KR20010008220A - A remediation method of contaminated materials by using pyrite, zero-valent iron and graphite as reactive material for the reactive wall - Google Patents
A remediation method of contaminated materials by using pyrite, zero-valent iron and graphite as reactive material for the reactive wall Download PDFInfo
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Abstract
Description
본 발명은 반응벽체를 이용한 오염물의 정화방법(이하, "반응벽체 방법"이라고도 한다)에 관한 것으로서, 더욱 상세하게는 반응벽체를 오염물이 존재하는 지반에 설치하여 지하수 오염대(contaminant plume)의 수리학적 흐름을 이용하여 반응매질(reactive media)과 오염물질 사이의 화학적 반응을 유도하여 오염 성분을 제거하는 방법에 관한 것이다. 특히, 본 발명은 상기 반응매질로서 황철광(pyrite; FeS, FeS2), 영가형 철 및 흑연을 포함하여 이루어지는 반응벽체를 사용함으로써 황철광에 의하여 pH의 상승이 억제되어 영가형 철에 의한 탈염효율을 증가시킬 수 있는 동시에 흑연에 의한 오염성분의 흡착이 유도됨으로써 오염물의 정화효율이 향상된 반응벽체 방법에 관한 것이다. 본 발명은 환경산업 중 특히, 지반환경 산업에 관련되는 것으로서 예를 들면, 지하 저유시설, 반도체 공장, 공단 밀집지역, 석유화학 단지, 변전시설 등의 산업시설 및 군사시설에 적용 가능한 방법이다.The present invention relates to a method for purifying contaminants using a reactive wall (hereinafter, also referred to as a "reactive wall method"), and more particularly, to repair a contaminant plume by installing a reactive wall on a ground where contaminants exist. The present invention relates to a method of removing contaminants by inducing a chemical reaction between a reactive medium and a contaminant using a physiological flow. In particular, the present invention by using a reaction wall comprising pyrite (FeS (FeS, FeS 2 ), zero valent iron and graphite as the reaction medium is suppressed the rise of pH by pyrite to reduce the desalination efficiency of the iron soluble iron The present invention relates to a reaction wall method which can increase the efficiency of purifying contaminants by increasing the adsorption of contaminants by graphite. The present invention relates to the ground environment industry, in particular, the environmental industry, for example, is applicable to industrial facilities and military facilities, such as underground storage facilities, semiconductor factories, industrial complexes, petrochemical complexes, substation facilities.
종래의 오염된 지하수를 정화하기 위한 반응벽체 방법은 반응매질로서 철가루를 이용하고 있었다. 미국특허 제5,575,927호에서는 반응매질로서 철과 황화철(ferrous sulfide)을 상대적인 양으로 조합하여 사용하는 경우, 철이나 황화철(ferrous sulfide)을 단독으로 사용하는 경우 보다 더 빠르게 할로게네이티드 하이드로카본(halogenated hydrocarbon)을 환원시킬 수 있는 방법을 개시하고 있다. 또한, 미국특허 제5,543,059호에서는, 반응매질로서 철 입자의 크기별로 구분된 최소한 3영역(zone)으로 이루어지는 층이 진 철 벽 또는 칼럼(iron wall or column)에 할로게네이티드 하이드로카본(halogenated hydrocarbon)을 포함하는 오염물을 통과시켜 이를 정화하는 방법을 개시하고 있다.The conventional reaction wall method for purifying contaminated groundwater uses iron powder as a reaction medium. U.S. Pat.No. 5,575,927 discloses that halogenated hydrocarbons are used more quickly when the reaction medium is used in combination in a relative amount of iron and ferrous sulfide, or when iron or ferrous sulfide is used alone. Is disclosed. In addition, US Pat. No. 5,543,059 discloses a halogenated hydrocarbon having a layer consisting of at least three zones separated by the size of iron particles as a reaction medium in an iron wall or column. Disclosed is a method for purifying the contaminants including the through.
상기와 같은 종래 기술에서 영가형 철에 의한 오염물질의 제거기작은 다음과 같은 것으로 밝혀졌다.In the prior art as described above, the removal mechanism of contaminants by zero-valent iron was found to be as follows.
즉, 영가형 철로 존재하는 철(Fe0)은 산화를 일으키며 산화환원쌍(redox couple)을 형성한다. 이는 영가 금속이 전자를 잃으며 양이온 형태로 존재하려는 경향에 의하여 자발적 산화에 의해 발생하는 부식반응과 유사하다. 철의 경우 산화환원전위는 -0.44V이다.That is, iron (Fe 0 ), which is present as a non-valent iron, causes oxidation and forms a redox couple. This is similar to the corrosion reaction caused by spontaneous oxidation due to the tendency of the noble metal to lose electrons and to exist in cation form. For iron, the redox potential is -0.44V.
