 염산 등의 산 또는 알칼리를 이용할 수 있고, 첨가하는 철염의 종류 및 양에 따라서는 산이나 알칼리를 별도로 첨가하지 않고 pH조정을 할 수도 있다.The pH of the crude inner solution (i.e., the mixed solution) of the biological treatment tank having the activated sludge added with the iron salt is preferably 5 to 6.5, particularly preferably 5.5 to 6.0. An acid such as hydrochloric acid or an alkali may be used for the pH adjustment, and depending on the type and amount of the iron salt to be added, the pH may be adjusted without separately adding an acid or an alkali.

철염 공존하에 pH를 상기 범위로 하면, 활성 슬러지는 단단하게 응집하여 여과성이 향상되기 때문에, 막 분리를 행할 경우의 막힘(파울링(fouling))을 효과적으로 방지할 수 있다. 또한, 철염 공존하에 pH를 상기 범위로 함으로써, 통상의 경우 활성 슬러지로부터 생산되는 점질물과 같은 대사산물이 거의 생산되지 않게 된다. 이 때문에, 점질물이 막에 부착함에 기인하는 파울링을 회피할 수 있다. 더 나아가, 생물 처리조로부터 유출되는 처리수에도 점질물에 유래한 유기물(TOC)이 포 함되기 어려워지므로, 처리수 수질도 향상시킬 수 있다.When the pH is in the above range in the coexistence of iron salts, the activated sludge is hardly aggregated and the filtration property is improved, so that clogging (fouling) when the membrane separation is performed can be effectively prevented. In addition, when the pH is in the above range in the coexistence of iron salts, metabolites such as viscous substances produced from activated sludge are hardly produced. For this reason, it is possible to avoid fouling caused by adhesion of the viscous substance to the film. Furthermore, since treated water flowing out of the biological treatment tank is less likely to contain organic matter (TOC) derived from viscous materials, the quality of the treated water can be improved.

막 분리장치로 액분과 분리된 고형분(분리 슬러지)은 필요에 따라 일부를 반송 슬러지로서 생물 처리조에 반송하고, 생물 처리조에서의 슬러지의 체류시간을 2 ~ 50일 정도, 특히 5 ~ 20일 정도로 하여 슬러지를 뽑아내는 것이 바람직하다. 뽑아낸 슬러지는 잉여 슬러지로서 배출할 수도 있고, 오존 반응조나 소화조(消化槽) 등의 감용화(減容化) 수단으로 감용화 할 수도 있다.Part of the solid (separated sludge) separated from the liquid component by the membrane separation device is returned to the biological treatment tank as a part of the conveying sludge if necessary, and the residence time of the sludge in the biological treatment tank is about 2 to 50 days, particularly about 5 to 20 days It is preferable to extract the sludge. The extracted sludge may be discharged as surplus sludge or may be reduced by means of reducing the ozone reaction tank or the digestion tank.

본 발명에 따르면, 고도로 맑고 TOC 농도도 낮은 처리수를 얻을 수 있다. 이 때문에, 본 발명은 지하수, 하천수, 호소(湖沼, 댐호수 포함)수 등의 자연수, 수도물, 또는 배수를 처리하여 얻게 된 회수수를 원수로서 처리하여 얻게 된 처리수를 순수 제조에 이용하는 경우에 바람직하게 이용할 수 있다.According to the present invention, a treated water having a high degree of clearness and a low TOC concentration can be obtained. Therefore, in the case of using treated water obtained by treating natural water, tap water, or wastewater treated as raw water such as ground water, river water, lake water (including lake water, lake water) Can be preferably used.

이러한 물은 원래 유기물 농도가 0.1 ~ 10 mg/L 정도로 낮다. 이러한 물을 순수 제조용수로 할 경우, 슈도모나스속 등의 저영양세균이라 불리는 미생물을 주체로 하는 생물활성탄 등으로 생물 처리한 후, 한외여과(UF)막이나 구멍 지름이 0.2 ㎛ 이하 정도의 막으로 고액 분리한다. 순수 제조용수의 처리에 이용되는 막은 구멍 지름이 작기 때문에 막히기 쉽다. 특히, 자연수에는 막을 잘 막히게 하는 부식질(腐植質)이나 요소가 포함되고, 불용성 현탁물(SS) 농도도 높은 경우가 있다. 그러나 본 발명에 따르면, 높은 파울링 방지 효과를 얻을 수 있기 때문에, 원수에 1 mg/L을 초과하는 고농도의 부식질이나 요소 중 어느 한쪽 또는 양쪽 모두가 포함되어 있어도 좋고, 또한 SS도 0.1 ~ 30 mg/L 정도의 범위로 포함되어 있어도 좋다.Such water has a low organic matter concentration of about 0.1 to 10 mg / L. When such water is used as a pure water for production, it is biologically treated with biologically activated carbon mainly composed of a microorganism called a hypotrophic bacterium such as Pseudomonas sp. And then subjected to ultrafiltration (UF) membrane or a membrane having a pore diameter of 0.2 μm or less Separate. The membrane used for the treatment of the pure water for preparation is liable to be clogged because the pore diameter is small. Particularly, natural water contains humic substances or urea that clogs the membrane well, and the concentration of insoluble suspended solids (SS) is also high. However, according to the present invention, it is possible to obtain a high anti-fouling effect, so that the raw water may contain either or both of a high concentration of humic substances and / or elements exceeding 1 mg / L, and the SS may be 0.1 to 30 mg / L. ≪ / RTI >

본 발명에서는 생물 처리조 내의 활성 슬러지에 철염을 포함시키고, pH를 소정 범위로 함으로써 활성 슬러지의 응집성을 높일 수 있다. 또한, 활성 슬러지에 의한 대사산물의 생산을 억제할 수 있다. 이 때문에, 생물 처리조 내의 혼합액을 막 분리할 때의 막힘을 효과적으로 회피할 수 있어 처리수 수질을 향상시킬 수 있다.In the present invention, the iron sulphate is contained in the activated sludge in the biological treatment tank and the pH is set to a predetermined range, so that the cohesiveness of the activated sludge can be increased. In addition, production of metabolites by activated sludge can be suppressed. Therefore, it is possible to effectively prevent clogging in the separation of the mixed liquid in the biological treatment tank, thereby improving the quality of treated water.

이하, 본 발명에 대해 도면을 이용하여 상세하게 설명한다. 이하, 동일 부재에 대해서는 동일한 부호를 붙이고, 설명을 생략 또는 간략화 한다.Hereinafter, the present invention will be described in detail with reference to the drawings. Hereinafter, the same reference numerals are assigned to the same members, and the description thereof will be omitted or simplified.

