• Title/Summary/Keyword: ZnS:Cu

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The Treatment of Heavy Metal-cyanide Complexes Wastewater by Zn$^{+2}$/Fe$^{+2}$ Ion and Coprecipitation in Practical Plant (II) (아연백법 및 공침공정을 이용한 복합 중금속-시안착염 폐수의 현장처리(II))

  • Lee, Jong-Cheul;Lee, Young-Man;Kang, Ik-Joong
    • Journal of Korean Society of Environmental Engineers
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    • v.30 no.5
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    • pp.524-533
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    • 2008
  • Industrial wastewater generated in the electroplating and metal finishing industries typically contain toxic free and complex metal cyanide with various heavy metals. Alkaline chlorination, the normal treatment method destroys only free cyanide, not complex metal cyanide. A novel treatment method has been developed which destroys both free and complex metal cyanide as compared with Practical Plant(I). Prior to the removal of complex metal cyanide by Fe/Zn coprecipitation and removal of others(Cu, Ni), Chromium is reduced from the hexavalent to the trivalent form by Sodium bisulfite(NaHSO$_3$), followed by alkaline-chlorination for the cyanide destruction. The maximum removal efficiency of chromium by reduction was found to be 99.92% under pH 2.0, ORP 250 mV for 0.5 hours. The removal efficiency of complex metal cyanide was max. 98.24%(residual CN: 4.50 mg/L) in pH 9.5, 240 rpm with 3.0 $\times$ 10$^{-4}$ mol of FeSO$_4$/ZnCl$_2$ for 0.5 hours. The removal efficiency of Cu, Ni using both hydroxide and sulfide precipitation was found to be max. 99.9% as Cu in 3.0 mol of Na$_2$S and 93.86% as Ni in 4.0 mol of Na$_2$S under pH 9.0$\sim$10.0, 240 rpm for 0.5 hours. The concentration of residual CN by alkaline-chlorination was 0.21 mg/L(removal efficiencies: 95.33%) under the following conditions; 1st Oxidation : pH 10.0, ORP 350 mV, reaction time 0.5 hours, 2nd Oxidation : pH 8.0, ORP 650 mV, reaction time 0.5 hours. It is important to note that the removal of free and complex metal cyanide from the electroplating wastewater should be employed by chromium reduction, Fe/Zn coprecipitation and, sulfide precipitation, followed by alkaline-chlorination for the Korean permissible limit of wastewater discharge, where the better results could be found as compared to the preceding paper as indicated in practical treatment(I).

암모니아의 농도에 따른 CBD-ZnS/CIGS 박막태양전지의 제작 및 분석

  • Jeong, Yong-Deok;Choe, Hae-Won;Jo, Dae-Hyeong;Park, Rae-Man;Lee, Gyu-Seok;Kim, Je-Ha
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.08a
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    • pp.298-299
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    • 2010
  • Cu(In, Ga)Se2 (CIGS) 박막 태양전지는 Soda lime glass/Mo/CIGS/CdS/ZnO/ITO/Al 의 구조를 가지고 있다. CIGS 화합물은 direct bandgap 구조를 하고 있으며, 광흡수율이 다른 어떤 물질들 보다 뛰어나 박막으로도 충분히 태양광을 흡수할 수 있다. 또한 Ga의 도핑 농도에 따른 밴드갭 조절도 가능하다. 이러한 성질들로 인해 현재 박막태양전지로서 20.1%의 최고효율을 가지고 있다.[1] CIGS 박막 태양전지에서 p-CIGS layer와 스퍼터링으로 증착되는 n-ZnO layer사이의 buffer 층으로 chemical bath deposition (CBD)-CdS 박막을 주로 사용한다. CBD-CdS 박막은 n-ZnO 스퍼터로 증착 시킬 때, CIGS 층의 손상을 최소화하고, 이 두 층 사이에서의 격자상수와 밴드갭의 차이를 줄여주어 CIGS 박막태양전지의 효율을 증가 시키는 역할을 한다. 하지만, Cd (카드뮴)의 심각한 독성과 낮은 밴드갭(2.4eV)으로 인해 CIGS 층에서의 광흡수율을 줄여, CdS를 대체할 새로운 buffer 층의 필요성이 대두되었다.[2] 그 대안으로 ZnS, Zn(O, S, OH), (Zn, Mg)O, In2S3 같은 물질이 연구되고 있다. 현재 CBD-ZnS를 buffer 층으로 사용한 CIGS 박막태양전지의 효율은 최고 18.6%로 CBD-CdS의 최고효율보다는 약 1.5% 낮지만, ZnS가 높은 밴드갭(3.7~3.8eV)과 Cd-free 물질이라는 점에서 CdS를 대체할 물질로 각광받고 있다. 본 연구에서는 기존의 CdS 박막을 제조하는 방법과 같은 방법인 CBD를 이용하여 ZnS 박막을 제조하였다. ZnS 박막을 제조하기 위해서는 Zinc sulfate, Thiourea, 암모니아가 사용된다. 암모니아의 mol 농도에 따른 CBD-ZnS/CIGS 박막태양전지의 효율 변화를 관찰하기 위해 암모니아의 mol 농도는 1 mol, 2 mol, 3 mol, 4 mol, 5 mol, 6 mol, 그 이상의 과량을 사용하여 실험하였다. 실험 결과, 암모니아농도 5 mol에서 효율 13.82%를 확인할 수 있었다. 최고효율을 보인 조건인 암모니아 농도가 5 mol 일 때, Voc는 0.602V, Jsc는 33.109mA/cm2, FF는 69.4%를 나타내었다.

