KR20050000062A - reactive solidification agent(RSA) for dewatering, detoxification, solidification of sludge and its manufacturing method, and recycling method of solidification of sludge - Google Patents

reactive solidification agent(RSA) for dewatering, detoxification, solidification of sludge and its manufacturing method, and recycling method of solidification of sludge Download PDF

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KR20050000062A
KR20050000062A KR1020030040627A KR20030040627A KR20050000062A KR 20050000062 A KR20050000062 A KR 20050000062A KR 1020030040627 A KR1020030040627 A KR 1020030040627A KR 20030040627 A KR20030040627 A KR 20030040627A KR 20050000062 A KR20050000062 A KR 20050000062A
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sludge
chloride
mixing
reactive
solidifying agent
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KR100550340B1 (en
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고용국
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고용국
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/12Treatment of sludge; Devices therefor by de-watering, drying or thickening
    • C02F11/14Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
    • C02F11/143Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00Treatment of sludge; Devices therefor
    • C02F11/008Sludge treatment by fixation or solidification
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/02Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/08Aluminium compounds, e.g. aluminium hydroxide
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/02Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/10Cements, e.g. Portland cement
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/20Sludge processing
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/20Waste processing or separation

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatment Of Sludge (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

PURPOSE: To provide a reactive solidification agent for solidifying sludge, a method for dewatering, detoxifying and solidifying sludge containing contaminants and having high moisture content using the reactive solidification agent, and a method for recycling solidified sludge obtained by the reactive solidification agent as covering soil and bank soil for waste landfill, riverbed reinforcement, slope reinforcement, soil for housing complex, plant growing soil and pipe line bedding. CONSTITUTION: The method for preparing a reactive solidification agent for preparing solidified sludge(5) by dewatering, detoxifying and solidifying sludge comprises a first mixing process of mixing 19 to 24 wt.% of sodium chloride(NaCl), 25 to 30 wt.% of potassium chloride(KCl) and 14 to 19 wt.% of magnesium chloride(MgCl); a second mixing process of mixing a mixture prepared by the first mixing process with 14 to 19 wt.% of calcium chloride(CaCl2), 1.5 to 2.5 wt.% of ferric chloride(Fe2Cl3) and 4 to 6 wt.% of ammonium chloride(NH4Cl) in such a way that 4 to 6 wt.% of aluminum chloride(Al2Cl3) is additionally added to be mixed with the mixture after mixing calcium chloride(CaCl2) with the mixture if sludge(1) contains a large amount of substances having strong ion exchangeability such as As, CN and the like; a third mixing process of preparing a solidification agent(ECO-CURE)(4) by mixing a mixture prepared by the second mixing process with 0.5 to 1.5 wt.% of carbon(C), 2 to 4 wt.% of citric acid, 5.5 to 8 wt.% of non-inoic surfactant and 2 to 4 wt.% of sodium sulfate(NaSO4); and a fourth mixing process of preparing a reactive solidification agent by injecting the solidification agent that is the mixture prepared by the third mixing process and a reactive material(3) into a mixture, thereby rotationally mixing them in such a mixing ratio that 0.1 to 1.0 kg of the reactive material is mixed with 0.7 to 1.5 kg of the solidification agent.

Description

슬러지를 탈수화 · 무해화 · 고형화 하여 고형화슬러지로 만드는 반응성 고화제 및 그 제조방법과, 반응성 고화제로 처리된 고형화슬러지의 재활용하는 방법{reactive solidification agent(RSA) for dewatering, detoxification, solidification of sludge and its manufacturing method, and recycling method of solidification of sludge}Reactive solidification agent to make sludge dehydrated, detoxified and solidified to make solidified sludge, and a method of manufacturing the same, and a method for recycling solidified sludge treated with reactive solidifying agent (reactive solidification agent (RSA) for dewatering, detoxification, solidification of sludge and its manufacturing method, and recycling method of solidification of sludge}

본 발명은 슬러지를 탈수화 · 무해화 · 고형화 하여 고형화슬러지로 만드는 반응성 고화제 및 그 제조방법과, 반응성 고화제로 처리된 고형화슬러지의 재활용하는 방법에 관한 것으로, 자세하게는 산업공단 및 수처리장 등에서 발생하는 슬러지에 반응성 물질을 혼합하여 슬러지 및 폐기물에 함유된 오염물질을 무해화하고, 고화성 물질을 혼합하여 슬러지 및 폐기물 내에 존재하는 수분을 제거하여 탈수화함과 동시에 단단하게 고형화하여, 이를 폐기물매립장의 일일, 중간 및 최종 복토재 및 제방 성토재로 재활용하거나, 하천의 바닥보강재, 법면보강재, 단지성토재, 식물식생토, 관로베딩(bedding)으로 재활용하는 기술에 관한 것이다.The present invention relates to a reactive solidifying agent for producing sludge by dehydrating, detoxifying and solidifying sludge, and a method for manufacturing the same, and a method for recycling solidified sludge treated with a reactive solidifying agent, and more particularly, in industrial complexes and water treatment plants. Reactive materials are mixed with the sludge produced to make the sludge and contaminants contained in the waste harmless, and mixed with high-density materials to remove the water present in the sludge and the waste to dehydrate and solidify it at the same time. The present invention relates to a technology for recycling into daily, intermediate and final cover soils and embankment soils, or recycled into river floor reinforcement, frontal reinforcement, complex soil material, plant vegetation, and pipe bedding.

슬러지에는 광산슬러지, 제지슬러지, 피혁슬러지, 도금슬러지, 하수슬러지, 상수슬러지, 관로퇴적슬러지, 하천퇴적슬러지, 호소퇴적슬러지, 해안퇴적슬러지 등이 있다.The sludge includes mine sludge, paper sludge, leather sludge, plated sludge, sewage sludge, water purification sludge, pipeline sediment sludge, river sediment sludge, lake sediment sludge, and coastal sludge.

이들은 생산공정 및 처리공정 중에 최종적으로 산출되는 부산물로 매우 함수비가 높고 연약하며 유기물질이나 중금속 등으로 오염되어 있는 경우가 많다.These are by-products that are finally produced during the production and treatment processes. They are very high in water content, fragile and often contaminated with organic materials or heavy metals.

이와 같은 슬러지를 처리하고자 할 경우에는 함수비가 높고 유해물질이 존재하기 때문에 이의 환경적인 및 구조적인 안정을 위하여 무해화, 고형화 및 고정화 작업이 요구된다.In order to treat such sludge, since the water content is high and harmful substances exist, harmlessness, solidification and immobilization work are required for its environmental and structural stability.

현재 국내 슬러지의 대부분은 폐기물매립지에 직매립을 하는 단순처리에 의존하고 있고 일부분 소각처리가 되고 있으며 재활용은 매우 미미한 실정이다.At present, most of domestic sludges rely on simple disposal of landfill directly, partly incinerated, and recycling is very insignificant.

국내의 경우 폐기물관리법의 개정에 의하여 2003년도 후반기부터 슬러지를 매립지에 직매립을 못하고 고화처리, 소각처리 등의 1차 처리를 하여 함수비를 저감시키고 어느 정도 안정화시킨 다음에 매립을 하도록 하고 있다.In Korea, due to the revision of the Waste Management Act, sludge cannot be landfilled directly in landfills since the second half of 2003, and the water treatment is reduced and stabilized to some extent by the first treatment of solidification and incineration.

따라서 이에 대한 대비책이 필요하나 아직까지 이에 대한 뚜렷한 대비책이 강구되지 않은 실정이다.Therefore, a countermeasure is needed, but no clear countermeasure has been taken.

국내 폐기물매립지의 경우 일일복토, 중간복토, 최종복토재로 토사가 사용되고 있으나 이의 채취 및 입수에 매우 어려움을 겪고 있다.In the case of domestic landfills, soil is used as daily cover, intermediate cover, and final cover, but it is very difficult to collect and obtain it.

그리고 하천준설의 경우 하천슬러지의 처리에 매우 골머리를 앓고 있으며 이의 재활용이 매우 저조한 실정이다.In the case of dredging, the river sludge is very troubled and its recycling is very poor.

현재까지의 슬러지 처리는 부분적으로 소각 및 고형화 기술이 적용되고 있다.The sludge treatment to date has been partially applied with incineration and solidification techniques.

현재의 고형화기술은 시멘트, 석회 등의 일반적인 고화제를 사용하거나, 일부 무기물을 함유한 고화제를 사용하는 비교적 단순한 고형화 기술이 개발된 정도이다.The current solidification technique is a relatively simple solidification technique using a general solidifying agent such as cement, lime, or using a solidifying agent containing some inorganic substances.