도 1은, 본 발명에 이용되는 유기물 함유수의 생물처리장치(이하, 간단히 처리장치라 함)(1)의 모식도이다. 처리장치(1)는, 생물 처리조(10), 막 분리장치로서의 침지막(11), 철염 첨가수단(12), 및 pH 조정수단(13)을 구비한다. 침지막(11)은 생물 처리조(10) 내에 침지되어 있다. 철염 첨가수단(12)은 철염 저장조(15) 및 철염 첨가로(16)로 구성되고, pH 조정수단(13)은 pH조정제 저장조(17)와 pH조정제 첨가로(18)로 구성되어 있다. 이하, 이 처리장치(1)를 이용하여 유기물 함유수를 처리할 경우의 처리방법에 대해서 설명한다.1 is a schematic diagram of a biological treatment apparatus (hereinafter, simply referred to as a treatment facility) 1 for organic-matter-containing water used in the present invention. The treatment apparatus 1 is provided with a biological treatment tank 10, an immersion film 11 as a membrane separation device, an iron salt addition means 12 and a pH adjustment means 13. The immersion membrane (11) is immersed in the biological treatment tank (10). The iron salt adding means 12 is composed of an iron salt storing tank 15 and an iron salt adding furnace 16 and the pH adjusting means 13 is composed of a pH adjusting agent reservoir 17 and a pH adjusting agent adding furnace 18. Hereinafter, a treatment method in the case of treating the organic substance-containing water by using the treatment apparatus 1 will be described.

생물 처리조(10)에는 원수관(31)이 연결되며, 원수관(31)을 통하여 유기물 함유수를 생물 처리조(10)에 도입한다. 본 실시형태의 생물 처리조(10)는 순수 제조용수의 처리를 목적으로 구성되고, 슈도모나스속 등의 저영양 호기성 세균을 주체로 하는 BOD 슬러지를 MLSS 농도 1,000 ~ 30,000 mg/L 정도로 유지한다.A raw water pipe (31) is connected to the biological treatment tank (10), and organic - containing water is introduced into the biological treatment tank (10) through a raw water pipe (31). The biological treatment tank 10 of the present embodiment is configured for the treatment of pure water for production, and maintains a BOD sludge composed mainly of low-nutritional aerobic bacteria such as Pseudomonas sp. At an MLSS concentration of about 1,000 to 30,000 mg / L.

생물 처리조(10) 내의 활성 슬러지는 철염을 포함하는데, MLVSS/MLSS는 0.05 ~ 0.75 정도, 특히 0.15 ~ 0.5 정도가 되도록 하는 것이 좋다. 생물 처리조(10) 내의 MLSS 농도 및 MLVSS/MLSS의 비를 상기 범위로 유지하기 위해서, 원수의 유기물 농도가 낮은 경우, 생물 처리조(10)에는 BOD 농도 1 ~ 10 mg/L 정도의 유기물 함유수를 도입하는 것이 바람직하다. 또한, 생물 처리조(10)는 BOD 슬러지 부하 0.01 ~ 0.2 kg-BOD/kg-MLVSS/day 정도, 슬러지 체류시간 2 ~ 50일 정도로 운전하여, BOD를 활성 슬러지에 의해 호기적으로 생물분해 하는 것이 좋다.Activated sludge in the biological treatment tank 10 includes iron salts, and MLVSS / MLSS is preferably 0.05 to 0.75, particularly 0.15 to 0.5. In order to keep the MLSS concentration and the MLVSS / MLSS ratio in the biological treatment tank 10 within the above range, when the organic substance concentration of the raw water is low, the biological treatment tank 10 is provided with an organic substance content of about 1 to 10 mg / It is preferable to introduce water. The biological treatment tank 10 is operated to aerate biodegradation of BOD with activated sludge by operating at a BOD sludge load of about 0.01 to 0.2 kg-BOD / kg-MLVSS / day and a sludge residence time of about 2 to 50 days good.

생물 처리조(10)에는 철염 저장조(15)로부터 철염 첨가로(16)를 통하여 철염을 첨가한다. 생물 처리조(10)에는 응집 작용이 있는 철염을 첨가하며, 그 종류는 상술한 바와 같다. 생물 처리조(10)에는 바람직하게는 도 1에 도시한 바와 같이 MLSS 측정기(M)를 마련하고, 철염의 첨가량은 상술한 바와 같이 생물 처리조(10)의 MLSS 농도의 10 ~ 40 질량％로 한다.In the biological treatment tank 10, an iron salt is added from the iron salt storage tank 15 through the iron salt additive passage 16. In the biological treatment tank 10, an iron salt having a cohesive action is added, and the kind thereof is as described above. 1, the MLSS measuring device M is preferably provided in the biological treatment tank 10, and the addition amount of the iron salt is preferably 10 to 40% by mass of the MLSS concentration of the biological treatment tank 10 as described above do.

처리장치(1)에서는, 침지막(11)을 생물 처리조(10) 내에 설치하였으므로, 생물 처리조(10) 내에서 침지막(11)에 의해 고형분과 액분을 막 분리한다. 분리된 고형분(분리 슬러지)은, 일부를 생물 처리조(10)에 연결된 분리 슬러지관(33)으로 배출하고, 나머지를 생물 처리조(10) 내에 보유한다. 분리 슬러지는 생물 처리조(10)의 슬러지 체류시간이 상술한 범위가 되도록 정기적으로 생물 처리조(10)로부터 뽑아낼 수 있다. 이와 같이, 처리장치(1)에서는 생물 처리조(10)에 첨가된 철염이 분리 슬러지를 뽑아냄에 따라 생물 처리조(10)로부터 반출되기 때문에, 철염의 첨가량은 원수관(31)으로부터 생물 처리조(10)에 도입되는 유기물 함유수의 유기물 농도를 기준으로 결정할 수 있다.Since the immersion membrane 11 is provided in the biological treatment tank 10 in the treatment apparatus 1, the solid and liquid components are separated by the immersion membrane 11 in the biological treatment tank 10. Part of the separated solid (separation sludge) is discharged to the separation sludge pipe 33 connected to the biological treatment tank 10, and the remainder is retained in the biological treatment tank 10. The separated sludge can be extracted from the biological treatment tank 10 regularly so that the sludge residence time of the biological treatment tank 10 is in the above-described range. As described above, in the treatment apparatus 1, since the iron salt added to the biological treatment tank 10 is taken out of the biological treatment tank 10 by extracting the separation sludge, the added amount of the iron salt is removed from the raw water tube 31 by biological treatment Can be determined based on the organic substance concentration of the organic substance-containing water introduced into the bath (10).

생물 처리조(10)에는 도 1에 도시한 바와 같이 바람직하게는 pH 측정기(H)를 설치한다. 그리고, pH조정제 첨가로(18)를 통하여 pH조정제로서 pH조정제 저장조(17)에 저장된 산 또는 알칼리를 첨가하여 조내액의 pH를 상기 범위로 한다.As shown in Fig. 1, a pH meter H is preferably provided in the biological treatment tank 10. [ Then, the acid or alkali stored in the pH adjuster reservoir 17 is added as a pH adjuster through the pH adjuster addition furnace 18 to adjust the pH of the crude inner liquid to the above-mentioned range.