Fe0↔ Fe2++ 2e- 식(1)Fe0↔ Fe2++ 2e- Formula (1)
도 1은 PCE(C2Cl4, tetrachloroethylene)의 탈염소화 과정과 표준환원전위를 도식화한 도면이다. 도 1에 있어서 B에서 A로 갈 수록 탈염반응은 점점 느려지게 된다. 그리고, C 지점은 산화상태가 가장 높은 지점을 나타내고 D 지점은 산화상태가 가장 낮은 지점을 나타낸다. 도 1에서 예측할 수 있는 바와 같이, 염화유기화합물과 반응 가능한 주요 환원제는 Fe0, Fe2+, H2이다. 부식반응의 경우로는 Fe0로부터 표면에 흡착된 염화 알킬로의 직접적인 전자교환에 의한 것(식(2))이 주종을 이루나, 이외에도 부식반으로 생성된 Fe2+의 탈염소화(식(3)), H2에 의한 탈염소화(식(4)) 또는 H2O에 의한 Fe의 작용 등이 있다. 이들 환원제에 의한 알킬 할라이드(alkyl halide: RX)의 탈염과정은 다음식과 같이 나타낼 수 있다.1 is a diagram illustrating the dechlorination process and standard reduction potential of PCE (C 2 Cl 4 , tetrachloroethylene). In FIG. 1, the desalination reaction is gradually slowed from B to A. FIG. The point C represents the highest oxidation state and the point D represents the lowest oxidation state. As can be expected from FIG. 1, the main reducing agents capable of reacting with chlorinated organic compounds are Fe 0 , Fe 2+ , and H 2 . In the case of the corrosion reaction, it is mainly caused by direct electron exchange from Fe 0 to alkyl chloride adsorbed on the surface (Equation (2)), but in addition, dechlorination of Fe 2+ produced by the corrosion plate (Eq. ), Dechlorination by H 2 (Formula (4)), or Fe by H 2 O. The desalination process of alkyl halides (RX) by these reducing agents can be expressed as follows.
Fe0+ RX + H+↔ Fe2++ RH + X-식(2)Fe 0 + RX + H + ↔ Fe 2+ + RH + X - Formula (2)
2Fe2++ RX + H+↔ 2Fe3++ RH + X-식(3)2Fe 2+ + RX + H + ↔ 2Fe 3+ + RH + X - Formula (3)
H2+ RX ↔ RH + H++ X-식(4)H 2 + RX ↔ RH + H + + X - Formula (4)
도 2는 영가형 철의 부식에 따른 전자교환에 의한 염화유기물의 환원적 탈염소화를 도식화한 도면이다. 도 2A는 영가형 철 표면에서 직접적으로 발생하는 영가형 철에 의한 염화유기화합물의 환원반응을 도식화한 도면이고, 도 2B는 철이온(ferrous ion)에 의해 간접적으로 일어나는 염화유기화합물의 환원반응을, 도 2C는 촉매존재하에서 H2에 의한 염화유기화합물의 환원반응에 영가형 철의 역할을 도식화한 도면이다.FIG. 2 is a diagram illustrating reductive dechlorination of chlorinated organics by electron exchange due to corrosion of zero valence iron. FIG. 2A is a diagram illustrating a reduction reaction of chlorinated organic compounds by zero valent iron directly occurring on the surface of the noble iron, and FIG. 2B illustrates a reduction reaction of chlorinated organic compounds indirectly caused by ferrous ions. 2C is a diagram illustrating the role of zero-valent iron in the reduction of chlorinated organic compounds by H 2 in the presence of a catalyst.