이들 고화제는 대부분이 슬러지를 단순히 고화원리에 의하여 단단하게 고형화하여 슬러지가 풀리지 않고 결합되도록 하며 슬러지내의 오염물질이 용출이 되지 않도록 불용출화하는 기능을 하게 된다.Most of these solidifying agents solidify the sludge solidly by the solidification principle, so that the sludge is combined without loosening, and functions to insolubilize the contaminants in the sludge so that it does not dissolve.

이는 장기적으로 슬러지내의 오염물질을 함유하게 되어 차후에 만약의 경우 고결성이 저하하게 되면 재용출이 될 수 있는 소지가 있다.This may contain contaminants in the sludge in the long run, which may lead to re-dissolution if the integrity is reduced in the future.

따라서 지금까지 개발된 고형화 기술은 슬러지내에 존재하는 오염물질을 분해시키거나 무해화시키는 기능을 가지지 못하므로 고형화는 시킬 수 있어도 슬러지내의 오염물질을 제거하지 못하여 항상 오염물질의 장기적인 용출 및 확산의 문제점을 가지고 있다.Therefore, the solidification technology developed so far does not have the function of decomposing or harming the contaminants present in the sludge, so that the solidification can not remove the contaminants in the sludge, so there is always the problem of long-term dissolution and diffusion of contaminants. have.

현재까지의 슬러지 재활용기술은 일부 제안된 것도 있기는 하지만 아직까지 실용적으로 상용화하여 적용할 수 있는 기술이 개발된 것이 없는 실정이다.The sludge recycling technology to date has some proposals, but there is no technology that can be commercially applied and applied.

따라서 매년 슬러지 발생량이 증가하고 있는 상황을 고려할 때 재활용재를 대단위적으로 사용할 수 있는 건설 및 환경분야에 대한 슬러지 재활용기술의 개발이 시급히 요구된다.Therefore, considering the situation in which sludge generation is increasing every year, it is urgently required to develop sludge recycling technology in the construction and environment fields where large quantities of recycled materials can be used.

상기와 같은 문제점을 해결하기 위한 본 발명의 목적은 슬러지를 고형화하는 반응성 고화제와, 이를 이용하여 오염물질이 함유된 고함수비의 슬러지를 탈수화 · 무해화 · 고형화 방법과, 이로부터 제공되는 고형화슬러지를 폐기물매립장의 복토재 및 제방성토재, 하천의 바닥보강재, 법면보강재, 단지성토재, 식물식생토, 관로베딩으로 재활용하는 방법을 제공하는데 있다.An object of the present invention for solving the above problems is a reactive solidifying agent for solidifying sludge, a method of dehydrating, detoxifying and solidifying a high water-containing sludge containing contaminants using the same, and the solidification provided therefrom. The present invention provides a method for recycling sludge into cover soil, embankment soil, river bottom reinforcement, frontal reinforcement, complex soil, plant vegetation, and pipeline bedding.

도 1은 본 발명의 기본도인 반응성 고화제를 이용한 슬러지의 처리 개념도,1 is a conceptual diagram of treatment of sludge using a reactive solidifying agent which is a basic diagram of the present invention;

도 2는 일반토사에 반응성 고화제로 처리된 슬러지를 일정한 비율로 혼합한 토사고형화슬러지 혼합토(믹싱혼합토, 적층혼합토)를 나타낸 도면,FIG. 2 is a diagram showing soil solidified sludge mixed soils (mixed mixed soils and laminated mixed soils) in which sludges treated with a reactive solidifying agent in a general soil are mixed at a constant ratio;

도 3은 반응성 고화제로 처리된 슬러지 및 토사고형화슬러지 혼합토를 폐기물매립장의 일일복토재, 중간복토재, 최종복토재 및 제방성토재로 재활용하는 시스템도,3 is a system diagram for recycling sludge mixed with sludge and solidified sludge sludge treated with a reactive solidifying agent into daily cover material, intermediate cover material, final cover material and embankment soil material in a landfill site;

도 4는 반응성 고화제로 처리된 슬러지 및 토사고형화슬러지 혼합토를 하천바닥보강재, 하천법면보강재, 단지성토재, 식물식생토, 관로베딩으로 재활용하는 시스템을 나타낸 도면4 is a view showing a system for recycling sludge mixed with sludge and solidified sludge mixed soil treated with a reactive solidifying agent into a river bottom reinforcement material, a river method cotton reinforcement material, a complex soil material, a plant vegetation soil, and a pipe bedding.

<도면의 주요부분에 대한 부호의 설명><Description of the symbols for the main parts of the drawings>

(1) : 슬러지 (2) : 토사(1): sludge (2): earth and sand

(3) : 반응제 (4) : 고화제(3): Reactant (4): Solidifying Agent

(5) : 고형화슬러지 (6) : 토사고형화슬러지 혼합토(5): solidified sludge (6): soil solidified sludge mixed soil

(7) : 폐기물매립장 (8) : 일일복토재(7): landfill (8): daily cover materials

(9) : 중간복토재 (10) : 최종복토재(9): intermediate cover material (10): final cover material

(11) : 제방 (12) : 하천(11): levee (12): river

(13) : 바닥보강재 (14) : 법면보강재(13): floor reinforcement (14): frontal reinforcement

(15) : 단지성토재 (16) : 식물식생토(15): Complex soil material (16): Plant vegetation

(17) : 관로베딩(17): Pipeline Bedding

상기한 바와 같은 목적을 달성하고 종래의 결점을 제거하기 위한 과제를 수행하는 본 발명은 슬러지에 반응성물질 및 고화제를 혼합하여 오염된 고함수비의 슬러지를 무해화하고 고형화하는 기술을 특징으로 한다.The present invention, which achieves the object as described above and accomplishes a problem for eliminating the conventional drawbacks, is characterized by a technique of mixing a reactive material and a solidifying agent with sludge to make the contaminated high water content sludge harmless and solidify.

즉, 슬러지에 반응성물질을 투여함으로 슬러지내의 오염물질이 화학적으로 분해되어 무해화 되고, 고화제를 투여함으로 슬러지내 수분이 탈수화 되고 및 슬러지내 구성입자가 고형화 된다.That is, by administering a reactive material to the sludge, contaminants in the sludge are chemically decomposed and harmless, and by administering a solidifying agent, the water in the sludge is dehydrated and the constituent particles in the sludge are solidified.

따라서 오염된 고함수비의 슬러지가 본 처리과정을 거침으로 청정하고 견고한 슬러지 고형체가 형성된다.Therefore, contaminated high water content sludge goes through this treatment to form a clean and solid sludge solid.

여기에서, 본 발명의 주요 핵심인 반응성 고화제의 구성성분은 다음과 같다.Here, the components of the reactive hardener which is the main core of the present invention are as follows.

1) 반응성 고화제의 구성성분1) Components of Reactive Solidifying Agent

구성성분Ingredient 구성비율 (%, 중량비)Composition ratio (%, weight ratio) 석탄비산재(fly ash)Fly ash 40∼6040-60 반응제(reactive material)Reactive material 0.1∼1.00.1-1.0 고화제(ECO-CURE)Solidifying Agent (ECO-CURE) 0.7∼1.50.7 to 1.5 보통 포틀란트시멘트Common Portland Cement 나머지(약 40~60)Rest (about 40 ~ 60)

상기 석탄비산재(fly ash)의 역할은 고화제의 포졸란반응을 촉진시켜 .침상결정구조를 치밀하게 하는 것이고, 석탄비산재를 사용하는 이유는 본 기술에서 슬러지의 주요 경화제인 시멘트보다는 기능이 떨어지지만 이와 동일한 기능을 가지고 있으면서 산업부산물이기 때문에 시멘트보다 매우 저렴하기 때문이며, 석탄비산재의 수치한정이유는 40wt% 미만이면 시멘트와의 대체량이 미소하고, 60wt%보다 크면 상대적으로 시멘트량이 줄어 들어 시멘트의 경화기능이 작아지기 때문에 그 수치를 한정하였다.The role of the fly ash (fly ash) is to promote the pozzolanic reaction of the solidifying agent to compact the needle crystal structure, the reason for using the coal fly ash is less functional than the cement which is the main hardener of the sludge in the present technology, but This is because it has the same function and is much cheaper than cement because it is an industrial by-product.The reason for the numerical limitation of coal fly ash is less than 40wt%, and the replacement amount with cement is small. Since it became small, the numerical value was limited.

상기 반응제(reactive material)의 역할은 대상 시료내의 오염물질을 화학적으로 분해하여 무해화 시키는 작용을 하는 것이고, 수치한정이유는 0.1wt% 미만이면 반응제의 오염물질 분해능력이 미약하고, 1.0wt%보다 크면 반응제의 오염물질 분해능력이 충분하기 때문에 그 수치를 한정하였다.The role of the reactive material is to chemically decompose the contaminants in the target sample and to detoxify them.If the numerical limitation is less than 0.1wt%, the decomposability of the contaminants is weak and 1.0wt. If greater than%, the value is limited because the reagent has a sufficient ability to decompose contaminants.