생물 처리조(10) 내에는 산기 수단으로서 산기관(散氣管,14)이 마련되어 있다. 산기관(14)으로부터는 생물 처리조(10) 내에 설치된 침지막(11)에 대해서도 폭기가 수행되며, 폭기에 의해 침지막(11)을 세정하면서 막 분리를 수행한다.In the biological treatment tank (10), a diffuser (14) is provided as a diffuser. Aeration is also performed on the immersion film 11 provided in the biological treatment tank 10 from the diffuser 14 and membrane separation is performed while cleaning the immersion film 11 by aeration.

침지막(11)으로서는 고액 분리에 일반적으로 이용되는 막이면 특별히 한정하지 않는다. 구체적으로는, 정밀여과(MF)막, 또는 한외여과(UF)막을 이용할 수 있고, 막 모듈의 형상은 중공계, 또는 평막 등일 수 있다.The immersion membrane 11 is not particularly limited as long as it is a membrane generally used for solid-liquid separation. Specifically, a microfiltration (MF) membrane or an ultrafiltration (UF) membrane can be used, and the shape of the membrane module can be a hollow system, a flat membrane, or the like.

침지막(11)에는 처리수관(32)이 장착되어 있다. 처리수관(32)의 도중에는 펌프(P)가 설치되고, 펌프(P)로 침지막(11) 내부를 흡인하여 생물 처리조(10) 내의 혼합액을 막 분리한다. 막 분리에 의해 고형분과 분리되어 맑아진 액은 처리수로서 처리수관(32)을 통하여 생물 처리조(10)로부터 취출된다. 한편, 분리 슬러지는 상술한 바와 같이, 생물 처리조(10) 내에 보유되며, 일부는 분리 슬러지관(33)으로부터 잉여 슬러지로 배출될 수 있다.A treatment water pipe (32) is mounted on the immersion membrane (11). A pump P is provided in the middle of the treatment water pipe 32 and sucks the inside of the immersion membrane 11 with the pump P to separate the mixed solution in the biological treatment tank 10. The liquid separated and separated from the solid content by the membrane separation is taken out from the biological treatment tank 10 through the treatment water pipe 32 as treated water. On the other hand, the separation sludge is retained in the biological treatment tank 10 as described above, and a part of it can be discharged from the separation sludge pipe 33 to the excess sludge.

본 발명은, 상기 방법에 한정되지 않는다. 다음에, 본 발명의 다른 실시양태로서, 도 2에 도시하는 처리장치(2)를 이용한 처리방법을 설명한다. 처리장치(2)는 유기물 농도가 20 ~ 100 mg/L 정도의 유기물 함유수를 처리하고, 잉여 슬러지의 발생량이 많을 경우에 적합한 장치이며, 슬러지 감용화 수단으로서의 오존 반응조(19)를 더 구비한다. 오존 반응조(19)는 분리 슬러지관(33)을 통하여 생물 처리 조(10)와 연결되며, 생물 처리조(10)로부터 배출되는 잉여 슬러지를 오존에 의해 가용화한다.The present invention is not limited to the above method. Next, as another embodiment of the present invention, a processing method using the processing apparatus 2 shown in Fig. 2 will be described. The treatment device 2 is an apparatus suitable for treating an organic substance-containing water having an organic substance concentration of about 20 to 100 mg / L and generating a large amount of surplus sludge, and further includes an ozone reaction tank 19 as sludge sensitization means . The ozone reaction tank 19 is connected to the biological treatment tank 10 through a separation sludge pipe 33 and solubilizes excess sludge discharged from the biological treatment tank 10 by ozone.

오존 반응조(19)에는 배니관(35)을 연결하여 가용화된 슬러지를 취출한다. 배니관(35)으로부터는 반송관(34)을 분기시키고, 반송관(34)을 생물 처리조(10)와 연결함으로서 가용화된 슬러지를 생물 처리조(10)에 반송할 수 있다. 한편, MLVSS/MLSS의 비를 상기 범위로 유지하기 위해서는 배니관(35)으로부터 적절하게 무기물이 집적된 슬러지를 배출한다.A banny tube (35) is connected to the ozone reaction tank (19) to extract the solubilized sludge. The sludge that has been solubilized can be returned to the biological treatment tank 10 by branching the return pipe 34 from the vanny tube 35 and connecting the return pipe 34 to the biological treatment tank 10. On the other hand, in order to keep the ratio of MLVSS / MLSS within the above range, the sludge in which the inorganic matter is accumulated appropriately is discharged from the vanny tube 35.

이 처리장치(2)를 이용하는 처리방법에서는, 잉여 슬러지를 가용화해서 생물 처리조(10)에 반송함으로써 잉여 슬러지의 발생량을 줄일 수 있다. 또한, 잉여 슬러지가 생물 처리조(10)로 반송되기 때문에, 처리장치(2) 계외로 반출되는 철염의 양이 줄어든다. 이 때문에, 처리장치(2)를 이용하는 처리방법에서는, 생물 처리조(10)의 MLSS 농도에 대한 철염 농도가 소정의 범위가 되도록 필요에 따라 적절하게 철염을 첨가할 수 있다. 이와 같이, 처리장치(2)를 이용하는 처리방법에서는, 처리장치(1)처럼 유기물 함유수의 유기물 농도를 기준으로 하여 철염을 연속적으로 첨가할 필요가 없기 때문에, 철염의 사용량을 줄일 수 있다.In the treatment method using the treatment device 2, the surplus sludge is solubilized and transported to the biological treatment tank 10, whereby the amount of surplus sludge generated can be reduced. Further, since the surplus sludge is returned to the biological treatment tank 10, the amount of the iron salts carried out of the system 2 is reduced. Therefore, in the treatment method using the treatment device 2, iron salts can be appropriately added as needed so that the concentration of the iron salt with respect to the MLSS concentration of the biological treatment tank 10 is within a predetermined range. Thus, in the treatment method using the treatment device 2, it is not necessary to continuously add the iron salt based on the organic substance concentration of the organic substance-containing water as in the treatment device 1, so that the use amount of the iron salt can be reduced.

지금까지 막 분리를 침지막(11)에 의해 수행하는 처리방법에 대해서 서술했으나, 침지막(11) 대신 도 3에 도시하는 가압형 막 모듈(21)을 막 분리장치로 구비한 처리장치(3)를 이용할 수도 있다. 막 모듈(21)에 이용하는 막의 종류는 MF막이나 UF막일 수 있으며, 모듈 형식은 중공계막, 평막 이외에 스파이럴막일 수 있다.The treatment method in which the membrane separation is carried out by the immersion membrane 11 has been described so far. However, instead of the immersion membrane 11, the treatment type membrane module 21 shown in Fig. 3 is replaced with a treatment apparatus 3 ) May be used. The membrane used for the membrane module 21 may be an MF membrane or a UF membrane, and the membrane module may be a spiral membrane other than a hollow membrane and a flat membrane.