상기와 같은 종래의 반응벽체 방법에서는 과립형의 철가루를 별도의 처리를 하거나 다른 성분물질과 혼합하지 않고 그대로 사용하였으므로, 오염성분의 제거과정에서 pH의 상승 등으로 인하여 철가루에 불순물이 침적되는 현상이 발생하였다. 이러한 불순물의 침적은 반응벽체의 반응성을 떨어뜨려 오염물의 정화에 소요되는 시간이 길어지는 동시에 반응벽체에 포함되어 있는 반응물질의 간극을 막아 반응벽체의 사용가능기간을 단축시키는 문제점이 있었다. 또한, 유기성분이 고농도로 포함되어 있는 오염물에 대하여는 반응물질로 사용되는 철가루의 표면에너지가 부족하여 충분히 탈염을 일으킬 수가 없다는 문제점이 있었다.In the conventional reaction wall method as described above, since granular iron powder is used as it is, without being treated separately or mixed with other ingredients, impurities are deposited in iron powder due to a rise in pH during the removal of contaminants. The phenomenon occurred. Deposition of such impurities decreases the reactivity of the reaction wall to increase the time required for purifying contaminants, and at the same time, there is a problem of shortening the usable period of the reaction wall by blocking the gap between the reactants contained in the reaction wall. In addition, the contaminants containing a high concentration of organic components have a problem that the surface energy of the iron powder used as the reactant is insufficient to cause desalination.
또한, 상기 미국특허 제5,575,927호와 같이 철과 황철광(ferrous sulfide)을 혼합 적용함으로써 pH 상승을 억제하는 시스템의 경우 탈염효율이 향상되나 탈염반응만을 이용한 것으로 반응속도는 철에 의한 탈염반응, 즉 1차반응이라는 제한을 가진다는 문제점이 있었다.In addition, as in the US Patent No. 5,575,927, iron and pyrite (ferrous sulfide) by mixing the application of the system to suppress the rise in pH desalination efficiency is improved, but using only the desalination reaction reaction rate is the desalination reaction by iron, that is 1 There was a problem of having a limitation of difference reaction.
본 발명은 상기와 같은 문제점을 해결하기 위하여, 종래 반응물질로 사용되어 오던 영가형 철 이외에 황철광을 적용하여 pH 상승을 억제함과 동시에 침적되는 불순물 및 고농도로 포함되어 있는 유기성분을 흡착시켜 제거할 수 있는 흑연을 추가로 포함하여 이루어지는 반응벽체를 이용한 효율이 향상된 오염물의 정화방법을 제공하는 것을 목적으로 한다.In order to solve the above problems, by applying pyrite or pyrite in addition to the iron-free iron that has been used as a conventional reactant to suppress the rise in pH, it is possible to remove by adsorbing organic components contained in impurities and high concentrations deposited It is an object of the present invention to provide a method for the purification of contaminants with improved efficiency using a reaction wall which further comprises graphite.
도 1은 PCE의 탈염소화 과정과 표준환원전위를 도식화한 도면이고,1 is a diagram illustrating a dechlorination process and a standard reduction potential of PCE.
도 2A는 영가형 철 표면에서 직접적으로 발생하는 영가형 철에 의한 염화유기화합물의 환원반응을 도식화한 도면이고,2A is a diagram illustrating a reduction reaction of an organic chloride compound by zero-valent iron directly occurring on the surface of zero-valent iron.
도 2B는 철이온(ferrous ion)에 의해 간접적으로 일어나는 염화유기화합물의 환원반응에 영가형 철의 역할을 도식화한 도면이고,FIG. 2B is a diagram illustrating the role of zero-valent iron in the reduction of chlorinated organic compounds indirectly caused by ferrous ions.
도 2C는 촉매존재하에서 H2에 의한 염화유기화합물의 환원반응에 영가형 철의 역할을 도식화한 도면,2C is a diagram illustrating the role of zero-valent iron in the reduction of chlorinated organic compounds by H 2 in the presence of a catalyst.
도 3은 본 발명의 실시예에 따라 농도가 100μM인 PCE 수용액을 정화하는 경우 PCE의 농도변화를 나타내는 도면이고,3 is a view showing a change in the concentration of PCE when purifying the PCE aqueous solution having a concentration of 100μM according to an embodiment of the present invention,
도 4는 본 발명의 실시예에 따라 농도가 100μM인 TCE 수용액을 정화하는 경우 PCE의 농도변화를 나타내는 도면이고,4 is a view showing the concentration change of PCE when purifying the aqueous solution of TCE concentration of 100μM according to an embodiment of the present invention,
도 5는 본 발명의 실시예에 따라 농도가 100μM인 PCE 수용액을 정화하는 경우 pH 변화를 나타내는 도면이다.5 is a view showing a pH change when purifying the PCE aqueous solution having a concentration of 100μM according to an embodiment of the present invention.