상기 고화제(ECO-CURE, solidification agent or binder)의 역할은 시멘트 및 석탄비산재의 반응성을 증가시키는 것이고, 수치한정이유는 0.7wt% 미만이면 고형화 정도가 떨어지고, 1.5wt%보다 크면 고형화 정도가 증가하기는 하나 크게 증가하지 않기 때문에 그 수치를 한정하였다.The role of the solidifying agent (ECO-CURE, solidification agent or binder) is to increase the reactivity of cement and coal fly ash, the numerical limitation is less than 0.7wt%, the degree of solidification falls, if greater than 1.5wt%, the degree of solidification increases The following values are limited because they do not increase significantly.

상기 보통 포틀란트 시멘트의 역할은 수화반응 및 포졸란반응을 통하여 슬러지를 응결 및 경화함으로 고형화 및 안정화하여 강성을 증진시키고 고형체의 매트릭스를 형성하는 것이고, 구성비율을 약 40∼60%(중량비)로 한 이유는 시멘트가 석탄비산재보다 고가이기 때문에 시멘트를 비산재로 대치하기 위함이며, 수치한정이유는 약 40wt% 미만이면 시멘트의 수화반응 및 포졸란반응이 열악하고, 약 60wt%보다 크면 석탄비산재와의 대체량이 작아지고 또한 시멘트의 수화반응 및 포졸란반응이 충분하기 때문에 그 수치를 한정하였다. 여기에서 보통 포틀란트 시멘트의 함량비는 40∼60%(중량비)로 편의상 설명되나 실제로는 석탄비산재에 반응제, 고화제를 첨가한 나머지의 중량비 조성비율을 가진다.The role of the ordinary portland cement is to solidify and stabilize the sludge by solidifying and curing the sludge through a hydration reaction and a pozzolan reaction to enhance rigidity and to form a matrix of solids, and the composition ratio is about 40 to 60% (weight ratio). The reason is to replace cement with fly ash because cement is more expensive than coal fly ash.The reason for numerical limitation is that the hydration reaction and pozzolanic reaction of cement is poor when it is less than about 40wt%, and when it is higher than about 60wt%, The numerical value was limited because the replacement amount was small and the hydration reaction and pozzolanic reaction of the cement were sufficient. Although the content ratio of the portland cement is usually 40-60% (weight ratio) for convenience, it actually has a weight ratio composition ratio of the remainder of the addition of the reactant and the hardener to the coal fly ash.

2) 반응제의 구성성분2) Components of Reactant

구성성분Ingredient 구성비율 (%, 중량비)Composition ratio (%, weight ratio) 철분iron content 0∼1000-100 제철슬래그Steel Slag 100∼0100 to 0

즉, 상기표와 같이 반응제는 철분 또는 제철슬래그로 이루어진 군중에서 선택된 하나 또는 하나이상을 혼합하여 사용한다.That is, as shown in the above table, the reactants are used by mixing one or more selected from the group consisting of iron or steel slag.

여기에서 철분, 즉 0가 철(Fe0)은 철공소 등지에서 폐기 처리되는 고철을 사용하고, 제철슬래그는 포항제철, 광양제철, 인천제철, 동국제강 등의 제철공장에서 폐기 처리되는 슬래그를 사용한다.Here, iron powder, that is, zero valent iron (Fe 0 ), uses scrap steel that is disposed of in ironworks, etc., and steel slag uses slag that is disposed of in steel mills such as Pohang, Gwangyang, Incheon, and Dongkuk Steel. .

3) 고화제(ECO-CURE)의 구성성분3) Ingredients of ECO-CURE

아래와 같이 11종의 무기성 재료를 혼합하여 고화제를 구성한다.11 kinds of inorganic materials are mixed as follows, and a solidifying agent is comprised.

구성성분Ingredient 화학식Chemical formula 구성비율 (%, 중량비)Composition ratio (%, weight ratio) 염화나트륨Sodium chloride NaClNaCl 19∼2419-24 염화칼륨Potassium chloride KClKCl 25∼3025-30 염화마그네슘Magnesium chloride MgClMgCl 14∼1914-19 염화칼슘Calcium chloride CaCl2 CaCl 2 14∼1914-19 염화알루미늄Aluminum chloride Al2Cl3 Al 2 Cl 3 4∼64 to 6 염화제2철Ferric chloride Fe2Cl3 Fe 2 Cl 3 1.5∼2.51.5 to 2.5 염화암모늄Ammonium chloride NH4ClNH 4 Cl 4∼64 to 6 탄소carbon CC 0.5∼1.50.5 to 1.5 구연산Citric acid C6H8O7 C 6 H 8 O 7 2∼42 to 4 비이온계 계면활성제Nonionic surfactant 5.5∼85.5 to 8 황산나트륨Sodium sulfate NaSO4 NaSO 4 2∼42 to 4

상기 각 성분의 사용이유 및 수치의 한정이유는 다음과 같다.The reason for use of each component and the reason for limitation of numerical values are as follows.

상기 염화나트륨의 사용이유는 고형화 대상 재료내에 모노설페이트라는 염의 생성을 촉진시킴으로 조기강성을 촉진하는 작용이 있기 때문이고, 수치한정이유는 19wt% 미만이면 조기강성의 발현이 늦고, 24wt%보다 크면 조기강성의 발현이 충분하기 때문에 그 수치를 한정하였다.The reason for the use of sodium chloride is to promote the early stiffness by promoting the production of a salt called monosulfate in the solidification target material, the numerical limit is less than 19wt%, the early stiffness is late, if greater than 24wt% early stiffness Since the expression is sufficient, the numerical value was limited.

상기 염화칼륨의 사용이유는 수화반응을 촉진하는 작용이 있기 때문이고, 수치한정이유는 25wt% 미만이면 수화반응이 나쁘고, 30wt%보다 크면 수화반응이 충분하기 때문에 그 수치를 한정하였다.The reason for the use of the potassium chloride is because it has an action to promote the hydration reaction, the numerical value is limited because the hydration reaction is bad when less than 25wt%, the hydration reaction is sufficient when it is greater than 30wt%.

상기 염화마그네슘의 사용이유는 수분흡수를 증진시키는 작용이 있기 때문이고, 수치한정이유는 14wt% 미만이면 수분흡수 능력이 나쁘고, 19wt%보다 크면 수분흡수 능력이 더 이상 크게 커지지 않기 때문에 그 수치를 한정하였다.The reason for the use of magnesium chloride is because it has the effect of promoting the absorption of water, the numerical limit is less than 14wt% water absorption capacity is bad, if greater than 19wt% water absorption capacity is no longer greatly increased because the number is limited It was.

상기 염화칼슘의 사용이유는 발열반응을 촉진하는 작용이 있기 때문이고, 수치한정이유는 14wt% 미만이면 발열반응이 나쁘고, 19wt%보다 크면 발열반응이 크게증가하지 않기 때문에 그 수치를 한정하였다.The reason for the use of the calcium chloride is because it has an action to promote the exothermic reaction, the numerical value is limited because the exothermic reaction is bad when less than 14wt%, the exothermic reaction does not increase significantly when it is greater than 19wt%.

상기 염화알루미늄의 사용이유는 이온교환반응을 하는 작용을 하여 염화알루미늄의 3가 양이온인 Al2이 고화 대상 재료내의 1가 양이온과 교환을 하여 강성을 증진시키는 작용을 하기 때문이고, 수치한정이유는 4wt% 미만이면 이온교환반응에 필요한 3가 양이온이 작게 되고, 6wt%보다 크면 이온교환반응에 필요한 3가 양이온이 과다하기 때문에 그 수치를 한정하였다.The reason for the use of aluminum chloride is that the Al 2, which is a trivalent cation of aluminum chloride, acts as an ion exchange reaction to enhance the rigidity by exchanging monovalent cations in the material to be solidified. If it is less than 4wt%, the trivalent cation required for ion exchange reaction will become small, and if it is larger than 6wt%, the trivalent cation required for ion exchange reaction will be excessive, and the numerical value was limited.

상기 염화제2철의 사용이유는 이온교환반응을 하는 작용을 하여 염화제2철의 3가 양이온인 Fe2이 고화 대상 재료내의 1가 양이온과 교환을 하여 강성을 증진시키는 작용을 하기 때문이고, 수치한정이유는 1.5wt% 미만이면 이온교환반응에 필요한 3가 양이온이 작게 되고, 2.5wt%보다 크면 이온교환반응에 필요한 3가 양이온이 과다하기 때문에 그 수치를 한정하였다.The reason for the use of the ferric chloride is that the effect of the ion exchange reaction to the ferric chloride trivalent cation Fe 2 to exchange the monovalent cation in the material to be solidified to enhance the rigidity, The reason for the numerical limitation is that since the trivalent cation required for the ion exchange reaction becomes smaller at less than 1.5 wt%, the trivalent cation necessary for the ion exchange reaction is exceeded because the numerical value is limited.