막 모듈(21)은 송액관(36)을 통하여 생물 처리조(10)와 연결되어 있다. 펌 프(P)는 송액관(36)의 도중에 설치되어 있다. 혼합액은 생물 처리조(10)로부터 취출되고, 철염과 함께 응집된 활성 슬러지를 포함하여, pH를 상기 범위로 한 상태에서 펌프(P)에 의해 막 모듈(21)로 보내져 가압 여과된다.The membrane module (21) is connected to the biological treatment tank (10) through a liquid delivery pipe (36). The pump (P) is installed in the middle of the liquid delivery pipe (36). The mixed liquid is taken out from the biological treatment tank 10 and is sent to the membrane module 21 by the pump P under pH in the above range including the activated sludge agglomerated together with the iron salt and pressure filtered.

막 모듈(21)에는 처리수관(32)과 분리 슬러지관(33)이 연결되고, 막 모듈(21)에 의해 고형분을 분리한 처리수는 처리수관(32)으로부터 취출되고, 분리 슬러지는 분리 슬러지관(33)으로부터 취출된다. 분리 슬러지관(33)으로부터는 반송관(34)을 분기시키고, 반송관(34)을 생물 처리조(10)와 연결함으로써 분리 슬러지의 일부를 생물 처리조(10)로 반송한다. 분리 슬러지의 일부는 잉여 슬러지로서 분리 슬러지관(33)으로부터 뽑아낼 수 있다. 이 처리장치(3)를 이용하는 경우에는 분리 슬러지의 반송량과 뽑아내는 양을 조정하여 생물 처리조(10)의 슬러지 체류시간, MLSS 농도, MLVSS/MLSS의 비를 조정할 수 있다.The treated water pipe 32 and the separated sludge pipe 33 are connected to the membrane module 21 and the treated water separated from the solid component by the membrane module 21 is taken out from the treated water pipe 32, And is taken out from the pipe 33. A part of the separated sludge is returned to the biological treatment tank 10 by branching the return pipe 34 from the separated sludge pipe 33 and connecting the return pipe 34 to the biological treatment tank 10. A part of the separation sludge can be extracted from the separation sludge pipe 33 as surplus sludge. In the case of using the treatment device 3, the sludge residence time, MLSS concentration, MLVSS / MLSS ratio of the biological treatment tank 10 can be adjusted by adjusting the transport amount and the extraction amount of the separation sludge.

처리장치(3)를 이용할 경우, 분리 슬러지관(33)으로부터 연속적으로 잉여 슬러지로서 분리 슬러지를 뽑아내는 경우에는, 처리장치(1)를 이용하는 경우와 마찬가지로, 생물 처리조(10)에 도입되는 유기물 함유수의 유기물 농도를 기준으로 하여 철염을 첨가할 수 있다. 한편, 분리 슬러지관(33)을 감용화 수단과 연결해서 잉여 슬러지를 가용화하여 생물 처리조(10)에 반송하는 경우에는, 처리장치(2)를 이용하는 경우와 마찬가지로, 철염은 필요에 따라 생물 처리조(10)에 첨가할 수 있다.In the case of using the treatment device 3, when the separated sludge is taken out continuously as the excess sludge from the separated sludge pipe 33, as in the case of using the treatment device 1, The iron salt may be added based on the organic substance concentration of the water containing water. On the other hand, in the case where the separated sludge pipe 33 is connected to the humidifying means so that the excess sludge is solubilized and transferred to the biological treatment tank 10, as in the case of using the treatment device 2, Can be added to the bath (10).

이와 같이, 상기 실시양태는 적절히 변경가능하며, 예를 들면 생물 처리조에 질화균을 주체로 하는 질화 슬러지를 보유하는 경우에도 적용할 수 있다. 또는, 생 물 처리조에 탈질균을 주체로 하는 탈질 슬러지를 보유하는 경우에도 적용할 수 있다. 이러한 경우도 생물 처리조 내의 MLSS 농도에 대하여, 철염을 상기 범위가 되도록 첨가하고 pH를 상기 범위로 할 수 있다.As described above, the embodiment can be suitably modified, and can be applied to, for example, a case where nitrification sludge mainly composed of nitrifying bacteria is contained in a biological treatment tank. Alternatively, the present invention can be applied to a case where denitrification sludge mainly containing denitrifying bacteria is contained in a biological treatment tank. In this case also, the iron salt may be added to the above range to the MLSS concentration in the biological treatment tank, and the pH may be set within the above range.

본 발명자의 견해에 따르면, 이러한 여러가지 양태 중에서, BOD를 제거하는 호기성 세균을 주체로 하는 활성 슬러지에 의해 유기물 함유수를 처리할 경우에 있어서, 상기 수치 범위의 MLSS 농도로, 상기 수치 범위의 철염공존하에서 pH를 상기 범위로 할 경우에 높은 파울링 방지 효과를 얻을 수 있다. 또한, 막 분리장치로서는 펌프에 의한 송액시의 플록 파괴의 우려가 낮은 침지막형이 바람직하다.According to the opinion of the present inventors, in the case of treating the organic-matter-containing water with the activated sludge mainly composed of aerobic bacteria that remove BOD, the MLSS concentration in the above-mentioned numerical range, A high fouling preventing effect can be obtained when the pH is in the above range. It is preferable that the membrane separation apparatus is of the immersion type which is less likely to cause floc destruction at the time of pumping by the pump.

(실시예)(Example)

[비교예 1][Comparative Example 1]

이하, 실시예 및 비교예에 대해 설명한다. 우선, 비교예 1로서, 하천수(BOD 농도 1.2 mg/L, SS농도 3 mg/L)에 인산1칼륨을 첨가하여, 인 농도를 0.3 mg/L로 한 유기물 함유수를 처리하였다. 이 하천수의 부식질 함유량을 파악하기 위해, 부식질과 상관성이 높은 260 ㎚ 파장의 자외선 흡광도 E260을 측정하였더니, E260의 값은 0.42였다.Examples and Comparative Examples are described below. First, as a comparative example 1, potassium phosphate was added to river water (BOD concentration 1.2 mg / L, SS concentration 3 mg / L) to treat organic-matter-containing water having a phosphorus concentration of 0.3 mg / L. The ultraviolet absorbance of 260 nm wavelength E260, which is highly correlated with humic substances, was measured to determine the humus content of this stream water, and the value of E260 was 0.42.