본 발명의 영가형 철 및 흑연을 이용한 오염물의 정화방법은 반응물질로서 흙, 영가형 철, 황철광 및 흑연을 포함하여 이루어지는 반응벽체를 만들고, 이를 오염물질이 통과하는 장소에 설치하는 단계; 오염물질을 상기 반응벽체를 통과시켜 오염성분을 제거하는 것을 특징으로 한다.The method for purifying contaminants using zero-valent iron and graphite of the present invention includes the steps of making a reaction wall including soil, zero-valent iron, pyrite and graphite as a reactant, and installing the contaminant in a place where the contaminants pass; Contaminants are passed through the reaction wall to remove contaminants.
본 발명의 영가형 철 및 흑연을 이용한 오염물의 정화방법에 사용되는 흙은 반응벽체의 설치를 위하여 트렌치를 파고 난 후의 굴착토를 사용한다. 일반적으로 상기 흙은 반응벽체 설치 장소에서 채취한 것이 그대로 사용된다. 이는 인접지반과의 투수계수, 물리화학적 특성, 미생물의 조건 등의 유사성을 확보하기 위한 것이다.The soil used in the method for purifying contaminants using the iron and graphite of the present invention uses excavated soil after digging a trench for installing a reaction wall. In general, the soil is used as it is collected at the reaction wall installation site. This is to ensure the similarity of permeability coefficient, physicochemical properties, microbial conditions, etc. with adjacent ground.
본 발명의 영가형 철 및 흑연을 이용한 오염물의 정화방법에 반응물질로서 사용되는 영가형 철에는 대상 오염물질의 탈염에 필요한 에너지(산화환원전위; redox potential)에 따라 입자크기 별로 구분된 나노미터 크기의 철(Fe), 마이크로미터 크기의 철(Fe) 및 과립형 철(granular Fe)의 세가지가 사용된다.The zero-valent iron used as a reactant in the method for purifying contaminants using iron and graphite of the present invention has nanometer size divided by particle size according to the energy (redox potential) required for desalination of the target pollutant. Three kinds of iron (Fe), micrometer-sized iron (Fe) and granular iron (granular Fe) are used.
상기와 같이 각각 다른 크기의 철을 사용하는 이유는 반응물질의 비표면적은 반응율과 직접적인 관계가 있으므로 오염물질의 탈염(dehalogenation)에 요구되는 에너지에 적합한 반응물질을 적용하기 위한 것이다.The reason for using iron of different sizes as described above is that the specific surface area of the reactants is directly related to the reaction rate, so that the reactants suitable for the energy required for dehalogenation of contaminants are applied.
상기 나노미터 크기의 철은 1.6M의 소듐 보로하이드라이드(sodium borohydride: NaBH4) 용액을 1.0M의 염화철(ferric chloride : FeCl3ㆍ6H2O) 용액에 천천히 반응시킴으로써 하기 식(5)과 같이 Fe0의 침전을 유도하여 제조한다.The nanometer-sized iron is slowly reacted with 1.6 M sodium borohydride (NaBH 4 ) solution to 1.0 M ferric chloride (FeCl 3 · 6H 2 O) solution, as shown in Equation 5 below. Prepared by inducing precipitation of Fe 0 .
Fe(H2O)6 3-+ 3BH4-+ 3H2O → Fe0↓+ 3B(OH)3+ 10.5H2식(5)Fe (H 2 O) 6 3- + 3BH 4- + 3H 2 O → Fe 0 ↓ + 3B (OH) 3 + 10.5H 2 Formula (5)
상기 마이크로미터 크기 철은 일반적으로 325∼100메쉬 크기 범위를 가지는 상업용 철가루 또는 제강/철강 부산물을 활용한다.The micrometer size iron generally utilizes commercial iron powder or steel / steel by-products having a size range of 325 to 100 mesh.
본 발명의 영가형 철 및 흑연을 이용한 오염물의 정화방법에 반응물질로서 사용되는 황철광은 FeS, FeS2(pyrite) 등이 포함될 수 있으며, 상기한 영가형 철과 혼합되어 사용되며, 반응벽체의 pH를 중성으로 유지시키기 위하여 사용된다. 영가형 철을 반응물질로 이용한 반응벽체 방법에서 pH가 높아질 경우, 반응물질인 철 표면에 금속수산화물(metal hydroxide) 등이 침적되어 유효표면적을 저감시키는 부동태화(passivation)가 발생하기 때문에 영가형 철(Fe0)에 의한 환원적 탈염소화 과정은 반응벽체 시스템의 pH에 매우 민감하다. 영가형 철을 반응물질로 한 반응벽체 방법에서는 지하수를 해리시킴으로써 수산화 라디칼(hydroxyl radical ;ㆍOH)이 지속적으로 방출되어 pH가 상승하게 된다. 따라서, 이러한 pH 상승으로 인한 유효표면적 감소현상을 방지하기 위하여 상기한 활철광을 영가형 철과 혼합하여 사용하게 된 것이다.Pyrite used as a reactant in the method for purifying contaminants using the noble iron and graphite of the present invention may include FeS, FeS 2 (pyrite), and the like. It is used to keep the neutral. When the pH is increased in the reaction wall method using zero-valent iron as a reactant, since the metal hydroxide is deposited on the iron surface as a reactant, passivation occurs to reduce the effective surface area. The reductive dechlorination process by (Fe 0 ) is very sensitive to the pH of the reaction wall system. In the reaction wall method using zero-valent iron as a reactant, by dissociating groundwater, hydroxyl radicals (OH) are continuously released to increase pH. Therefore, in order to prevent the reduction of the effective surface area due to such a rise in pH, the above-mentioned hematite is mixed with zero valence iron.