상기 염화암모늄의 사용이유는 수화속도를 빠르게 하는 작용이 있기 때문이고, 수치한정이유는 4wt% 미만이면 수화작용이 저하되고, 6wt%보다 크면 수화작용이 충분하기 때문에 그 수치를 한정하였다.The reason for the use of the ammonium chloride is because it has a function to speed up the hydration rate, the numerical value is limited because the hydration action is lowered if less than 4wt%, the hydration action is sufficient if more than 6wt%.

상기 탄소의 사용이유는 탄화반응을 촉진하는 작용이 있기 때문이고, 수치한정이유는 0.5wt% 미만이면 탄화반응이 나쁘고, 1.5wt%보다 크면 탄화반응이 너무 크기 때문에 그 수치를 한정하였다.The reason for the use of the carbon is because it has a function of promoting the carbonization reaction, the numerical limit is less than 0.5wt%, the carbonization reaction is bad, if it is greater than 1.5wt%, the numerical value is limited.

상기 구연산의 사용이유는 각종 반응을 촉진하는 작용이 있기 때문이고, 수치한정이유는 2wt% 미만이면 각종 반응의 촉진이 매우 미소하고, 4wt%보다 크면 각종 반응의 증진이 더 이상 크게 증가하지 않기 때문에 그 수치를 한정하였다.The reason for the use of citric acid is because there is an action to promote various reactions, the numerical limit is less than 2wt%, the promotion of various reactions is very small, if it is more than 4wt%, since the enhancement of various reactions does not increase significantly anymore. The numerical value was limited.

상기 비이온계 계면활성제(non-ionic surfactant)는 폴리옥시에틸렌에테르(polyoxyethylene), 폴리졸베이트(polysolbate) 등을 선택하여 사용하고, 그 사용이유는 흡착, 습윤, 침투, 유화, 분산 등의 계면활성작용에 의해 고화 대상 재료를 세정하거나 오염을 흡착·제거하는 작용이 있기 때문이고, 수치한정이유는 5.5wt% 미만이면 계면활성작용이 미약하고, 8wt%보다 크면 계면활성작용이 크게 증가하지 않고 경제적이지 않기 때문에 그 수치를 한정하였다.The non-ionic surfactant is used by selecting polyoxyethylene, polysolbate, and the like, and the reason for the use is an interface such as adsorption, wetting, penetration, emulsification, and dispersion. This is because there is an action of cleaning the material to be solidified by adsorption or adsorbing and removing contaminants, and the numerical limitation is less than 5.5wt%, the surfactant activity is weak, and if it is more than 8wt%, the surfactant activity does not increase significantly. The figures were limited because they were not economical.

상기 황산나트륨의 사용이유는 황화반응을 하는 작용이 있기 때문이고, 수치한정이유는 2wt% 미만이면 황화반응에 나쁘고, 4wt%보다 크면 황화반응의 촉진이 더 이상 크게 커지지 않기 때문에 그 수치를 한정하였다.The reason for the use of the sodium sulfate is because the action of the sulfidation reaction, the numerical limit is less than 2wt% bad for the sulfidation reaction, if greater than 4wt% because the acceleration of the sulfidation reaction is no longer greatly increased the number.

상기 본 발명의 반응성고화제를 제조하는 방법은 4개의 혼합공정으로 구성된다.The method of preparing the reactive hardener of the present invention comprises four mixing processes.

제1혼합공정은 염화나트륨(NaCl), 염화칼륨(KCl), 염화마그네슘(MgCl)을 상기표의 중량비율로 순서대로 혼합기에 투입하여 회전시키면서 혼합시키는 공정이다.In the first mixing step, sodium chloride (NaCl), potassium chloride (KCl), and magnesium chloride (MgCl) are added to the mixer in order of weight ratio in the above table and mixed while rotating.

제2혼합공정은 제1혼합공정을 거쳐 생성된 혼합물질에 염화칼슘(CaCl2), 염화제2철(Fe2Cl3), 염화암모늄(NH4Cl)4∼6wt%를 상기표의 중량비율로 순서대로 혼합기에 투입하여 회전시키면서 혼합시키는 공정이다. 이때 슬러지 성분중 이온치환성이 강한 물질(예를 들면 As, CN 등)이 많이 함유되어 있으면 염화칼슘(CaCl2)을 혼합한 후에 염화알루미늄(Al2Cl3) 4∼6wt% 더 투입하여 혼합한다.In the second mixing process, 4 to 6 wt% of calcium chloride (CaCl 2 ), ferric chloride (Fe 2 Cl 3 ), and ammonium chloride (NH 4 Cl) are added to the mixture produced through the first mixing process. It is a process of mixing while rotating by putting into a mixer in order. At this time, if the sludge component contains a large amount of ion-exchangeable substances (for example, As, CN, etc.), add 4 to 6 wt% of aluminum chloride (Al 2 Cl 3 ) after mixing calcium chloride (CaCl 2 ). .

제3혼합공정은 제2혼합공정을 거쳐 생성된 혼합물질에 탄소(C), 구연산(citric acid), 비이온계 계면활성제(non-ionic surfactant), 황산나트륨(NaSO4)을 상기표의 중량비율로 순서대로 혼합기에 투입하여 회전시키면서 혼합시키는 공정이다. 제3혼합공정을 통하여 생성된 혼합물질은 고화제(ECO-CURE)가 된다.In the third mixing process, carbon (C), citric acid, non-ionic surfactant, and sodium sulfate (NaSO 4 ) are added to the mixture produced through the second mixing process. It is a process of mixing while rotating by putting into a mixer in order. The mixture produced through the third mixing process becomes an ECO-CURE.

제4혼합공정은 제3혼합공정을 거쳐 생성된 혼합물질인 고화제(ECO-Cure)에 반응제를 고화제 0.7∼1.5kg에 반응제 0.1∼1.0kg의 비율로 혼합기에 투입하여 회전시켜 혼합시키는 공정이다. 제4혼합공정을 통하여 생성된 최종산물인 혼합물질은 반응성 고화제(reactive solidification agent or binder)가 된다.In the fourth mixing process, the reactant is added to the mixer at a ratio of 0.1 to 1.0 kg of the reactant to 0.7 to 1.5 kg of the solidifying agent (ECO-Cure). It is a process to make it. The mixture, the final product produced through the fourth mixing process, becomes a reactive solidification agent or binder.

상기의 방식에 의해 조성된 반응성 고화제는 슬러지 1.0m3 보통포틀란트시멘트 70∼90kg(석탄비산재를 사용하지 않는 경우) 또는 35∼45kg(석탄비산재를 사용하는 경우), 석탄비산재 35∼45kg(보통 포틀란트시멘트를 45∼35kg 사용하는 경우), 반응제 0.1∼1.0kg, 고화제(ECO-CURE) 0.7∼1.5kg(물 1,000ml에 반응성 고화제 0.7∼1.5kg을 용해시켜 용액형으로 사용함, 물에 용해된 고화제 용액은 수용액 상태에서 24시간을 초과하여 사용하면 효력이 저감되기 때문에 수용액 상태에서는 24시간 이내에 사용하는 것이 바람직함)를 투입하여 사용한다.The reactive hardener formed by the above method was 1.0 m of sludge.3Party 70 to 90 kg (if coal fly ash is not used) or 35 to 45 kg (if coal fly ash is used), 35 to 45 kg coal fly ash (usually 45 to 35 kg portland cement), 0.1 ~ 1.0kg of reactant, 0.7 ~ 1.5kg of ECO-CURE (dissolve 0.7 ~ 1.5kg of reactive solidifying agent in 1,000ml of water, and use it as a solution type. If used over time, the effect is reduced, so it is preferable to use within 24 hours in aqueous solution.

이하 본 발명의 실시예인 구성과 그 작용을 첨부도면에 연계시켜 상세히 설명하면 다음과 같다.Hereinafter, the configuration and the operation of the embodiment of the present invention will be described in detail with reference to the accompanying drawings.

도 1은 본 발명의 기본도인 반응성 고화제를 이용한 슬러지의 처리 개념도로서, 고형화슬러지(5)는 슬러지(1)에 반응제(3), 고화제(4), 시멘트, 석탄비산제가 혼합되어 조성된 반응성고화제를 혼합하여 만든다. 반응성고화제의 조성범위는 전술한 바와 같다.1 is a conceptual view of treatment of sludge using a reactive solidifying agent which is a basic diagram of the present invention, and the solidified sludge 5 includes a sludge 1 mixed with a reactant 3, a solidifying agent 4, cement, and a coal scattering agent. It is made by mixing the formed reactive hardener. The composition range of the reactive hardener is as described above.