비교예 1에서는, 도 1에 도시하는 처리장치(1)를 모방한 실험장치를 이용하였다. 생물 처리조의 크기는 0.2 ㎥로, 내부에 침지막을 침지시켰다. 침지막은 4 ㎥ 크기의 평막 타입, 구멍 지름 0.1 ㎛ MF막(미쯔비시레이온주식회사 제조)을 이용하였다.In Comparative Example 1, an experimental apparatus simulating the processing apparatus 1 shown in Fig. 1 was used. The size of the biological treatment tank was 0.2 m 3, and the immersion membrane was immersed therein. The immersion membrane was a flat membrane type having a size of 4 m < 3 > and an MF membrane having a pore diameter of 0.1 mu m (manufactured by Mitsubishi Rayon Co., Ltd.).

상기 유기물 함유수를 3㎥/day 유량으로 생물 처리조에 공급하였다. 침지막 에 연결된 처리수관의 도중에 설치된 진공 펌프로 감압하여, 처리수관으로부터 처리수를 취출하였다. 비교예 1에서는, 실험 개시로부터 1일에 막이 막혀서 처리수를 뽑아낼 수 없게 되었다. 이 시점에서의 처리수의 TOC 농도는 2.2 mg/L이며, 조내의 혼합액의 성상은 이하와 같았다.The organic substance-containing water was supplied to the biological treatment tank at a flow rate of 3 m 3 / day. The pressure was reduced by a vacuum pump installed in the middle of the treatment water pipe connected to the immersion membrane, and the treated water was taken out from the treatment water pipe. In Comparative Example 1, the membrane was blocked on the first day from the start of the experiment, and the treated water could not be extracted. At this point, the TOC concentration of the treated water was 2.2 mg / L, and the properties of the mixed solution in the tank were as follows.

[생물 처리조 내의 혼합액][Mixed solution in biological treatment tank]

철함유 비율; MLSS의 4.8 질량％ (철로서)Iron content; 4.8% by mass of MLSS (as iron)

MLSS 농도; 490 mg/LMLSS concentration; 490 mg / L

MLVSS 농도; 180 mg/LMLVSS concentration; 180 mg / L

pH; 7.1pH; 7.1

[실시예 1][Example 1]

(제 1 단계)(First step)

비교예 1에서 처리수를 뽑아내지 못한 생물 처리조를 비우고, 생물 처리조에 활성 슬러지를 MLSS 농도 100 mg/L 가 되도록 첨가하고, 이 혼합액에 철염으로 염화제2철을 철로서 1,000 mg/L의 비율로 첨가하였다. 또한, 생물 처리조에 pH 측정기를 설치하여 수산화나트륨으로 pH조정을 하여 pH 6으로 유지하였다. 그리고, 비교예 1의 처리 대상인 유기물 함유수에 염화제2철을 4 mg/L 첨가하고, 1.2 ㎥/day 유량으로 생물 처리조에 공급하였더니, 통수(通水) 개시후 3일 후부터 침지막의 차압상승이 없어졌다. 이 시점에서의 처리수의 TOC 농도는 145 ng/L이며, 생물 처리조 내의 혼합액의 성상은 이하와 같았다.The biological treatment tank in which the treated water could not be extracted in Comparative Example 1 was evacuated and the activated sludge was added to the biological treatment tank so as to have an MLSS concentration of 100 mg / L. Ferric chloride was added to this mixed solution in an amount of 1,000 mg / L . In addition, a pH meter was provided in the biological treatment tank, and pH was adjusted to 6 with sodium hydroxide. Then, 4 mg / L of ferric chloride was added to the organic-matter-containing water to be treated in Comparative Example 1, and the resulting mixture was supplied to the biological treatment tank at a flow rate of 1.2 m 3 / day. After three days from the start of the water- The rise is gone. At this point, the TOC concentration of the treated water was 145 ng / L, and the characteristics of the mixed solution in the biological treatment tank were as follows.

[생물 처리조 내의 혼합액][Mixed solution in biological treatment tank]

철함유 비율; MLSS의 35 질량％ (철로서)Iron content; 35% by mass of MLSS (as iron)

MLSS 농도; 1940 mg/LMLSS concentration; 1940 mg / L

MLVSS 농도; 110 mg/LMLVSS concentration; 110 mg / L

pH; 6pH; 6

(제 2 단계)(Second step)

제 1 단계를 종료하고, 제 2 단계로서 생물 처리조에 대한 유기물 함유수의 공급량을 3㎥/day로 하였다. 제 2 단계에서는 생물 처리조로부터 20 L/day로 조 내의 슬러지를 뽑아냈다. 그 밖의 조건은 제 1 단계와 동일하게 하여, 생물 처리조에는 염화제2철을 4 mg/L로 첨가한 유기물 함유수를 공급하고, 생물 처리조 내의 pH도 6으로 유지하였다. 제 2 단계에서는, 2개월간 침지막의 차압상승은 인식되지 않았고, 처리수의 TOC 농도는 20 ng/L 이하로 안정적이었다. 제 2 단계에서의 생물 처리조 내의 혼합액의 성상은 이하와 같았다.The first step was terminated and in the second step, the supply amount of the organic-substance-containing water to the biological treatment tank was set at 3 m 3 / day. In the second step, the sludge in the tank was extracted from the biological treatment tank at 20 L / day. The other conditions were the same as in the first step, and organic water containing 4 mg / L of ferric chloride was added to the biological treatment tank, and the pH in the biological treatment tank was maintained at 6. In the second step, the pressure difference of the immersion membrane was not recognized for 2 months, and the TOC concentration of the treated water was stable to 20 ng / L or less. The properties of the mixed solution in the biological treatment tank in the second step were as follows.

[생물 처리조 내의 혼합액][Mixed solution in biological treatment tank]

철함유 비율; MLSS의 22질량％ (철로서)Iron content; 22% by mass of MLSS (as iron)

MLSS 농도; 3,700 mg/LMLSS concentration; 3,700 mg / L

MLVSS 농도; 1,670 mg/LMLVSS concentration; 1,670 mg / L

pH; 6pH; 6

(제 3 단계)(Third step)

제 2 단계에 이어서, 제 3 단계로서 생물 처리조에 대한 유기물 함유수의 공급량을 4 ㎥/day로 한 것 이외에는 제 2 단계와 동일하게 하여 1개월간 처리를 계 속했다. 1개월간의 제 3 단계 기간 동안, 침지막의 차압상승은 인식되지 않았고, 처리수의 TOC 농도는 100 ng/L이하로 안정적이었다. 제 3 단계에서의 생물 처리조 내의 혼합액의 성상은 이하와 같았다.Following the second step, treatment was continued for one month in the same manner as in the second step except that the supply amount of the organic substance-containing water to the biological treatment tank was set at 4 m 3 / day as the third step. During the third stage of the one month period, no increase in the pressure difference of the immersion membrane was recognized, and the TOC concentration of the treated water was stable to 100 ng / L or less. The properties of the mixed solution in the biological treatment tank in the third step were as follows.