본 발명의 영가형 철 및 흑연을 이용한 오염물의 정화방법에 반응물질로서 사용되는 흑연은 유기오염물 및 각종 침전물을 흡착시켜 제거할 수 있는 물질이다. 본 발명에 사용되는 흑연은 비표면적이 크고, 유기오염물 및 각종 침전물에 대한 흡착효과가 큰 무정형질 흑연(amorphous graphite)이 바람직하다. 본 발명에서는 상기와 같은 무정형질 흑연을 상기의 영가형 철 및 황철광과 혼합하여 적용함으로써 전체 반응벽체 시스템의 효율을 증가시킨다.Graphite, which is used as a reactant in the method for purifying contaminants using zero-valent iron and graphite of the present invention, is a substance capable of absorbing and removing organic contaminants and various precipitates. The graphite used in the present invention is preferably amorphous graphite having a large specific surface area and a large adsorption effect on organic contaminants and various precipitates. In the present invention, by applying the amorphous graphite as described above mixed with the above-mentioned noble iron and pyrite ore to increase the efficiency of the entire reaction wall system.
상기 흑, 영가형 철, 활철광 및 흑연으로 이루어지는 반응벽체에서 황철광의 최소 함량은 pH 완충능을 보이는 최소의 양 이상이 포함되어야 한다. 황철광이 상기 pH 완충능을 보이는 최소의 양은 영가철에 대하여 중량기준으로 1/1000 수준이다. 또한, 흙 : 영가철 및 황철광 : 흑연의 혼합비율은 각각 무게비 약 78∼79 : 20 : 1∼2이 바람직하다. 더욱 바람직하기로는 79 : 20 : 1이다. 이는 흙, 영가철, 황철광 및 흑연의 각 함량에 따라 이루어지는 각 반응벽체의 투수계수 측정 하여 상기 투수계수가 오염물이 통과되는 시간에 따라 현저하게 감소되지 않고 일정하게 유지될 수 있는 혼합비율이다.The minimum content of pyrite in the reaction wall consisting of black, zero-valent iron, hematite and graphite should include at least the minimum amount showing the pH buffering capacity. The minimum amount of pyrite shows the pH buffering capacity is 1/1000 on a weight basis with respect to zero iron. In addition, the mixing ratio of soil: ductile iron and pyrite or graphite is preferably about 78 to 79: 20: 1 to 2 by weight. More preferably, it is 79: 20: 1. This is a mixing ratio that can be kept constant without significantly reducing the permeability coefficient of each reaction wall by measuring the permeability coefficient of each reaction wall made according to the respective contents of soil, ductile iron, pyrite and graphite.
상기의 흙, 영가형 철, 활철광, 흑연을 포함하여 이루어지는 반응벽체의 제조과정은 다음과 같다. 먼저, 현장에서 백호(backhoes)와 크렘셀(clamshells)을 사용하여 도랑(trench)을 파서 도랑안에 설치한다. 영가형 철과 영가형 철의 1/1000 중량의 황철광을 혼합하고, 여기에 투수계수 측정에 따른 혼합비율에 해당하는 굴착토를 현장에서 혼합플랜트(mixing plant)를 이용하여 직접적으로 혼합하여 도랑에 부어 넣는다. 또한, 여기에 상기 투수계수 측정에 따른 혼합비율에 해당하는 흑연을 혼합한다. 한편, 반응매질을 설치하는 동안 도랑(trench)의 안정성을 확보하기 위하여 임시로 강철시트파일(steel sheet pile)을 근입시키면서 설치한다.The manufacturing process of the reaction wall including the soil, ductile iron, hematite, graphite is as follows. First, in the field, backhoes and clamshells are used to dig a trench and install it in the trench. Mix 1/1000 weight iron pyrite of zero-valent iron and zero-valent iron, and mix the excavated soil corresponding to the mixing ratio according to the measurement of permeability coefficient in the field by using a mixing plant. Pour in. In addition, graphite corresponding to the mixing ratio according to the permeability coefficient measurement is mixed here. On the other hand, in order to ensure the stability of the trench (trench) during the installation of the reaction medium while installing a steel sheet pile (steel sheet pile) temporarily.