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Concentration of Heavy Metals in Seawater, Fish, and Shellfish at Lake Shihwa (시화호 내 수질 및 어패류의 중금속 분포 연구)

  • Lee, Gyuyoung;Lee, Seunghun;Oh, Sehun;Choi, Minji;Lee, Yong-Woo
    • Journal of Korean Society on Water Environment
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    • v.34 no.2
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    • pp.157-163
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    • 2018
  • This study aims to determine the pollution levels of nine kinds of heavy metals (As, Cd, Cu, Cr, Hg, Mn, Ni, Pb, and Zn) in Lake Shihwa, which is susceptible to the inflow of pollutants, and the levels of heavy metal exposure in its fish and shellfish. Shihwa Lake's water quality did not exceed the short-term standard for protection of marine ecosystems, but concentrations of As, Cu, Cr, Hg, Ni, and Zn exceeded the long-term standard for protection of a marine ecosystem. In comparison to findings in prior research, performed in 2010, levels of Cr, Ni, As, and Zn are now 4.1 times lower. However, when compared to Saemangeum Lake, the environment is similar to that of Lake Shihwa, Cu, Ni, Hg, Mn, and Zn were 244.4 times higher. The levels of Pb, Cd, and Hg in fish's muscles did not exceed the average values set by the marine safety standard. However, when compared to the fish from the Korean coast, the levels of heavy metals were 9.7 times higher, on average. The levels of heavy metals in fish's livers were on average 26.8 times higher than in the muscles. In the case of shellfish, the levels of Pb, Cd, and Hg did not exceed the standard values, but in comparison to the shellfish from the south coast, the levels of heavy metals were 6.2 times higher on average. In particular, Mn (153.5 times higher) from fish and Cd (14.7 times higher) from shellfish were found in high amounts, indicating a concerning level of these specific heavy metals.

Acute toxicity of antifouling agents(TBT, Sea-nine, Cu-pyrithione and Zn-pyrithione) to rockfish Sebastes schlegeli and amphipod Monocorophium acherusicum (방오도료(TBT, Sea-nine, Cu-pyrithione과 Zn-pyrithione)의 조피볼락 Sebastes schlegeli 과 단각류 Monocorophium acherusicum에 대한 급성독성 비교)

  • Park Kun-Ho;Lee Kyu-Tae;Lee Jung-Suk;Han Kyung-Nam
    • Journal of the Korean Society for Marine Environment & Energy
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    • v.9 no.1
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    • pp.21-28
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    • 2006
  • Since the usage of tributyltin(TBT) has been banned, many chemicals including Sea-Nine 211, Cu-pyrithione, and Zn-pyrithione were developed to use as antifouling agents for ships and coastal structures. However, the toxicity of these antifouling chemicals have not been systematically evaluated in ecotoxicological and biological studies. In this study, we investigated the effect of four antifouling substances on survival of estuarine rockfish, Sebastes schlegeli and amphipod, Monocorophium acherusicum. Survival of S. schlegeli and M. acherusicum during the 96-h exposure period were used to estimate the median lethal concentrations(LC50s) of test chemicals for each test species. Among antifouling agents, Cu-pyrithione($56{\mu}g{\cdot}1^{-1}$;96-h LC50) was most toxic to S. schlegeli, followed by $TBT(73{\mu}g{\cdot}1^{-1}),\;Sea-Nine(184{\mu}g{\cdot}1^{-1})\;and\;Zn-pyrithione(l707{\mu}g{\cdot}1^{-1})$, while TBT($26{\mu}g{\cdot}1^{-1}$) was most toxic to M. acherusicum followed by Sea-Nine($49{\mu}g{\cdot}1^{-1}$), Cu-pyrithione($119{\mu}g{\cdot}1^{-1}$) and Zn-pyrithione($334{\mu}g{\cdot}1^{-1}$). Effect concentrations of the antifouling chemicals estimated in this study can be used when assessing the potential risks of these substances, of which usage is increasing in the coastal environment.