[생물 처리조 내의 혼합액][Mixed solution in biological treatment tank]

철함유 비율; MLSS의 19.7 질량％ (철로서)Iron content; 19.7 mass% of the MLSS (as iron)

MLSS 농도; 4,900 mg/LMLSS concentration; 4,900 mg / L

MLVSS 농도; 2,350 mg/LMLVSS concentration; 2,350 mg / L

pH; 6pH; 6

(제 4 단계)(Step 4)

제 3 단계에 이어서, 제 4 단계로서 생물 처리조에 공급하는 유기물 함유수에 이소프로필알콜(IPA)을 8 mg/L 더 첨가하였다. 유기물 함유수에 IPA를 첨가한 것 이외에는 제 3 단계와 동일하게 하여 1개월간 처리를 계속했다. 1개월간의 제 4 단계 기간 동안, 침지막의 차압상승은 인식되지 않았고, 처리수의 TOC 농도는 133 ng/L이었다. 제 4 단계에서의 생물 처리조 내의 혼합액의 성상은 이하와 같았다.Following the third step, 8 mg / L of isopropyl alcohol (IPA) was further added to the organic-substance-containing water supplied to the biological treatment tank as the fourth step. The treatment was continued for one month in the same manner as in the third step except that IPA was added to the organic substance-containing water. During the first stage of the one-month period, the pressure rise of the immersion membrane was not recognized, and the TOC concentration of the treated water was 133 ng / L. The properties of the mixed solution in the biological treatment tank in the fourth step were as follows.

[생물 처리조 내의 혼합액][Mixed solution in biological treatment tank]

철함유 비율; MLSS의 15.3 질량％ (철로서)Iron content; 15.3% by mass of MLSS (as iron)

MLSS 농도; 5,690 mg/LMLSS concentration; 5,690 mg / L

MLVSS 농도; 2,810 mg/LMLVSS concentration; 2,810 mg / L

pH; 6pH; 6

(제 5 단계)(Step 5)

제 4 단계에 이어서, 제 5 단계로서 유기물 함유수로의 IPA의 첨가량을 10 mg/L로 늘리고, 생물 처리조로의 유기물 함유수의 공급량을 3㎥/day로 하였다. 유기물 함유수로의 IPA 첨가량을 늘리고, 통수량을 내린 것 이외에는 제 4 단계와 동일하게 하여 1주간 처리를 계속했다. 1주간의 제 5 단계 기간 동안, 침지막의 차압은 거의 상승하지 않았고 처리수의 TOC 농도는 274 ng/L이었다. 제 5 단계에서의 생물 처리조 내의 혼합액의 성상은 이하와 같았다.Following the fourth step, as the fifth step, the addition amount of IPA to the organic substance-containing water was increased to 10 mg / L, and the supply amount of the organic substance-containing water to the biological treatment tank was 3 m 3 / day. The treatment was continued for one week in the same manner as in the fourth step except that the amount of IPA added to the organic substance-containing water was increased and the flow rate was reduced. During the 5th period of one week, the differential pressure of the immersion membrane did not rise substantially, and the TOC concentration of the treated water was 274 ng / L. The properties of the mixed solution in the biological treatment tank in the fifth step were as follows.

[생물 처리조 내의 혼합액][Mixed solution in biological treatment tank]

철함유 비율; MLSS의 12.9 질량％ (철로서)Iron content; 12.9% by mass of MLSS (as iron)

MLSS 농도; 2700 mg/LMLSS concentration; 2700 mg / L

MLVSS 농도; 1377 mg/LMLVSS concentration; 1377 mg / L

pH; 6pH; 6

(제 6 단계)(Step 6)

제 5 단계에 이어서, 제 6 단계로서 유기물 함유수로의 IPA 첨가량을 50 mg/L로 늘렸다. 유기물 함유수로의 IPA 첨가량을 늘린 것 이외에는 제 5 단계와 동일하게 하여 1주간 처리를 계속했다. 제 6 단계에서는, 침지막의 차압은 상승하기 시작하여 1주간 후의 제 6 단계 종료 시점에서는 제 6 단계 개시시에 비해 40 kP의 차압상승이 있었고, 처리수의 TOC 농도는 1.6 mg/L이었다. 제 6 단계 종료 시점에서의 생물 처리조 내의 혼합액의 성상은 이하와 같았다.Following the fifth step, as the sixth step, the amount of IPA added to the organic substance-containing water was increased to 50 mg / L. The treatment was continued for one week in the same manner as in the fifth step except that the amount of IPA added to the organic substance-containing water was increased. In the sixth step, the differential pressure of the immersion membrane began to increase. At the end of the sixth step after one week, there was a differential pressure rise of 40 kP as compared with that at the start of the sixth step, and the TOC concentration of the treated water was 1.6 mg / L. The characteristics of the mixed liquid in the biological treatment tank at the end of the sixth step were as follows.

[생물 처리조 내의 혼합액][Mixed solution in biological treatment tank]

철함유 비율; MLSS의 9.4 질량％ (철로서)Iron content; 9.4% by mass of MLSS (as iron)

MLSS 농도; 5700 mg/LMLSS concentration; 5700 mg / L

MLVSS 농도; 3477 mg/LMLVSS concentration; 3477 mg / L

pH; 6pH; 6

(제 7 단계)(Step 7)

제 7 단계를 시작하기 전에, 생물 처리조로부터 침지막을 취출하여, 수산화나트륨, 구연산, 및 차아염소산나트륨 용액으로 세정하였다. 또한, 생물 처리조 내의 활성 슬러지를 반 정도 뽑아냄과 동시에, 생물 처리조에 MLSS에 대한 철염의 함유 비율이 15 질량％가 되도록 염화제2철을 첨가하였다. 이후, 제 7 단계로서 유기물 함유수로의 IPA의 첨가량을 10 mg/L로 줄이고, 그 이외는 제 6 단계와 동일하게 하여 1주간 처리를 계속했다. 1주간의 제 7 단계 기간 동안, 침지막의 차압은 상승하지 않았고, 처리수의 TOC 농도는 192 ng/L이었다. 제 7 단계에서의 생물 처리조 내의 혼합액의 성상은 이하와 같았다.Before starting the seventh step, the immersion membrane was taken out from the biological treatment tank and washed with sodium hydroxide, citric acid, and sodium hypochlorite solution. Activated sludge in the biological treatment tank was extracted to about half, and ferric chloride was added to the biological treatment tank so that the content of the iron salt in the MLSS was 15 mass%. Then, in the seventh step, the treatment was continued for one week in the same manner as in the sixth step except that the addition amount of IPA to the organic substance-containing water was reduced to 10 mg / L. During the seventh stage of the one week period, the differential pressure of the immersion membrane did not rise and the TOC concentration of the treated water was 192 ng / L. The properties of the mixed liquid in the biological treatment tank in the seventh step were as follows.