본 발명에 적용될 수 있는 오염물질은 PCE(C2Cl4, tetrachloroethylene), TCE(C2HCl3, trichoroethylene), DCE(C2H2Cl2, dichloroethylene), VC(C2H3Cl, vinyl chloride), CT(CCl4, carbon tetrachloride), 트리클로로메탄(CHCl3:trichloromethane), 디클로로메탄(CH2Cl2:dichloromethane), 클로로메탄(CH3Cl: chloromethane), PCBs(polychlorinated biphenyls) 등의 유기화합물이 포함될 수 있으며, 이들은 영가형 철(Fe0)의 부식과정에서 발생되는 전자에 의하여 Cl-이온을 H+이온으로 대체시키는 환원적 탈염소화(reductive dehalgenation) 반응을 통하여 에탄(ethane)과 같은 무해물질로 변환된다.Contaminants applicable to the present invention are PCE (C 2 Cl 4 , tetrachloroethylene), TCE (C 2 HCl 3 , trichoroethylene), DCE (C 2 H 2 Cl 2 , dichloroethylene), VC (C 2 H 3 Cl, vinyl chloride), CT (CCl 4 , carbon tetrachloride), trichloromethane (CHCl 3 : trichloromethane), dichloromethane (CH 2 Cl 2 : dichloromethane), chloromethane (CH 3 Cl: chloromethane), PCBs (polychlorinated biphenyls) Organic compounds may be included, and they may contain ethane and ethane through a reductive dehalgenation reaction in which Cl − ions are replaced with H + ions by electrons generated during the corrosion of ferrous iron (Fe 0 ). Converted to the same harmless substance.
실시예Example
본 실시예에서는 영가형 철(elemental Fe)을 포함하여 만들어진 반응벽체, 영가형 철 및 황철광을 혼합하여 만들어진 반응벽체 및 영가형 철, 황철광 및 흑연을 혼합하여 만들어진 반응벽체를 각각 폭 1m, 깊이 0.5m, 두께 0.01m로 설치하고, 여기에 PCE 및 TCE의 농도가 100μM인 수용액을 통과시켰다. 여기에 사용된 영가형 철은 100, 50메쉬의 크기였으며, 사용된 영가형 철의 크기는 각 도면에 나타내었다. 또한, 영가형 철을 포함하여 만들어진 반응벽체는 흙 : 영가형 철은 79 : 21이었다. 영가형 철 및 황철광을 혼합하여 만들어진 반응벽체는 흙 : 영가형 철 및 활청광은 79 : 21이었고 황철광은 영가형 철의 중량에 대하여 1/1000 수준으로 함유되었다. 영가형 철, 황철광 및 흑연을 혼합하여 만들어진 반응벽체는 흙 : 영가형 철 및 황철광 : 흑연은 79 : 20 : 1이었고 황철광은 영가형 철의 중량에 대하여 1/1000 수준으로 함유되었다.In the present embodiment, a reaction wall made of mixed elemental Fe, a reaction wall made of a mixture of Young's iron and pyrite, and a reaction wall made of a mixture of Young's iron, pyrite and graphite are each 1 m in width and 0.5 in depth. m and a thickness of 0.01 m were installed, and an aqueous solution having a concentration of PCE and TCE of 100 µM was passed therethrough. The zero-valent iron used here was 100, 50 mesh in size, and the size of the zero-valent iron used was shown in each drawing. In addition, the reaction wall made of iron soluble iron was 79:21 for soil: iron soluble iron. Reaction walls made of a mixture of noble iron and pyrite were soil: noble iron and slidable rock 79:21, and pyrite contained 1/1000 of the weight of noble iron. The reaction wall made of a mixture of noble iron, pyrite and graphite contained soil: noble iron and pyrite or graphite: 79: 20: 1 and pyrite contained 1/1000 of the weight of noble iron.