보다 자세하게 본 발명의 착안점인 고화제에 의한 슬러지내의 오염물질의 이온교환 및 불용출화 메카니즘은 다음과 같다.More specifically, the mechanism of ion exchange and insolubilization of contaminants in sludge by solidifying agent, which is the focus of the present invention, is as follows.

1) 고화제의 화학약품에 존재하는 양이온 Al3+, Fe2+, Mg2+, Ca2+등과 슬러지내에 존재하는 중금속의 오염물질이 이온교환반응을 일으킨다.1) Ion exchange reactions are caused by the cationic Al 3+ , Fe 2+ , Mg 2+ , Ca 2+ and other heavy metal contaminants in the solidifying agent.

2) 고화제에 의하여 슬러지의 입자사이에 에트린가이트(ettringite)의 침상결정구조가 생성되어 슬러지내의 유기물질 및 중금속이 침상결정구조의 간극속에 갇히게 되어 흡착되고 불용출화 된다.2) A solidifying agent forms a needle crystal structure of ettringite between the particles of the sludge, so that organic substances and heavy metals in the sludge are trapped in the gap of the needle crystal structure and are adsorbed and insoluble.

반응성 고화제에 의한 슬러지 고형화 및 슬러지내 오염물질의 무해화 메카니즘은 다음과 같다.The sludge solidification by reactive solidifying agents and the detoxification mechanism of contaminants in the sludge are as follows.

1) TCE, PCE 등의 염화유기오염물은 고화제 내의 반응제에 의한 탈염반응(dehalogenation)에 의하여 무해화된다.1) Chlorinated organic contaminants such as TCE and PCE are harmless by dehalogenation by the reactants in the solidifying agent.

반응제 + RCl + H+→ RH + Cl- Reagents + RCl + H + → RH + Cl -

2) Cr6+등과 같은 중금속은 주로 중금속염(예, 크롬산염 CrO4 2-)의 형태로 존재하게 되는데 고화제 내의 반응제에 의하여 Cr3+로 환원되어 무해화 된다.2) Heavy metals such as Cr 6+ are mainly present in the form of heavy metal salts (eg, chromate CrO 4 2- ), which are reduced to Cr 3+ by the reactants in the solidifying agent and are innocuous.

반응제 + CrO4 2-+ 8H → Cr3++ 4H2OReactant + CrO 4 2- + 8H → Cr 3+ + 4H 2 O

3) 우라늄(U)과 같은 방사성오염물은 고화제 내의 반응제에 의하여 산화침전물로 되어 무해화된다.3) Radioactive contaminants, such as uranium (U), become oxidized precipitates and become harmless by the reactants in the solidifying agent.

반응제 + UO2 2- (aq) UO2(s) Reactant + UO 2 2- (aq) UO 2 (s)

도 2는 반응성 고화제로 처리된 슬러지와 일반토사를 부피비로 90 : 10 ∼10 : 90의 비율로 혼합한 토사고형화슬러지 혼합토(믹싱혼합토, 적층혼합토)를 나타낸 도면인데, 본 발명은 또한 혼합장비를 이용하여 토사(2)와 고형화슬러지(5)를 전체적으로 혼합하는 믹싱혼합토방식과 일반토사와 고형화슬러지를 층상으로 교번하여 혼합하는 적층혼합토방식으로 구분된다.Figure 2 is a diagram showing the soil solidified sludge mixed soil (mixing mixed soil, laminated mixed soil) mixed with sludge treated with a reactive solidifying agent in a ratio of 90: 10 to 10: 90 by volume ratio, the present invention is also a mixing equipment It is divided into a mixed mixed soil method for mixing the soil (2) and the solidified sludge (5) as a whole, and a laminated mixed soil method for mixing the mixed soil and solidified sludge alternately in layers.

토사고형화슬러지 혼합토(6)는 재활용시 고형화슬러지(5)만을 사용하기에 재질기준이 부족한 경우에 토사(2)와 부피비로 90 : 10 ∼ 10 : 90의 비율로 혼합하여 양질의 재료를 만들고자 하는 경우에 적용한다.Soil solidified sludge mixed soil (6) is to use the solidified sludge (5) when recycling, when the material standard is insufficient, to mix the earth and sand (2) in the ratio of 90:10 to 10:90 by volume ratio to make a high quality material Applies to the case.

상기에서, 믹싱혼합토방식은 반응성 고화제로 처리된 고형화슬러지(5)와 일반토사(2)를 부피비로 90 : 10 ∼ 10 : 90으로 혼합하는 것이고,In the above, the mixing mixed soil method is to mix the solidified sludge (5) and the general earth (2) treated with a reactive solidifying agent in a volume ratio of 90:10 to 10:90,

적층혼합토방식은 일반토사(2)와 반응성 고화제로 처리된 고형화슬러지(5)를 부피비로 일반토사(2) 10∼90을 층상으로 포설하고 난 다음에 반응성 고화제로 처리된 고형화슬러지(5) 90∼10을 층상으로 포설하여 이를 반복적으로 교번하여 적층으로 포설하는 것이다.In the laminated mixed soil method, the solidified sludge (5) treated with the general soil (2) and the reactive solidifying agent (5) was laid in layers by volume in the general soil (2), and then the solidified sludge treated with the reactive solidifying agent (5). ) 90 ~ 10 are laid in layers and they are alternately alternately laid in layers.

도 3은 반응성 고화제로 처리된 고형화슬러지(5) 및 토사고형화슬러지 혼합토(6)를 폐기물매립장의 일일복토재, 중간복토재, 최종복토재 및 제방성토재로 재활용하는 시스템을 나타낸 것으로, 고형화슬러지(5) 및 토사고형화슬러지 혼합토(6)를 폐기물매립장에서 폐기물매립 후 매일 실시하는 일일복토재, 폐기물매립이 7일간 정지되는 경우에 실시하는 중간복토재, 폐기물매립 종료 후 실시하는 최종복토재로 사용하거나 매립장내에 조성되는 소제방의 성토재료로 사용하여 시공하면 된다.FIG. 3 shows a system for recycling solidified sludge (5) and soil solidified sludge mixed soil (6) treated with a reactive solidifying agent into daily cover material, intermediate cover material, final cover material and embankment soil in a landfill, and solidified sludge (5). And the earth and sand solidified sludge mixed soil (6) is used as daily cover material that is carried out every day after landfilling in the landfill, intermediate cover material that is carried out when the landfill is stopped for 7 days, and as final cover material which is carried out after the end of landfill, or It can be used as a fill material for small banks.

여기에서, 반응성 고화제로 처리된 고형화슬러지(5) 및 토사고형화슬러지 혼합토(6)의 제원은 일일복토재는 두께 15cm, 투수계수 1×10-5cm/sec 정도이고, 중간복토재는 두께 30cm, 투수계수 1×10-5cm/sec 정도이며, 최종복토재는 두께 60cm, 투수계수 1×10-6cm/sec 이하가 된다.Here, the specifications of the solidified sludge (5) and the soil solidified sludge mixed soil (6) treated with a reactive solidifying agent is about 15cm thick daily covering material, 1 × 10 -5 cm / sec permeability, the intermediate cover material is 30cm thick, The permeability coefficient is about 1 × 10 -5 cm / sec, and the final covering material has a thickness of 60 cm and a permeability coefficient of 1 × 10 -6 cm / sec or less.

도 4는 반응성 고화제로 처리된 고형화슬러지(5) 및 토사고형화슬러지 혼합토(6)를 하천의 바닥보강재, 법면보강재, 단지성토재, 식물식생토로 재활용하는 시스템을 나타낸 것으로, 하천슬러지를 주변에서 바로 재활용하고자 하는 경우 하천슬러지를 고형화하거나 고형화슬러지를 토사와 혼합하여 하천의 바닥보강재, 법면보강재 및 하천주변의 단지성토재, 식물식생토, 관로베딩으로 재활용하면 간편하게 시공된다.4 shows a system for recycling solidified sludge (5) and soil solidified sludge mixed soil (6) treated with a reactive solidifying agent into a bottom reinforcement, a surface reinforcement, a complex soil material, and a plant vegetation soil in a stream. If you want to recycle, solidify the stream sludge or mix the solidification sludge with soil and recycle it to the bottom reinforcement, the surface reinforcement and the complex soil material around the river, plant vegetation, and pipeline bedding.

미설명부호 7은 폐기물매립장, 8은 일일복토재, 9는 중간복토재, 10은 최종복토재, 11은 제방, 12는 하천, 13은 바닥보강재, 14는 법면보강재, 15는 단지성토재, 16은 식물식생토, 17은 관로베딩이다.Unexplained code 7 is landfill, 8 is daily cover material, 9 is intermediate cover material, 10 is final cover material, 11 is levee, 12 is river, 13 is floor reinforcement material, 14 is reinforcement material, 15 is complex soil material, 16 is plant vegetation. Sat, 17 is pipe bedding.