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Effect of Alloying Element Addition on the Microstructure, Tensile and Impact Toughness of the Modified Al-6.5Si Alloy (개량 Al-6.5Si 합금의 미세조직, 인장 및 충격 인성에 미치는 합금 원소 첨가의 영향)

  • Park, T.H.;Baek, M.S.;Yoon, S.I.;Kim, J.P.;Lee, K.A.
    • Transactions of Materials Processing
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    • v.29 no.3
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    • pp.135-143
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    • 2020
  • Low-cost alloying elements were added to a modified Al-6.5Si alloy and its microstructure, tensile and impact toughness properties were investigated. The alloying elements added were Mg, Zn, and Cu, and two kinds of alloy A (Mg:0.5, Zn:1, Cu:1.5 wt.%) and alloy B (Mg:2, Zn:1.5, Cu:2 wt.%) were prepared. In the as-cast Al-6.5Si alloys, Si phases were distributed at the dendrite interfaces, and Al2Cu, Mg2Si, Al6 (Fe,Mn) and Al5 (Fe,Mn)Si precipitates were also observed. The size and fraction of casting defects were measured to be higher for alloy A than for alloy B. The secondary dendrite arm spacing of alloy B was finer than that of alloy A. It was confirmed by the JMatPro S/W that the cooling rate of alloy B could be more rapid than alloy A. The alloy B had higher hardness and strength compared to the values of alloy A. However, the alloy A showed better impact toughness than alloy B. Based on the above results, the deformation mechanism of Al-6.5Si alloy and the improving method for mechanical properties were also discussed.

Distributions and Pollution History of Heavy Metals in Nakdong Estuary Sediments (낙동강 하구역 퇴적물 중금속의 분포와 오염의 역사 추정)

  • Cho, Jin-Hyung;Park, Nam-Joon;Kim, Kee-Hyun
    • The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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    • v.5 no.4
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    • pp.285-294
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    • 2000
  • In order to determine the horizontal and vertical distributions of metals and prospect the recent metal pollution history in Nakdong Estuary, we took surface and core sediments. Maximum value of organic matter occurs at the upstream site located 4 km from Nakdong barrage, and the concentration of trace metals (Zn, Cu, and Pb etc.) decrease seaward in the estuary. The sedimentation rates, based on $^{210}$Pb$_{ex}$ and $^{137}$Cs activities, were 0.34 cm/yr in inside of barrage (core 1) and 0.25 cm/yr in Changrim (core 4). Sediment mixing layer does not exist in core 1, where anoxic condition is known to be prevail. The topmost sediment layer of core 4 (<3.5 cm) is severely mixed. At sites 1 and 4, concentrations of Cu slowly increased during the period of 1920-1970, rapidly increased during 1970-1990, and followed by slight decrease after 1990. Zn contents increased in early 1960s and peaked in 1993, and followed by decrease after 1990s. Pb has increased continuously since early 1970s. At the downstream of the barrage, Cu and Zn have increased in the topmost layer. The trend of increase of Cu is evident after 1950 (11 cm in sediment depth). Overall trend of heavy metal concentration clearly indicates the pollution has been increasing after the construction of the barrage.