상기 영가형 철을 포함하여 만들어진 반응벽체, 영가형 철 및 황철광을 혼합하여 만들어진 반응벽체 및 영가형 철, 황철광 및 흑연을 혼합하여 만들어진 반응벽체의 투수계수는 측정결과 각각 5cm/hr, 4.7cm/hr, 4.3cm/hr이었고, 동수구배는 세가지 모두 1/50이었다. 이로부터 산정된 다시(darcy) 유속은 각각 0.1cm/hr, 0.094cm/hr, 0.086cm/hr로 나타났으며, 본 발명의 평가에 사용되는 지하수의 최대유속은 각각 상기 다시 유속값의 10배에 해당하는 1cm/hr, 0.94cm/hr, 0.86cm/hr로 설정하였다.The permeability coefficients of the reaction wall made of a mixture of the zero-valent iron, the reaction wall made of a mixture of zero-valent iron and pyrite, and the reaction wall made of a mixture of zero-valent iron, pyrite and graphite are 5 cm / hr and 4.7 cm /, respectively. hr, 4.3cm / hr, and all three gradients were 1/50. The calculated darcy flow rates were 0.1 cm / hr, 0.094 cm / hr, and 0.086 cm / hr, respectively. The maximum flow rate of groundwater used in the evaluation of the present invention was 10 times the flow rate value, respectively. Corresponding to 1 cm / hr, 0.94 cm / hr, 0.86 cm / hr was set.
pH 변화의 측정은 pH 미터(pH meter)(model 720A, Orion, 미국)로 측정하였다. 본 실시예 사용된 PCE, TCE의 농도는 가스 크로마토그래피(gas chromatography)(6890 series, Hewlett Packard Co. 미국)를 사용하여 분석하였다. 가스 크로마토그래피의 분석조건을 표 1에 나타내었다.The measurement of pH change was measured with a pH meter (model 720A, Orion, USA). The concentrations of PCE and TCE used in this example were analyzed using gas chromatography (6890 series, Hewlett Packard Co. USA). Table 1 shows the analysis conditions of gas chromatography.
표 1. 가스 크로마토그래피 분석조건.Table 1. Gas Chromatographic Analysis Conditions.
본 실시예에 따른 결과는 도 3, 4, 5에 나타내었다. 도 3 또는 4는 본 실시예에 사용된 영가형 철(elemental Fe)을 포함하여 만들어진 반응벽체, 영가형 철 및 황철광을 혼합하여 만들어진 반응벽체 및 영가형 철, 황철광 및 흑연을 혼합하여 만들어진 반응벽체에 각각 PCE 및 TCE의 농도가 100μM인 수용액을 통과시켰을 경우의 농도변화를 나타내는 도면이다. 도 3에서 볼 수 있는 바와 같이, PCE의 농도는 반응시간이 약 100시간 경과되었을 때 영가형 철, 황철광 및 흑연을 혼합하여 만들어진 반응벽체, 영가형 철 및 황철광을 혼합하여 만들어진 반응벽체 및 영가형 철을 포함하여 만들어진 반응벽체의 순서로 빨리 감소하는 것을 알 수 있었다. 도 4에서 볼 수 있는 바와 같이, TCE의 농도는 반응시간이 약 100시간 경과되었을 때 영가형 철, 황철광 및 흑연을 혼합하여 만들어진 반응벽체, 영가형 철 및 황철광을 혼합하여 만들어진 반응벽체 및 영가형 철을 포함하여 만들어진 반응벽체의 순서로 빨리 감소하는 것을 알 수 있었다.Results according to this example are shown in FIGS. 3, 4, and 5. 3 or 4 is a reaction wall made by mixing elemental Fe used in the present embodiment, a reaction wall made by mixing zero-valent iron and pyrite and a reaction wall made by mixing zero-valent iron, pyrite and graphite. It is a figure which shows the density | concentration change at the time of letting an aqueous solution of PCE and TCE concentration of 100 micrometers pass, respectively. As can be seen in Figure 3, the concentration of PCE is a reaction wall made of a mixture of zero-valent iron, pyrite and graphite, reaction wall made of a mixture of zero-valent iron and pyrite when the reaction time is about 100 hours It was found to decrease rapidly in the order of reaction walls made of iron. As can be seen in Figure 4, the concentration of TCE is a reaction wall made of a mixture of zero-valent iron, pyrite and graphite, reaction walls made of a mixture of zero-valent iron and pyrite when the reaction time is about 100 hours It was found to decrease rapidly in the order of reaction walls made of iron.