이하 본 발명의 바람직한 실시예이다.Hereinafter is a preferred embodiment of the present invention.

(실시예 1)(Example 1)

실시예의 하나로 고형화슬러지를 폐기물매립지의 복토재로 사용하는 방안을 보여준다.One example shows the use of solidified sludge as cover material for landfills.

현재 폐기물매립지에서 복토재는 일반토사를 사용하고 있는데 이는 주변 산지에서의 채취에 따른 자연파괴, 주변지역에서의 반입물 감소 및 반입의 어려움, 주변 공사장에서의 건설토사 감소 및 원거리 운송 등에 의하여 구입에 많은 문제점이 있으며, 대체 복토재의 개발이 시급한 상황이다. 현재 슬러지는 폐기물매립지내에 단순 매립되어 매립지의 매립용량을 감소시키고 있으므로 이를 적정하게 처리함으로 일반토사와 유사한 기능을 가지게 하여 매립지의 복토재로 재활용하게 된다면 매립지 매립용량의 증가 및 일반토사의 구입비용 절감 등의 이익을 얻게 된다.At the present time, landfill materials are generally used in landfills, which are difficult to purchase due to natural destruction due to harvesting from surrounding mountains, difficulty in importing and bringing in from surrounding areas, reduction of construction soil at nearby construction sites, and long distance transportation. There is a problem, and the development of alternative cover material is urgently needed. At present, sludge is simply landfilled in the landfill to reduce the landfill capacity of landfill, so if it is properly treated, it will have similar function to that of general soil, and if it is recycled as landfill material of landfill, it will increase landfill capacity and reduce the purchase cost of general soil. You will get a profit.

고형화슬러지를 폐기물매립지의 복토재로 사용하는 경우에는 먼저 고화제(ECO-CURE) 1.0kg과 반응제 0.5kg을 혼합기에 투입하여 혼합시켜 반응성 고화제를 만든다.In the case of using the solidified sludge as a cover material of the landfill, first, 1.0 kg of the ECO-CURE and 0.5 kg of the reactant are added to the mixer to make a reactive solidifying agent.

다음에 물 1,000ml에 반응성 고화제 1.0kg을 용해시켜 수용성 반응성 고화용액을 만든다.Next, 1.0 kg of a reactive solidifying agent is dissolved in 1,000 ml of water to form a water-soluble reactive solidifying solution.

다음에 슬러지 1.0m3당 보통포틀란트시멘트 40kg, 석탄비산재 40kg, 수용성 반응성 고화용액 1,000ml을 혼합한다.Next, 40 kg of ordinary portant cement, 40 kg of coal fly ash and 1,000 ml of water-soluble reactive solidifying solution are mixed per 1.0 m 3 of sludge.

여기에서 혼합은 1) 배치플랜트(batch plant)의 혼합기에 투입하여 혼합하거나 2) 포크레인 등의 교반기를 사용하여 혼합시킨다.In this case, the mixing is carried out by 1) mixing the batch plant (batch plant) by mixing or 2) mixing using a stirrer such as a fork crane.

이와 같은 과정을 거쳐 당초슬러지는 반응형고형화슬러지가 되어 당초슬러지내의 오염물질 제거, 일축압축강도 약 5.0kg/cm2, 투수계수 약 1×10-6cm/sec 정도가 되는 특성을 가짐으로 일반토사와 유사하거나 양호한 특성을 가지게 된다.Through this process, the original sludge becomes a reactive solidified sludge to remove contaminants in the original sludge, its uniaxial compressive strength is about 5.0kg / cm 2 , and the permeability coefficient is about 1 × 10 -6 cm / sec. It will have similar or better characteristics to earth and sand.

이와 같은 특성을 가진 고형화슬러지를 폐기물매립지에서 매립된 폐기물 상부에 일일복토재 15cm, 중간복토재 30cm 및 최종복토재 60cm로 포설하여 일반토사의 대용으로 사용한다.Solidified sludge with such characteristics is installed on the top of the landfilled waste in landfill with 15cm of daily cover material, 30cm of intermediate cover material and 60cm of final cover material to be used as a substitute for general soil.

(실시예 2)(Example 2)

실시예의 또 다른 하나로 고형화슬러지를 하천의 바닥 및 법면 보강재로 사용하는 방안을 보여준다.As another example, the method of using the solidified sludge as the bottom and surface reinforcement of the stream is shown.

현재 국내의 하천에는 바닥에 하천슬러지가 다량으로 침적 및 누적되어 있어 하천수의 오염, 하천 생태계 파손, 물고기 생육 저해, 하천 통수단면적의 저감으로 인한 하천범람 및 제방붕괴 원인제공 등의 문제점을 안고 있다. 현재 일부 하천에서 하천침전슬러지를 준설하고 있으나 주로 원거리로 운송하여 매립이나 투기를 하고 있는 실정이다. 따라서 이를 적정하게 처리함으로 현지에서 재활용하게 된다면 처리비용 및 운송비용 절감 등의 이익을 얻게 된다.At present, domestic sludge has accumulated and accumulated a large amount of river sludge on the bottom, which causes problems such as pollution of river water, damage to river ecosystem, inhibition of fish growth, and the cause of river flood and dike collapse due to reduction of river passage area. Currently, some rivers are dredging sedimentary sludge, but they are mainly transported over long distances to landfill or dump. Therefore, if it is properly processed and recycled locally, it will benefit from the reduction of processing cost and transportation cost.

고형화슬러지를 하천의 바닥 및 법면 보강재로 사용하는 경우에는 먼저 고화제(ECO-CURE) 1.2kg과 반응제 0.5kg을 혼합기에 투입하여 혼합시켜 반응성 고화제를 만든다.In the case of using the solidified sludge as the bottom and the surface reinforcement of the stream, 1.2 kg of the ECO-CURE and 0.5 kg of the reactant are added to the mixer to make a reactive solidifier.

다음에 물 1,000ml에 반응성 고화제 1.2kg을 용해시켜 수용성 반응성 고화용액을 만든다.Next, 1.2 kg of a reactive solidifying agent was dissolved in 1,000 ml of water to form a water-soluble reactive solidifying solution.

다음에 하천슬러지 1.0m3당 보통포틀란트시멘트 100kg, 수용성 반응성 고화용액 1,000ml을 혼합한다.Next, 100 kg of ordinary portant cement and 1,000 ml of a water-soluble reactive solidifying solution are mixed per 1.0 m 3 of river sludge.

여기에서 혼합은 1) 배치플랜트(batch plant)의 혼합기에 투입하여 혼합하거나 2) 포크레인 등의 교반기를 사용하여 혼합시킨다.In this case, the mixing is carried out by 1) mixing the batch plant (batch plant) by mixing or 2) mixing using a stirrer such as a fork crane.

이와 같은 과정을 거쳐 당초슬러지는 반응형고형화슬러지가 되어 당초슬러지내의 중금속 등 오염물질 제거, 일축압축강도 10.0kg/cm2이상, 투수계수 1×10-7m/sec 이하가 되는 특성을 가진다.Through this process, the original sludge becomes a reactive solidified sludge, and has the characteristics of removing contaminants such as heavy metals in the original sludge, uniaxial compressive strength of 10.0kg / cm 2 or more, and permeability coefficient of 1 × 10 -7 m / sec or less.

이와 같은 특성을 가진 고형화슬러지를 하천의 바닥 및 법면에 30∼100cm의 두께로 포설하고 다짐하여 유수에 의한 침식 및 세굴 보강재로 사용한다.Solidified sludge having such characteristics is laid on the bottom and the surface of the river with a thickness of 30-100 cm and compacted to be used as erosion and scour reinforcement by running water.

본 발명은 상술한 특정의 바람직한 실시예에 한정되지 아니하며, 청구범위에서 청구하는 본 발명의 요지를 벗어남이 없이 당해 발명이 속하는 기술분야에서 통상의 지식을 가진 자라면 누구든지 다양한 변형실시가 가능한 것은 물론이고, 그와 같은 변경은 청구범위 기재의 범위 내에 있게 된다.The present invention is not limited to the above-described specific preferred embodiments, and various modifications can be made by any person having ordinary skill in the art without departing from the gist of the present invention claimed in the claims. Of course, such changes will fall within the scope of the claims.

상기와 같이 이루어지는 본 발명은 반응성 고화제를 이용하여 슬러지를 탈수화, 무해화, 고형화하여 다음과 같은 효과를 얻을 수 있다.The present invention made as described above can be obtained by dehydrating, detoxifying, solidifying the sludge by using a reactive solidifying agent.

