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분말 바이오-숯으로부터 중금속 오염수 처리용 바이오-숯 비드 제조 및 적용
최유림,노훈,이규범,신복수,주완호,김남국,김진홍,양재규,조성희,장윤영,Choi, Yu-Lim,Roh, Hoon,Lee, Kyu-Beom,Shin, Bok-Su,Joo, Wan-Ho,Kim, Nam-Kook,Kim, Jin-Hong,Yang, Jae-Kyu,Reddy Koduru, Janardhan,Cho, Sung-Heui,Chang, Yoon-Young 한국지하수토양환경학회 2015 지하수토양환경 Vol.20 No.6
In this study, biochar-bead, prepared from biochar powder derived from woody biomass, was used for removal cadmium ion in aqueous solution. Various mixing ratios of alginate solution and biochar powder were used for the production of round shape biochar-bead. An optimum mixing ratio was selected as 1.5% alginate solution and 20 wt% biochar. The produced biochar-bead was characterized by SEM, FT-IR, and XRD analyses. The adsorption capacity of Cd(II) by biochar-bead was found to be 9.72 mg/g which was higher than that by GAC and PAC. According to this study, round shape biochar-bead is expected to be used as a media for reactive barrier or water filtration.
One-pot 합성 방법을 이용한 나노 철입자가 담지된 폐목재 기반 하이드로차의 제조 및 특성 평가
최유림,김동수,안혜영,박광진,양재규,장윤영,Choi, Yu-Lim,Kim, Dong-Su,Angaru, Ganesh Kumar Reddy,Ahn, Hye-Young,Park, Kwang-Jin,Yang, Jae-Kyu,Chang, Yoon-Young 한국지하수토양환경학회 2020 지하수토양환경 Vol.25 No.1
In this study, iron nanoparticles impregnated hydrochar (FeNPs@HC) was synthesized using lignocellulosic waste and simple one-pot synthetic method. During hydrothermal carbonization (HTC) process, the mixture of lignocellulosic waste and ferric nitrate (0.1~0.5 M) as a precursor of iron nanoparticles was added and heated to 220℃ for 3 h in a teflon sealed autoclave, followed by calcination at 600℃ in N<sub>2</sub> atmosphere for 1 h. For the characterization of the as-prepared materials, X-ray diffraction (XRD), cation exchange capacity (CEC), fourier transform infrared spectrometer (FT-IR), Brunauer-Emmett-Teller (BET), transmission electron microscope (TEM), Energy Dispersive X-ray Spectroscopy (EDS) were used. The change of Fe(III) concentration in the feedstock influenced characteristics of produced FeNPs@HC and removal efficiency towards As(V) and Pb(II). According to the Langmuir isotherm test, maximum As(V) and Pb(II) adsorption capacity of Fe<sub>0.25</sub>NPs@HC were found to be 11.81 and 116.28 mg/g respectively. The results of this study suggest that FeNPs@HC can be potentially used as an adsorbent or soil amendment for remediation of groundwater or soil contaminated with arsenic and cation heavy metals.
인산 개질 바이오차와 레드머드를 이용한 비소 및 중금속 복합 오염토양 안정화
최유림 ( Yu-lim Choi ),김동수 ( Dong-su Kim ),김세희 ( Se-hee Kim ),강태준 ( Tae-jun Kang ),도지영 ( Ji-young Do ),박광진 ( Gwang-jin Park ),양재규 ( Jae-kyu Yang ),장윤영 ( Yoon-young Chang ) 한국폐기물자원순환학회(구 한국폐기물학회) 2021 한국폐기물자원순환학회 춘계학술발표논문집 Vol.2021 No.-
토양안정화기술은 토양 중 오염물질을 제거하여 함유량을 감소시키는 기존 공법과는 달리 안정화제를 오염 토양에 주입함으로써 오염물질을 안정화된 형태로 변환시켜 이동성 및 생물유효도를 저감시키는 기술이다. 토양안정화기술은 준금속 및 중금속 오염 토양에 적용이 가능하며 빠르고 간편하게 적용할 수 있으며 토양의 특성, 생태적 기능 및 부지의 용도를 유지할 수 있는 위해도 기반의 토양 오염복원기술로 알려져 있다. 레드머드는 보크사이트(bauxite) 제조 과정에서 발생하는 부산물로서 수 마이크로미터의 입자크기에 형태에 다량의 Fe<sub>2</sub>O<sub>3</sub>와 Al<sub>2</sub>O<sub>3</sub> 성분을 보유하며 강알칼리성을 가지고 있는 물질이다. 강알칼리성의 특성으로 인해 산성 오염 토양 등에 적용될 수 있으나 적용 비율이 높아지는 경우에는 토양의 pH가 작물이 밭토양의 적정 pH 보다 더 높아질 수 있다. 한편 바이오차(biochar)는 고온과 산소가 제한된 조건에서 바이오매스(biomass)를 통해 얻어지는 물질로서 높은 pH, 비표면적, 산소함유관능기를 보유하고 있어 수처리 또는 토양안정화 분야에서 널리 이용되고 있는 물질이다. 최근에는 비표면적을 넓히고 표면의 특성을 개질하거나 탄화의 필요한 온도를 낮출 수 있는 화학적 활성화 방법을 이용한 바이오차 제조가 여러 연구자들에 의해 진행되고 있다. 본 연구에서는 비소와 중금속으로 오염된 복합오염토양의 안정화를 위해 인산으로 개질된 바이오차와 레드머드를 적용하였다. 인산으로 개질된 바이오차와 레드머드의 안정화 효과를 확인하기 위해 적용 2주 후의 토양의 이화학적 특성 변화를 분석하고 비소 및 중금속 용출 시험을 실시하였다.