도 5는 본 실시예에 사용된 다양한 반응물질로 구성된 반응벽체에 PCE의 농도가 100μM인 수용액을 통과시켰을 경우의 pH 변화를 나타내는 도면이다. 도 5에서 볼 수 있는 바와 같이, 영가형 철, 황철광 및 흑연을 포함하여 구성된 반응벽체와 영가형 철 및 황철광을 포함하여 구성된 반응벽체가 가장 안정된 pH 값을 유지하였고, 영가형 철만을 포함하여 이루어진 반응벽체에서는 반응시간이 경과함에 따라 알칼리성으로 변화하였다.FIG. 5 is a view showing a pH change when an aqueous solution having a concentration of 100 μM is passed through a reaction wall composed of various reactants used in this example. As can be seen in Figure 5, the reaction wall composed of noble iron, pyrite and graphite and the reaction wall composed of zero valent iron and pyrite maintained the most stable pH value, made only containing zero valent iron In the reaction wall, the reaction time was changed to alkaline.
본 발명에 따르면, 종래의 흙, 영가형 철을 포함하여 구성되는 반응벽체 또는 흙, 영가형 철 및 황철광을 포함하여 구성되는 반응벽체에 비하여 반응벽체에 흑연을 첨가하므로써 염화유기화물의 탈염효율이 현저하게 향상되고, pH의 변화가 적어 오염물의 정화효율이 현저하게 향상된다.According to the present invention, the desalination efficiency of chlorinated organics is improved by adding graphite to the reaction wall as compared with the conventional reaction wall composed of soil, zero-valent iron or the reaction wall composed of soil, zero-valent iron and pyrite. It is remarkably improved and the change of pH is small, and the purification efficiency of a contaminant is remarkably improved.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005014487A1 (en) * | 2003-08-09 | 2005-02-17 | Park, Tae-Hyok | Treating composition and method for wastewater or sewage and cleaning composition and method for air |
KR100482713B1 (en) * | 2002-10-31 | 2005-04-14 | (주)덕일엔지니어링 | The water transmission characteristic interception wall which purifies the underground water which be imbrued |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100735635B1 (en) | 2005-07-21 | 2007-07-04 | 델라웨어 대학교 | Process for treating refractory wastewater using zero-valent iron treatment and biodegradation |
KR100644164B1 (en) | 2005-11-07 | 2006-11-10 | 광주과학기술원 | Mobile reactive barrier and in situ remediation of soil or groundwater |
KR101241377B1 (en) * | 2010-10-14 | 2013-03-11 | 효림산업주식회사 | D-NVI attached to the surface of iron sulfide sediment and method for purifying polluted soil and groundwater environmental pollutants |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6427690A (en) * | 1987-07-20 | 1989-01-30 | Agency Ind Science Techn | Treatment of water containing organic compounds having difficulty in decomposition |
GB8926853D0 (en) * | 1989-11-28 | 1990-01-17 | Gillham Robert W | Cleaning halogenated contaminants from water |
GB2255087B (en) * | 1991-04-25 | 1995-06-21 | Robert Winston Gillham | System for cleaning contaminated water |
JPH0812033A (en) * | 1994-06-29 | 1996-01-16 | P F C:Kk | Harmful substance leak preventing structure for refuse buried place |
US5575927A (en) * | 1995-07-06 | 1996-11-19 | General Electric Company | Method for destruction of halogenated hydrocarbons |
JP3490247B2 (en) * | 1997-03-27 | 2004-01-26 | 同和鉱業株式会社 | How to clean the soil |
JP3216014B2 (en) * | 1997-11-27 | 2001-10-09 | 大成建設株式会社 | Continuous underground water purification wall |
JP2888428B1 (en) * | 1998-02-10 | 1999-05-10 | 有信株式会社 | Improvement of contaminated soil |
EP1166904B1 (en) * | 1998-11-17 | 2016-06-15 | Dowa Eco-System Co., Ltd. | Method for detoxification treatment of soil |
KR100363209B1 (en) * | 2000-02-16 | 2002-12-05 | 장덕진 | Dechlorination method of chlorinated organic compounds sewage and a device thereof |
KR100341957B1 (en) * | 2000-03-02 | 2002-06-24 | 이기세 | Method of purifying soil contaminated with oil and an apparatus thereof |
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KR100482713B1 (en) * | 2002-10-31 | 2005-04-14 | (주)덕일엔지니어링 | The water transmission characteristic interception wall which purifies the underground water which be imbrued |
WO2005014487A1 (en) * | 2003-08-09 | 2005-02-17 | Park, Tae-Hyok | Treating composition and method for wastewater or sewage and cleaning composition and method for air |
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