첫째, 고화제를 이용하여 슬러지를 탈수화 및 고형화하여 1차 처리함으로 고함수비이고 연약한 슬러지를 건조하고 단단하게 함으로서 슬러지의 운반 및 이동을 용이하게 하고, 1차 처리 후 직매립하여야 하는 기준을 만족시키게 하며, 슬러지를 건설 및 환경분야에서 재활용할 수 있는 재료를 제공한다.First, the sludge is dehydrated and solidified using a solidifying agent to facilitate the transport and movement of the sludge by drying and hardening the sludge with a high water content ratio and satisfying the criteria to be directly buried after the primary treatment. To provide materials that can be recycled in the construction and environment sectors.

둘째, 고화제내에 함유된 반응성물질에 의하여 슬러지내에 존재하는 오염물질을 분해, 환원, 침전, 이온교환, 흡착하여 무해화 및 불용출화 함으로서 오염된 슬러지를 청정의 슬러지로 변환하게 한다.Second, the pollutants in the sludge are decomposed, reduced, precipitated, ion exchanged and adsorbed by the reactive materials contained in the solidifying agent to be detoxified and insoluble to convert the contaminated sludge into clean sludge.

셋째, 반응성 고화제로 처리된 슬러지를 일반토사와 90 : 10 ∼ 10 : 90의 부피 비율로 혼합하여 토사고형화슬러지 혼합토를 만듬으로 슬러지를 일반토사화 및 대체토사화 하여 건설재료난을 해소하는데 기여한다.Third, the sludge treated with reactive solidifying agent is mixed with general soil in the volume ratio of 90: 10 ~ 10: 90 to contribute to resolving the construction material shortage by making the soil to be general soil and alternative soil by making the soil mixed with solidified sludge. do.

넷째, 고형화슬러지 및 토사고형화슬러지 혼합토를 폐기물매립장의 복토재 및 제방성토재, 하천의 바닥보강재, 법면보강재, 단지성토재, 식물식생토로 재활용함으로서 경제적이고 친환경적인 재료를 얻고 슬러지의 재활용을 촉진하는 계기를 마련한다.Fourth, by recycling solidified sludge and soil solidified sludge mixed soil into cover soil and embankment soil of landfill, bottom reinforcement material of river, legal reinforcement material, complex soil material, plant vegetation soil, obtain economic and eco-friendly materials and promote the recycling of sludge. do.

이상과 같이 본 발명은 슬러지내의 오염물질을 무해화하고 견고하게 고형화하여 슬러지의 운반 및 직매립, 오염 슬러지의 청정 슬러지 전환, 슬러지의 건설 및 환경 재료로의 재활용을 가능하게 해준다는 장점을 가진 유용한 발명으로 산업상의 이용이 크게 기대되는 발명인 것이다.As described above, the present invention is useful to have the advantage of making harmless and solidifying the contaminants in the sludge so as to transport and landfill the sludge, convert the sludge to clean sludge, construct the sludge and recycle it to environmental materials. It is an invention which industrial use is expected largely by invention.

Claims (8)