[생물 처리조 내의 혼합액][Mixed solution in biological treatment tank]

철함유 비율; MLSS의 15.1 질량％ (철로서)Iron content; 15.1 mass% of the MLSS (as iron)

MLSS 농도; 2,840 mg/LMLSS concentration; 2,840 mg / L

MLVSS 농도; 1,510 mg/LMLVSS concentration; 1,510 mg / L

pH; 6pH; 6

(제 8 단계)(Step 8)

제 7 단계에 이어서, 제 8 단계로서 생물 처리조 내의 혼합액의 pH를 5로 유지하였다. 혼합액의 pH를 내린 것 이외에는 제 7 단계와 동일하게 하여 1주간 처리 를 계속하였더니, 침지막의 차압은 상승하지 않았고, 처리수의 TOC 농도는 222 ng/L이었다. 제 8 단계에서의 생물 처리조 내의 혼합액의 성상은 이하와 같았다.Following the seventh step, the pH of the mixed solution in the biological treatment tank was maintained at 5 as the eighth step. When the treatment was continued for one week in the same manner as in the seventh step except that the pH of the mixed solution was lowered, the differential pressure of the immersion film did not rise and the TOC concentration of the treated water was 222 ng / L. The properties of the mixed solution in the biological treatment tank in the eighth step were as follows.

[생물 처리조 내의 혼합액][Mixed solution in biological treatment tank]

철함유 비율; MLSS의 16.7 질량％ (철로서)Iron content; 16.7% by mass of MLSS (as iron)

MLSS 농도; 3,160 mg/LMLSS concentration; 3,160 mg / L

MLVSS 농도; 1,630 mg/LMLVSS concentration; 1,630 mg / L

pH; 5pH; 5

(제 9 단계)(Step 9)

제 8 단계에 이어서, 제 9 단계로서 생물 처리조 내의 혼합액의 pH를 5.5로 유지하였다. 혼합액의 pH를 올린 것 이외에는 제 8 단계와 동일하게 하여 1주간 처리를 계속하였더니, 침지막의 차압은 상승하지 않았고, 처리수의 TOC 농도는 197 ng/L이었다. 제 9 단계에서의 생물 처리조 내의 혼합액의 성상은 이하와 같았다.Following the eighth step, as the ninth step, the pH of the mixed solution in the biological treatment tank was maintained at 5.5. When the treatment was continued for one week in the same manner as in the eighth step except that the pH of the mixed solution was increased, the differential pressure of the immersion film did not rise and the TOC concentration of the treated water was 197 ng / L. The properties of the mixed solution in the biological treatment tank in the ninth step were as follows.

[생물 처리조 내의 혼합액][Mixed solution in biological treatment tank]

철함유 비율; MLSS의 18.4 질량％ (철로서)Iron content; 18.4% by mass of MLSS (as iron)

MLSS 농도; 3,360 mg/LMLSS concentration; 3,360 mg / L

MLVSS 농도; 1,690 mg/LMLVSS concentration; 1,690 mg / L

pH; 5.5pH; 5.5

(제 10 단계)(Step 10)

제 9 단계에 이어서, 제 10 단계로서 생물 처리조 내의 혼합액의 pH를 7로 올렸다. 혼합액의 pH를 올린 것 이외에는 제 9 단계와 동일하게 하여, 제 10 단계 개시 다음날로부터 침지막의 차압이 상승하였고, 2일로 처리를 계속할 수 없게 되었다. 처리 정지 2시간전의 처리수의 TOC 농도는 910 ng/L이며, 이 시점에서의 생물 처리조 내의 혼합액의 성상은 이하와 같았다.Following the ninth step, as the tenth step, the pH of the mixed solution in the biological treatment tank was raised to 7. The pressure difference of the immersion membrane was increased from the day after the start of the tenth step and the treatment could not be continued for two days in the same manner as in the ninth step except for increasing the pH of the mixed solution. The TOC concentration of the treated water two hours before stopping the treatment was 910 ng / L, and the properties of the mixed solution in the biological treatment tank at this point were as follows.

[생물 처리조 내의 혼합액][Mixed solution in biological treatment tank]

철함유 비율; MLSS의 19.5 질량％ (철로서)Iron content; 19.5% by mass of MLSS (as iron)

MLSS 농도; 3,660 mg/LMLSS concentration; 3,660 mg / L

MLVSS 농도; 1,720 mg/LMLVSS concentration; 1,720 mg / L

pH; 7pH; 7

[비교예 2][Comparative Example 2]

비교예 2에서는, 수도물(TOC 농도 0.3 mg/L, SS 농도 1 mg/L 이하)을 유기물 함유수로서 처리했다. 비교예 2에서는, 비교예 1 및 실시예 1과 같은 구성의 처리장치를 이용하였다.In Comparative Example 2, tap water (TOC concentration: 0.3 mg / L, SS concentration: 1 mg / L or less) was treated as organic-containing water. In Comparative Example 2, a treatment apparatus having the same structure as Comparative Example 1 and Example 1 was used.

비교예 2에서는, 상기 유기물 함유수에 염화제2철을 3 mg/L의 첨가량으로 첨가해서 3㎥/day의 유량으로 생물 처리조에 공급하였다. 처리수는 처리수관의 도중에 설치한 진공 펌프로 감압하여 침지막을 감압하고 취출하였다. 비교예 2에서는, 처리개시후 곧 침지막의 차압이 상승하기 시작하였고, 실험 개시로부터 10일에 막이 막혀서 처리수를 뽑아낼 수 없게 되었다. 이 시점에서의 처리수의 TOC 농도는 234 ng/L이었고, 조내의 혼합액의 성상은 이하와 같았다.In Comparative Example 2, ferric chloride was added to the organic-substance-containing water in an amount of 3 mg / L and supplied to the biological treatment tank at a flow rate of 3 m 3 / day. The treated water was decompressed by a vacuum pump installed in the middle of the treated water pipe, and the immersion membrane was decompressed and taken out. In Comparative Example 2, the differential pressure of the immersion membrane began to rise immediately after the start of the treatment, and the membrane became clogged after 10 days from the start of the experiment and the treated water could not be extracted. At this point, the TOC concentration of the treated water was 234 ng / L, and the characteristics of the mixed solution in the tank were as follows.