철 나노 입자가 담지된 바이오차 기반 비드 형태 안정화제를 이용한 비소 및 납 오염토양의 안정화
최유림 ( Yu-lim Choi ),김동수 ( Dong-su Kim ),강태준 ( Tae-jun Kang ),양재규 ( Jae-kyu Yang ),장윤영 ( Yoon-young Chang ) 한국환경영향평가학회 2021 환경영향평가 Vol.30 No.4
본 연구에서는 기존 바이오차의 제한점인 비소 오염 토양 안정화에 대한 낮은 효율과 비산에 의한 유실 가능성을 개선할 수 있는 철 나노입자가 담지된 바이오차 기반 비드 형태 안정화제인 INPBC/bead (Iron Nano-Particles Impregnated BioChar/bead)를 제조하였다. 폐목재 바이오매스를 Fe(III) 용액과 함께 수열 반응을 진행하고 이후 소성을 거쳐 INPBC를 제조하였다. INPBC/bead는 알지네이트의 crosslinking 반응을 통해 제조 하였다. 제조한 INPBC/bead의 특성을 평가하기 위해 FT-IR, XRD, BET 비표면적, SEM-EDS 분석을 실시하였다. 특성 평가 결과 입자 크기가 1-4 mm인 INPBC/bead는 여러 산소 함유 관능기를 보유하며 표면의 철 결정성은 Fe<sub>3</sub>O<sub>4</sub>인 것으로 확인되었다. INPBC/bead의 성능을 평가하기 위해 폐광산 주변 지역에서 채취한 비소 및 중금속 오염 토양을 이용하여 배양 실험을 실시하였다. 4주 동안의 배양이 종료된 후 처리된 토양을 대상으로 TCLP, SPLP 시험을 실시한 결과 안정화제 적용 비율이 증가함에 따라 안정화 효율은 높아지는 것으로 확인되었다. SPLP 시험 결과, INPBC/bead 5%의 비소 안정화 효율은 81.56%이며 납의 경우에는 농도가 검출한계 미만으로 저감되었다. 상기의 결과를 종합하였을 때 INPBC/bead는 토양 중 비소와 납에 대한 안정화 효과를 동시에 보유하고 토양의 pH 변화를 일으키지 않으며 비드 형태로써 적용 과정에서 비산되는 것이 방지할 수 있는 안정화제이기 때문에 비소 및 중금속 복합 오염 토양 안정화에 적용 가능성이 높은 안정화제 인 것으로 판단된다. In this work, Iron Nano-Particles Impregnated BioChar/bead (INPBC/bead) soil amendment was developed to increase biochar’s reactivity to As in soil and preventing possible wind loss. Prior to preparation of INPBC/bead, INPBC was produced utilizing lignocellulosic biomass and Fe(Ⅲ) solution in a hydrothermal method, followed by a calcination process. Then, the bead type amendment, INPBC/bead was produced by cross-linking reaction of alginate with INPBC. FT-IR, XRD, BET, and SEM-EDS analyses were utilized to characterize the as-synthesised materials. The particle size range of INPBC/bead was 1-4 mm, and different oxygen-containing functional groups and Fe<sub>3</sub>O<sub>4</sub> crystalline phase were produced on the surface of INPBC/bead, according to the characterization results. The soil cultivation test was carried out in order to assess the stabilization performance of INPBC/bead utilizing As and Pb-contaminated soil obtained from an abandoned mining location in South Korea. After 4 weeks of culture, TCLP and SPLP extraction tests were performed to assess the stabilization efficacy of the amendment. The TCLP and SPLP findings revealed that raising the application ratio improved stabilizing efficiency. The As stabilization efficiency was determined to be 81.56 % based on SPLP test findings for a 5% in (w/w) INPBC/bead treatment, and the content of Pb in extracts was reduced to the limit of detection. According to the findings of this study, INPBC/bead that can maintain pH of origin soil and minimize wind loss might be a potential amendment for soil polluted with As and heavy metals.