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Separation of Heavy Metals from Metal-EDTA in Spent Soil Washing Solution by using Na2S (Na2S를 이용한 EDTA 토양세척수로부터의 중금속 분리)

  • Oh, Sanghwa;Shin, Won Sik
    • Journal of Soil and Groundwater Environment
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    • v.20 no.7
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    • pp.103-111
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    • 2015
  • Soil washing with ethylenediaminetetraacetic acid (EDTA) is highly effective in the remediation of soils contaminated with heavy metals. The EDTA recycling process is a requisite for reducing the operating cost. The applicability of Na2S addition on the precipitation of heavy metals from the spent soil washing solution and thereby recycling of EDTA was investigated. Addition of Na2S into the single metal-EDTA and the mixed metal-EDTA solutions ([Na2S]/[metal-EDTA] ratio = 30, reaction time = 30 min and pH = 7~9) was highly effective in the separation of Cu and Pb from metal-EDTA complexes, but not for Ni. The Zn removal efficiency varied with pH and slightly increased upto 40% as the reaction time increased from 0 to 240 min which was longer than those for Cu and Pb. Ca(OH)2 was subsequently added to induce further precipitation of Zn and Ni and to reduce the Na2S dose. At the [Na2S]/[metal-EDTA] ratio of 10, the removal efficiencies of all heavy metals excluding Ni were above 98% with the dose of Ca(OH)2 at 0.002, 0.006 and 0.008 g into 100 mL of Cu-, Pb- and Zn-EDTA solutions, respectively. However, Ca(OH)2 addition was not effective for Ni-EDTA solution. A further research is needed to improve metal removal efficiency and subsequent EDTA recycling for the real application in field-contaminated soils.

Characteristics of Metal-Phthalocyanine for Catalytic Combustion of Methanol (메탄올의 촉매연소에 대한 금속-프탈로시아닌의 특성)

  • Seo, Seong-Gyu;Yoon, Hyung-Sun;Lee, Sun-Won
    • Journal of Korean Society of Environmental Engineers
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    • v.22 no.10
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    • pp.1809-1816
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    • 2000
  • The catalytic combustion of methanol as a model volatile organic compound(VOC) was been investigated over metal-phthalocyanine(PC) in a fixed bed flow reactor system. The catalytic activity of Co-PC pretreated with air and methanol mixture at $450^{\circ}C$ and 60 cc/min for 1 hr was very excellent. The order of catalytic activity on methanol combustion was summarized as follows: metal free-PC < Zn-PC < Fe-PC < Cu($\alpha$)-PC < Co-PC. By TG/DTA analysis, the tendency of thermal decomposition was increased as follows: metal free-PC < Zn-PC < Cu($\alpha$)-PC < Co-PC < Fe-PC. Under this pretreatment condition, the basic structures of Co-PC, Cu($\alpha$)-PC and Fe-PC were destroyed, and the new metal oxide such as $Co_3O_4$ from Co-PC was confirmed by EA and XRD analysis. But Zn-PC and metal free-PC were retained its basic structure under this pretreatment condition. On the combustion of methanol over Co-PC, HCHO and $HCOOCH_3$ were observed as an intermediate products in the high concentration of reactant or the short contact time(W/F).

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Reaction Characteristics of Water Gas Shift Catalysts in Various Operation Conditions of Blue Hydrogen Production Using Petroleum Cokes (석유코크스 활용 블루수소생산을 위한 Water Gas Shift 촉매의 조업조건에 따른 반응특성)

  • Park, Ji Hye;Hong, Min Woo;Yi, Kwang Bok
    • Clean Technology
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    • v.28 no.1
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    • pp.1-8
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    • 2022
  • To confirm the applicability of the water gas shift reaction for the production of high purity hydrogen for petroleum cokes, an unutilized low grade resource, Cu/ZnO/MgO/Al2O3 (CZMA), catalyst was prepared using the co-precipitation method. The prepared catalyst was analyzed using BET and H2-TPR. Catalyst reactivity tests were compared and analyzed in two cases: a single LTS reaction from syngas containing a high concentration of CO, and an LTS reaction immediately after the syngas passed through a HTS reaction without condensation of steam. Reaction characteristics in accordance with steam/CO ratio, flow rate, and temperature were confirmed under both conditions. When the converted low concentration of CO and steam were immediately injected into the LTS, the CO conversion was rather low in most conditions despite the presence of large amounts of steam. In addition, because the influence of the steam/CO ratio, temperature, and flow rate was significant, additional analysis was required to determine the optimal operating conditions. Meanwhile, carbon deposition or activity degradation of the catalyst did not appear under high CO concentration, and high CO conversion was exhibited in most cases. In conclusion, it was confirmed that when the Cu/ZnO/MgO/Al2O3 catalyst and the appropriate operating conditions were applied to the syngas composition containing a high concentration of CO, the high concentration of CO could be converted in sufficient amounts into CO2 by applying a single LTS reaction.