[생물 처리조 내의 혼합액][Mixed solution in biological treatment tank]

철함유 비율; MLSS의 46 질량％ (철로서)Iron content; 46% by mass of MLSS (as iron)

MLSS 농도; 1,160 mg/LMLSS concentration; 1,160 mg / L

MLVSS 농도; 71 mg/LMLVSS concentration; 71 mg / L

pH; 6.8pH; 6.8

[비교예 3][Comparative Example 3]

비교예 2에서 처리수를 뽑아내지 못하게 된 생물 처리조로부터 침지막을 취출하여, 구연산으로 세정하고, 생물 처리조에 다시 침지시켰다. 또한, 생물 처리조에 pH 측정기를 설치하고, 1 질량％ 농도의 황산을 첨가하여 pH를 5.8 ~ 6.2 범위로 유지하였다. 그 외에는 비교예 2와 동일한 조건으로 실험을 수행하였더니, 침지막의 차압은 서서히 상승해서 실험 개시로부터 1개월에 처리수를 뽑아낼 수 없게 되었다. 이 시점에서의 처리수의 TOC 농도는 0.266 mg/L이며, 생물 처리조 내의 혼합액의 성상은 이하와 같았다.In Comparative Example 2, the immersion membrane was taken out from the biological treatment tank where the treated water could not be drained, washed with citric acid, and immersed again in the biological treatment tank. In addition, a pH meter was installed in the biological treatment tank, and the pH was maintained in the range of 5.8 to 6.2 by adding 1 mass% sulfuric acid. Experiments were carried out under the same conditions as those of Comparative Example 2 except that the differential pressure of the immersion membrane was gradually increased and the treated water could not be extracted within one month from the start of the experiment. The TOC concentration of the treated water at this point was 0.266 mg / L, and the properties of the mixed solution in the biological treatment tank were as follows.

[생물 처리조 내의 혼합액][Mixed solution in biological treatment tank]

철함유 비율; MLSS의 49 질량％ (철로서)Iron content; 49% by mass (as iron) of MLSS

MLSS 농도; 1,740 mg/LMLSS concentration; 1,740 mg / L

MLVSS 농도; 49 mg/LMLVSS concentration; 49 mg / L

pH; 5.8 ~ 6.2pH; 5.8 ~ 6.2

[실시예 2][Example 2]

비교예 3에서 처리수를 뽑아내지 못하게 된 생물 처리조로부터 침지막을 취출하여, 구연산으로 세정하고, 생물 처리조에 다시 침지시켰다. 또한, 비교예 3에서 처리한 수도물에 IPA를 2 mg/L 및 인산2암모늄을 N으로 1 mg/L가 되도록 더 첨 가했다. 그 외에는 비교예 3과 동일한 조건으로 실험을 수행하였더니, 1개월에 걸쳐 침지막의 차압상승은 인식되지 않았다. 실시예 2의 실험 개시로부터 1개월 후의 처리수의 TOC 농도는 217 ng/L이며, 생물 처리조 내의 혼합액의 성상은 이하와 같았다.In Comparative Example 3, the immersion membrane was taken out from the biological treatment tank which was unable to extract the treated water, washed with citric acid, and immersed again in the biological treatment tank. Further, the tap water treated in Comparative Example 3 was further added with 2 mg / L of IPA and 2 mg / L of ammonium phosphate so as to be 1 mg / L. Otherwise, the experiment was carried out under the same conditions as in Comparative Example 3, and the increase in the pressure difference of the immersion membrane over one month was not recognized. The TOC concentration of the treated water one month after the start of the experiment of Example 2 was 217 ng / L, and the properties of the mixed solution in the biological treatment tank were as follows.

[생물 처리조 내의 혼합액][Mixed solution in biological treatment tank]

철함유 비율; MLSS의 38 질량％ (철로서)Iron content; 38% by mass of MLSS (as iron)

MLSS 농도; 2,920 mg/LMLSS concentration; 2,920 mg / L

MLVSS 농도; 674 mg/LMLVSS concentration; 674 mg / L

pH; 5.8 ~ 6.2pH; 5.8 ~ 6.2

이상, 생물 처리조의 MLSS에 대한 철염의 비율을 소정 범위로 함으로써, 막의 파울링을 효과적으로 방지하고, 높은 투과 유속으로 처리할 수 있음이 나타났다.As described above, by setting the ratio of the iron salts to the MLSS of the biological treatment tank within a predetermined range, it is possible to effectively prevent the fouling of the membrane and to treat it at a high permeation flux.

본 발명은 유기물 함유수의 처리에 이용할 수 있다.The present invention can be used for the treatment of organic substance-containing water.

도 1은 본 발명에 이용되는 제 1 생물처리장치의 모식도이다.1 is a schematic diagram of a first biological treatment apparatus used in the present invention.

도 2는 본 발명에 이용되는 제 2 생물처리장치의 모식도이다.2 is a schematic diagram of a second biological treatment apparatus used in the present invention.

도 3은 본 발명에 이용되는 제 3 생물처리장치의 모식도이다.3 is a schematic diagram of a third biological treatment apparatus used in the present invention.

<도면의 주요부분에 대한 부호의 설명>Description of the Related Art

1 ~ 3: 생물처리장치1 ~ 3: Biological treatment device

10: 생물 처리조10: biological treatment tank

11: 침지막11: Submerged membrane

12: 철염 첨가수단12: Iron salt addition means

13: pH 조정수단13: pH adjusting means

14: 산기관14:

15: 철염 저장조15: Iron salt storage tank

16: 철염 첨가로16: with iron salt addition

17: pH조정제 저장조17: pH adjusting agent storage tank

18: pH조정제 첨가로18: With the addition of pH adjusting agent

19: 오존 반응조19: ozone reaction tank

Claims (5)

유기물을 포함하는 유기물 함유수를 생물 처리조에 도입해서 활성 슬러지와 혼합하여 생물처리하고, 상기 유기물 함유수와 상기 활성 슬러지가 혼합된 혼합액을 막 분리하는 유기물 함유수의 생물처리방법에 있어서,A method for biological treatment of an organic substance-containing water for introducing an organic substance-containing water containing an organic substance into a biological treatment tank, mixing the activated sludge with a biological treatment, and separating a mixed solution obtained by mixing the organic substance- 상기 생물 처리조 내의 상기 혼합액은, 상기 활성 슬러지 농도에 대한 활성 슬러지 유기성 부유물질의 비인 MLVSS/MLSS가 0.15 이상 0.5 이하로 되도록 조정되고, 철로서의 농도가 상기 활성 슬러지 농도의 10 질량％ 이상 45 질량％ 이하의 비율이 되도록 철염의 첨가량이 조정되고, 동시에, pH가 5 이상 6.5 이하로 조정되어 있는 유기물 함유수의 생물처리방법.Wherein the mixed liquid in the biological treatment tank is adjusted so that MLVSS / MLSS, which is the ratio of the activated sludge organic suspended solids to the activated sludge concentration, is 0.15 or more and 0.5 or less, and the concentration as iron is 10 mass% or more and 45 mass % Or less, and at the same time, the pH is adjusted to 5 or more and 6.5 or less. 제 1 항에 있어서,The method according to claim 1, 상기 생물 처리조 내에 침지시킨 침지막 모듈에 의해 상기 혼합액을 막 분리하는 유기물 함유수의 생물처리방법.Wherein the mixed solution is membrane-separated by an immersion membrane module immersed in the biological treatment tank. 제 1 항 또는 제 2 항에 있어서,3. The method according to claim 1 or 2, 상기 유기물 함유수는 자연수, 수도물, 또는 회수수(回收水) 인 유기물 함유수의 생물처리방법.Wherein the organic substance-containing water is natural water, tap water, or recovered water. 삭제delete 삭제delete
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