비소 오염토양의 안정화를 위한 나노 Fe°담지 바이오차 적용 연구
최유림 ( Yu-lim Choi ),( Ganesh Kumar Reddy Angaru ),안혜영 ( Hye-young Ahn ),박광진 ( Kwang-jin Park ),주완호 ( Wan-ho Joo ),양재규 ( Jae-kyu Yang ),장윤영 ( Yoon-young Chang ) 한국환경영향평가학회 2020 환경영향평가 Vol.29 No.5
본 연구에서는 전정가지 부산물과 one-pot 합성방법을 이용하여 철 나노입자가 담지된 바이오차인 INPBC(Iron Nano-Particles Impregnated BioChar)를 제조하고 비소 오염토양의 안정화제로써의 적용가능성을 평가하였다. INPBC는 전정가지 부산물과 Fe(III) 용액을 220°C에서 3시간 동안 수열반응하고 이후 N<sub>2</sub> 분위기에서 1시간 동안 소성하여 제조하였으며 FT-IR, XRD, BET, SEM을 이용하여 INPBC의 특성을 분석하였다. INPBC의 안정화 성능평가는 국내 E폐광산과 S폐광산의 인근 농경지에서 채취한 비소로 오염된 토양 Soil-E와 Soil-S를 채취하여 4주 동안의 배양실험을 실시하였다. 배양실험 후 토양중 비소의 안정화 정도를 알아보기 위해 TCLP와 SPLP 용출시험을 실시하였다. TCLP와 SPLP의 용출시험결과, INPBC의 적용 농도의 증가에 따라 토양 중 비소의 용출농도는 감소하여 안정화 효율이 높아지는 것을 확인할 수 있었으며, 특히 Soil-E의 경우 SPLP 용출액 중 비소의 농도는 먹는물 수질기준치 이하의 낮은 값을 나타내었다. 안정화 토양의 연속추출시험에서는 쉽게 용출되는 1단계 및 2단계의 분획비율이 감소되고 그 보다 용출이 어려운 3단계 및 4단계의 분획비율이 증가되는 것을 확인할 수 있었으며, 이러한 결과는 오염토양에 주입한 INPBC의 표면에 존재하는 철 나노입자로 인해 토양에서 용출된 비소가 sorption에 의해 안정화된 것으로 판단된다. 본 연구에서 나타난 INPBC의 비소 오염토양의 안정화 효과는 대규모 비소오염토양의 위해성 저감을 위한 안정화제로서 높은 적용 가능성을 보여 준다. In this study, nano Fe°-impregnated biochar (INPBC) was prepared using pruning residues and one-pot synthetic method and evaluated its performance as an amendment agent for the stabilization of arsenic-contaminated soil. For the preparation of INPBC, the mixture of pruning residue and Fe (III) solution was heated to 220°C for 3hr in a teflon-sealed autoclave followed by calcination at 600°C under N<sub>2</sub> atmosphere for 1hr. As-prepared INPBC was characterized using FT-IR, XRD, BET, SEM. For the stabilization test of as-prepared INPBC, As-contaminated soils (Soil-E and Soil-S) sampled from agricultural sites located respectively near E-abandoned mine and S-abandoned mine in South Korea were mixed with different of dosage of INPBC and cultivated for 4 weeks. After treatment, TCLP and SPLP tests were conducted to determine the stabilization efficiency of As in soil and showed that the stabilization efficiency was increased with increasing the INPBC dosage and the concentration of As in SPLP extractant of Soil-E was lower than the drinking water standard level of Ministry of Environment of South Korea. The sequential fractionation of As in the stabilized soils indicated that the fractions of As in the 1st and 2nd stages that correspond liable and known as bioavailable fraction were decreased and the fractions of As in 3rd and 4th stages that correspond relatively non-liable fraction were increased. Such a stabilization of As shows that the abundant nano Fe° on the surface of INPBC mixed with As-contaminated soils played the co-precipitation of As leaching from soil by surface complexation with iron. The results of this study may imply that INPBC as a promising amendments for the stabilization of As-contaminated soil play an important role.