슬러지를 고화하는 고화제에 있어서,In the solidifying agent to solidify the sludge, 석탄비산재 60∼40wt%와 반응제 0.1∼1.0wt%와 고화제(ECO-CURE) 0.7∼1.5wt%와 나머지는 보통포틀란트시멘트로 조성한 것을 특징으로 하는 슬러지를 탈수화 · 무해화 · 고형화 하여 고형화슬러지로 만드는 반응성 고화제.Dehydration, decontamination and solidification of sludge characterized by 60 to 40 wt% of coal fly ash, 0.1 to 1.0 wt% of reactant, 0.7 to 1.5 wt% of solidifying agent (ECO-CURE), and the remainder of ordinary portant cement Reactive solidifying agent to solidify the sludge. 제 1항에 있어서,The method of claim 1, 상기 반응제는 철분, 제철슬래그로 이루어진 군중에서 선택된 하나 또는 하나 이상을 혼합조성한 것을 특징으로 하는 슬러지를 탈수화 · 무해화 · 고형화 하여 고형화슬러지로 만드는 반응성 고화제.The reactive agent is a reactive solidifying agent for dehydrating, detoxifying and solidifying the sludge to be solidified sludge, characterized in that a mixture of one or more selected from the group consisting of iron, steel slag. 제 1항에 있어서,The method of claim 1, 상기 고화제(ECO-CURE)는 염화나트륨19∼24wt%와 염화칼륨25∼30wt%와 염화마그네슘14∼19wt%와, 염화칼슘14∼19wt%와 염화알루미늄4∼6wt%와 염화제2철1.5∼2.5wt%와 염화암모늄4∼6wt%와 탄소0.5∼1.5wt%와 구연산2∼4wt%와 비이온계 계면활성제5.5∼8wt%와 황산나트륨2∼4wt%로 조성된 것을 특징으로 하는 슬러지를 탈수화 · 무해화 · 고형화 하여 고형화슬러지로 만드는 반응성 고화제.The solidifying agent (ECO-CURE) is sodium chloride 19-24wt%, potassium chloride 25-30wt%, magnesium chloride 14-19wt%, calcium chloride 14-19wt%, aluminum chloride 4-6wt% and ferric chloride 1.5-2.5wt %, Ammonium chloride 4-6 wt%, carbon 0.5-1.5 wt%, citric acid 2-4 wt%, nonionic surfactant 5.5-8 wt% and sodium sulfate 2-4 wt% Reactive solidifying agent that solidifies and solidifies into solidified sludge. 염화나트륨(NaCl)19∼24wt%, 염화칼륨(KCl)25∼30wt%, 염화마그네슘(MgCl)14∼19wt%을 혼합시키는 제1혼합공정과,A first mixing step of mixing 19 to 24 wt% of sodium chloride (NaCl), 25 to 30 wt% of potassium chloride (KCl), and 14 to 19 wt% of magnesium chloride (MgCl), 상기 제1혼합공정을 거쳐 생성된 혼합물질에 염화칼슘(CaCl2)14∼19wt%, 염화제2철(Fe2Cl3)1.5∼2.5wt%, 염화암모늄(NH4Cl)4∼6wt%를 혼합시키되, 슬러지 성분중 이온치환성이 강한 물질(예를 들면 As, CN 등)이 많이 함유되어 있으면 염화칼슘(CaCl2)을 혼합한 후에 염화알루미늄(Al2Cl3) 4∼6wt% 더 투입하여 혼합하는 제2혼합공정과,14 to 19 wt% of calcium chloride (CaCl 2 ), 1.5 to 2.5 wt% of ferric chloride (Fe 2 Cl 3 ), and 4 to 6 wt% of ammonium chloride (NH 4 Cl) were added to the mixture produced through the first mixing process. If the sludge component contains a large amount of ion exchangeable substances (eg, As, CN, etc.), add 4 to 6 wt% of aluminum chloride (Al 2 Cl 3 ) after mixing with calcium chloride (CaCl 2 ). A second mixing step of mixing, 상기 제2혼합공정을 거쳐 생성된 혼합물질에 탄소(C)0.5∼1.5wt%, 구연산(citric acid)2∼4wt%, 비이온계 계면활성제(non-ionic surfactant)5.5∼8wt%, 황산나트륨(NaSO4)2∼4wt%을 혼합시켜 고화제(ECO-CURE)를 만드는 제3혼합공정과,0.5 to 1.5 wt% of carbon (C), 2 to 4 wt% of citric acid, 5.5 to 8 wt% of non-ionic surfactant, sodium sulfate ( A third mixing process of mixing NaSO 4 ) 2-4wt% to form a hardening agent (ECO-CURE), 상기 제3혼합공정을 거쳐 생성된 혼합물질인 고화제(ECO-Cure)에 반응제를 고화제 0.7∼1.5kg에 반응제 0.1∼1.0kg의 비율로 혼합기에 투입하여 회전시켜 혼합시켜 반응성 고화제(reactive solidification agent or binder)를 제조하는 제4혼합공정으로 이루어지는 것을 특징으로 하는 슬러지를 탈수화 · 무해화 · 고형화 하여 고형화슬러지로 만드는 반응성 고화제의 제조방법.The reactive agent is added to the mixture of the solidifying agent (ECO-Cure), which is a mixture produced through the third mixing process, in a ratio of 0.7 to 1.5 kg of the solidifying agent, at a ratio of 0.1 to 1.0 kg of the reactant, and then mixed by rotation. A process for producing a reactive solidifying agent which makes a sludge dehydrated, harmlessed and solidified by a fourth mixing process for producing a reactive solidification agent or binder. 슬러지 1.0m3에 반응성 고화제 70∼90kg을 첨가하여, 슬러지를 단단하게 고형화하여 불용출화하는 단계와, 슬러지내의 유기화합오염물, 중금속, 방사성물질을 제거, 무해화하는 단계로 이루어지되,70 to 90 kg of a reactive solidifying agent is added to sludge 1.0 m 3 to solidify the sludge and insoluble to dissolve the sludge, and to remove and harm the organic compound contaminants, heavy metals and radioactive substances in the sludge. 상기 반응성 고화제는 석탄비산재 60∼40wt%와 반응제 0.1∼1.0wt%와 고화제(ECO-CURE) 0.7∼1.5wt%와 나머지는 보통포틀란트시멘트로 조성하되,The reactive solidifying agent is composed of 60 to 40 wt% of coal fly ash, 0.1 to 1.0 wt% of reactant, 0.7 to 1.5 wt% of hardening agent (ECO-CURE), and the remainder of ordinary portant cement. 상기 반응제는 철분, 제철슬래그로 이루어진 군중에서 선택된 하나 또는 하나 이상을 혼합조성한 것을 사용하고,The reactant is a mixture of one or more selected from the group consisting of iron and steel slag, and using 상기 고화제(ECO-CURE)는 염화나트륨19∼24wt%와 염화칼륨25∼30wt%와 염화마그네슘14∼19wt%와, 염화칼슘14∼19wt%와 염화알루미늄4∼6wt%와 염화제2철1.5∼2.5wt%와 염화암모늄4∼6wt%와 탄소0.5∼1.5wt%와 구연산2∼4wt%와 비이온계 계면활성제5.5∼8wt%와 황산나트륨2∼4wt%로 조성된 것을 사용하며,The solidifying agent (ECO-CURE) is sodium chloride 19-24wt%, potassium chloride 25-30wt%, magnesium chloride 14-19wt%, calcium chloride 14-19wt%, aluminum chloride 4-6wt% and ferric chloride 1.5-2.5wt %, 4-6 wt% ammonium chloride, 0.5-1.5 wt% carbon, 2-4 wt% citric acid, 5.5-8 wt% nonionic surfactant, and 2-4 wt% sodium sulfate. 상기 불용출화하는 단계는 상기 고화제에 존재하는 양이온 Al3+, Fe2+, Mg2+, Ca2+등과 슬러지내에 존재하는 중금속의 오염물질이 이온교환반응을 일으켜 고화제에 의하여 슬러지의 입자사이에 에트린가이트(ettringite)의 침상결정구조가 생성되어 슬러지내의 유기물질 및 중금속이 침상결정구조의 간극속에 갇히게 되어 흡착되고 불용출화 되는 단계로 이루어지고,The step of insolubilizing the particles of the sludge by the solidifying agent is a contaminant of the heavy metals present in the sludge such as Al 3+ , Fe 2+ , Mg 2+ , Ca 2+, etc. The needle crystal structure of ettringite is formed between the organic material and the heavy metal in the sludge, trapped in the gap between the needle crystal structure, and is adsorbed and insoluble. 상기 슬러지내의 유기화합오염물, 중금속, 방사성물질을 제거, 무해화하는 단계는Removing the organic compound contaminants, heavy metals, radioactive materials in the sludge, harmless 1) TCE, PCE 등의 염화유기오염물은 고화제 내의 반응제에 의한 탈염반응(dehalogenation)에 의하여 무해화 되도록 반응식 [ 반응제 + RCl + H+→ RH + Cl-]을 거치게 하고,Subjected to, and, - 1) of chlorinated organic contaminants TCE, PCE, etc. Scheme [reactant + RCl + H + → RH + Cl] so that detoxification by dechlorination reaction (dehalogenation) by the reaction in the first agent 2) 중금속염(예, 크롬산염 CrO4 2-)의 형태로 존재하는 Cr6+등과 같은 중금속은 고화제 내의 반응제에 의하여 Cr3+로 환원되어 무해화 되도록 반응식 [ 반응제 + CrO4 2-+ 8H → Cr3++ 4H2O]을 거치게 하고,2) heavy metal salt (e.g., chromate CrO heavy metals such as Cr 6+ existing in the form of four 2) scheme is to screen and harmless is reduced to Cr 3+ by reaction in the first agent [reactant + CrO 4 2 - + 8H → Cr 3+ + 4H 2 O] 3) 우라늄(U)과 같은 방사성오염물은 고화제 내의 반응제에 의하여 산화침전물로 되어 무해화되도록 반응식 [반응제 + UO2 2- (aq) → UO2(s)]을 거쳐 처리하는 방법을 특징으로 하는 슬러지를 탈수화 · 무해화 · 고형화하여 고형화슬러지로 만드는 방법.3) Radioactive contaminants, such as uranium (U), become oxidized precipitates by the reactants in the solidifying agent so that they are harmless.2 2- (aq) → UO2 (s)] Dehydration, detoxification, and solidification of sludge characterized by the method of treatment to make a solidified sludge. 석탄비산재 60∼40wt%와 반응제 0.1∼1.0wt%와 고화제(ECO-CURE) 0.7∼1.5wt%와 나머지는 보통포틀란트시멘트로 조성하되; 반응제는 철분, 제철슬래그로 이루어진 군중에서 선택된 하나 또는 하나 이상을 혼합조성되고, 고화제(ECO-CURE)는 염화나트륨19∼24wt%와 염화칼륨25∼30wt%와 염화마그네슘14∼19wt%와, 염화칼슘14∼19wt%와 염화알루미늄4∼6wt%와 염화제2철1.5∼2.5wt%와 염화암모늄4∼6wt%와 탄소0.5∼1.5wt%와 구연산2∼4wt%와 비이온계 계면활성제5.5∼8wt%와 황산나트륨2∼4wt%로 조성된 반응성 고화제를 슬러지에 투입하여 생성된 고형화 슬러지를 폐기물매립장의 일일복토재, 중간복토재, 최종복토재 및 제방성토재, 하천의 바닥보강재, 법면보강재, 단지성토재, 식물식생토, 관로베딩 등으로 재활용하는 방법을 특징으로 하는 반응성 고화제로 처리된 고형화슬러지의 재활용하는 방법.60 to 40 wt% of coal fly ash, 0.1 to 1.0 wt% of reactant, 0.7 to 1.5 wt% of hardening agent (ECO-CURE), and the rest are composed of ordinary portant cement; The reactants are mixed with one or more selected from the group consisting of iron and steel slag, and the solidifying agent (ECO-CURE) is composed of 19 to 24 wt% sodium chloride, 25 to 30 wt% potassium chloride, 14 to 19 wt% magnesium chloride, and calcium chloride. 14-19 wt%, 4-6 wt% aluminum chloride, 1.5-2.5 wt% ferric chloride, 4-6 wt% ammonium chloride, 0.5-1.5 wt% carbon, 2-4 wt% citric acid, 5.5-8 wt% nonionic surfactant Solidified sludge produced by adding reactive solidifying agent composed of% and 2-4 wt% sodium sulfate to the sludge, daily cover material, intermediate cover material, final cover material and embankment soil, bottom reinforcement material of river, reinforcement material, complex soil material, plant A method of recycling solidified sludge treated with reactive solidifying agent, characterized by recycling by vegetation soil, pipe bedding or the like. 제 6항에 있어서,The method of claim 6, 상기 고형화 슬러지를 폐기물매립장의 일일복토재, 중간복토재, 최종복토재 및 제방성토재, 하천의 바닥보강재, 법면보강재, 단지성토재, 식물식생토, 관로베딩으로 재활용시 고형화 슬러지를 일반토사와 부피비로 90 : 10 ∼ 10 : 90의 비율로 혼합하여 토사고형화슬러지 혼합토를 조성하는 방법을 특징으로 하는 반응성 고화제로 처리된 고형화슬러지의 재활용하는 방법.90: 10 A method for recycling solidified sludge treated with a reactive solidifying agent, characterized by mixing at a ratio of 10 to 90 to form a mixed soil solidified sludge. 제 7항에 있어서,The method of claim 7, wherein 상기 고형화 슬러지와 일반토사를 부피비로 90 : 10 ∼ 10 : 90으로 혼합시전체적으로 혼합하는 믹싱혼합토방식 또는 일반토사와 고형화슬러지를 층상으로 교번하여 혼합하는 적층혼합토방식 중에서 선택된 하나로 혼합하는 방법을 특징으로 하는 반응성 고화제로 처리된 고형화슬러지의 재활용하는 방법.Characterized in that the mixture of the solidified sludge and the general soil in a volume ratio of 90: 10 to 10: 90 by mixing one of the mixed mixed soil method of mixing as a whole, or a mixed mixed soil method of mixing by mixing the general soil and the solidified sludge in layers. A method of recycling solidified sludge treated with a reactive solidifying agent.
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KR100812828B1 (en) * 2007-04-24 2008-03-12 임재삼 Solidifying agent for sewage or wastewater sludge and covering material for waste reclamation land prepared using this
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KR100812828B1 (en) * 2007-04-24 2008-03-12 임재삼 Solidifying agent for sewage or wastewater sludge and covering material for waste reclamation land prepared using this
KR100936674B1 (en) * 2008-06-03 2010-01-13 (주)포스벨엔지니어링 Composite reactive solidifying material and underground composite reactive water-proofing barrier using it
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