비소 및 중금속의 식물체 전이감소를 위한 철 나노 입자가 담지된 바이오차의 농경지 토양 안정화제 적용성 평가
고일하,김정은,박소영,최유림,김동수,문덕현,장윤영,Koh, Il-Ha,Kim, Jung-Eun,Park, So-Young,Choi, Yu-Lim,Kim, Dong-Su,Moon, Deok Hyun,Chang, Yoon-Young 한국지하수토양환경학회 2022 지하수토양환경 Vol.27 No.6
This study assessed the feasibility of iron oxide nanoparticles impregnated with biochar (INPBC), derived from woody biomass, as a stabilizing agent for the stabilization of farmland soil in the vicinity of an abandoned mine through pot experiments with 28 days of lettuce growth. The lettuce grown in the INPBC amended soils increased by more than 100% and the concentrations of inorganic elements (Cu, Ni, Zn) decreased by more than 40%. As, Cd and Pb were not transferred properly from the soils to the lettuce biomass. The bioavailability of arsenic and heavy metals in the INPBC amended soils were decreased by 26%~50%. It seems that the major mechanisms of stabilization were arsenic adsorption on iron oxides, heavy metal precipitation by soil pH increasing and heavy metal adsorption on organic matter. These results revealed that the lower bioavailability of the inorganic pollutants in the soils stabilized using INPBC induced lower transfer to the lettuce. Thus, INPBC could be used as an amendment material for the stabilization of farmland soils contaminated by arsenic and heavy metals. However, a pre-review of the chemical properties of the amended soil must be performed prior to applying INPBC in farmland soil because the concentration of the nutrients in the soil such as available phosphates and exchangeable cations (Ca, Mg, K) could be decreased due to adsorption on the surface of the iron oxides and organic matter.
화학적 개질방법을 적용하여 폐목재로부터 제조한 바이오차를 이용한 중금속 제거
김동수 ( Dong-su Kim ),최종수 ( Jong-soo Choi ),김세희 ( Se-hee Kim ),도지영 ( Ji-young Do ),박삼배 ( Sam-bae Park ),최유림 ( Yu-lim Choi ),장윤영 ( Yoon-young Chang ),양재규 ( Jae-kyu Yang ) 한국수처리학회(구 한국수처리기술연구회) 2020 한국수처리학회지 Vol.28 No.6
Wastewater containing various harmful heavy metals is commonly generated from small businesses in the Seoul metropolitan area, and it may cause serious pollution to the soil, surface water and underground water due to improper treatment. In order to treat wastewater containing heavy metal ions, adsorption technique using carbon-based material is generally applied. Among several carbon-based material, biochar has much attention because it is known to have a large surface area and high cation exchange capacity. In this study, bio-char powder was manufactured by pyrolysis of waste wood in the range of 400 to 900°C and/or was modified using several acidic solutions such as chloroacetic acid, nitric acid and phosphoric acid to improve adsorption of heavy metals. In order to save energy, pyrolysis was performed with three methods, namely, microwave, low temperature Dry Oven and tube furnace. In the case of biochar obtained by pyrolysis with microwave, removal capability for Pb(II) and Cd(II) was 91.7 mg/g and 75.1 mg/g, respectively. In addition, when low temperature pyrolysis was performed using dry oven after phosphoric acid refinement, the removal capacity for Pb(II) and Cd(II) was 70.1mg/g and 60.8 mg/g, respectively. Finally, in the case of pyrolysis using tube furnace, removal capability for Pb(II) and Cd(II) was 89.7 mg/g and 67.7 mg/g, respectively. The biochar obtained from phosphoric acid-low temperature pyrolysis in dry oven is considered to be the most practical modified method considering possibility of mass production and saving of energy input, although it has less relative removal of heavy metal ions than tube-furnace and microwave oven (700 W). The results of this study show that the chemical modification of biomass using phosphoric acid and low-temperature pyrolysis can be potentially applied in the treatment wastewater contaminated with heavy metal ion in the future