• Economic and Environmental Geology
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• v.55 no.2
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• pp.171-181
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• 2022

The Geochang Au-Ag deposit is located within the Yeongnam Massif. Within the area a number of hydrothermal quartz and calcite veins were formed by narrow open-space filling of parallel and subparallel fractures in the granitic gneiss and/or gneissic granite. Mineral paragenesis can be divided into two stages (stage I, ore-bearing quartz vein; stage II, barren calcite vein) by major tectonic fracturing. Stage I, at which the precipitation of major ore minerals occurred, is further divided into three substages (early, middle and late) with paragenetic time based on minor fractures and discernible mineral assemblages: early, marked by deposition of pyrite with minor pyrrhotite and arsenopyrite; middle, characterized by introduction of electrum and base-metal sulfides with minor sulfosalts; late, marked by hematite with base-metal sulfides. Fluid inclusion data show that stage I ore mineralization was deposited between initial high temperatures (≥380℃ ) and later lower temperatures (≤210℃ ) from H₂O-CO₂-NaCl fluids with salinities between 7.0 to 0.7 equiv. wt. % NaCl of Geochang hydrothermal system. The relationship between salinity and homogenization temperature indicates a complex history of boiling, fluid unmixing (CO₂ effervescence), cooling and dilution via influx of cooler, more dilute meteoric waters over the temperature range ≥380℃ to ≤210℃. Changes in stage I vein mineralogy reflect decreasing temperature and fugacity of sulfur by evolution of the Geochang hydrothermal system with increasing paragenetic time. The Geochang deposit may represents a mesothermal gold-silver deposit.

• Economic and Environmental Geology
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• v.54 no.6
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• pp.753-765
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• 2021

The Dongwon Au-Ag deposit is located within the Paleozoic Taebaeksan province, Okcheon belt. Mineral paragenesis can be divided into two stages (stage I, ore-bearing quartz veins; stage II, barren carbonate veins) by major tectonic fracturing. Stage I, at which the precipitation of major ore minerals occurred, is further divided into three substages(early, middle and late) with paragenetic time based on minor fractures and discernible mineral assemblages: early, marked by deposition of pyrite with minor magnetite, pyrrhotite and arsenopyrite; middle, characterized by introduction of electrum and base-metal sulfides with minor sulfosalts; late, marked by argentite, Cu-As (and/or Sb) and Ag-Sb sulfosalts with base-metal sulfides. Fluid inclusion data show that stage I ore mineralization was deposited between initial high temperatures (≥430℃) and later lower temperatures (≤230℃) from fluids with salinities between 6.0 to 0.4 wt. percent equiv. NaCl. The relationship of salinity and homogenization temperature suggest that ore mineralization at Dongwon was deposited mainly due to fluid boiling, cooling and dilution via influx of cooler, more dilute meteoric waters. Changes in stage I vein mineralogy reflect decreasing temperature and fugacity of sulfur by evolution of the Dongwon hydrothermal system with increasing paragenetic time. The Dongwon deposit may represents a Korean-type and/or Au-Ag type mesothermal/epithermal gold-silver deposit.

• Economic and Environmental Geology
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• v.48 no.1
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• pp.1-13
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• 2015

The geology of the Seungryung Zn deposit, located in the Muzu basin, consists of Precambrian leucocratic granitic gneiss, Cretaceous clastic rocks, pyroclastic rocks, and intrusive rocks. The deposit shows a weakly skarnized hydrothermal replacement ore developed along limestone bed in the gneiss. The mineralization can be divided into three stages: the early skarnization producing garnet and pyroxene, the main mineralization in the middle stage precipitating most metallic minerals such as magnetite, sphalerite, chalcopyrite, pyrrhotite, Pb-Ag-Bi-S system minerals, and the late stage for altered or low temperature minerals such as chlorite and marcasite. Pb-Ag-Bi-S system minerals include heyrovskite-eskimoite solid solution, lillianite-gustavite solid solution, and vikingite. Chalcopyrite diseases are quite common in sphalerite showing bead chains and dusting textures. The ${\delta}^{34}S$ values of sulfides minerals are concentrated within the narrow range of 3.4~4.1‰ for pyrite, 3.3~4.3‰ for sphalerite, 4.0~4.3‰ for chalcopyrite, and 2.8‰ for galena, suggesting that most sulfur is of igneous origin. Sulfur isotope geothermometry is calculated to be $346{\sim}431^{\circ}C$, implying that the mineralization occurred at relatively high temperature. FeS contents of sphalerite are relatively high in the range of 6.58~20.16 mole% (avg. 16.58 mole%) with the enrichment of Mn compared to Cd, similarly to representative skarn Pb-Zn deposits in South Korea. On the contrary, sphalerite from Au-Ag deposits in the Seolcheon mineralized zone around the Seungryung deposit is enriched in Cd, showing similar feature like representative epithermal Au-Ag deposits. This suggests that around the related igneous rocks, magnetite and sphalerite were produced at high temperature in the Seungryung deposit, and with decreasing temperature and compositional change of mineralizing fluids, Au-Ag mineralization proceeded in the Seolcheon mineralized zone.

• Economic and Environmental Geology
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• v.50 no.5
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• pp.325-340
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• 2017

The Seongdo Pb-Zn deposit, located in the northwestern part of the Ogcheon Metamorphic Belt, consists of skarn ore replacing limestone within the Hwajeonri Formation of Ogcheon Group and hydrothermal vein ore filling the fracture of host rock. Skarn minerals comprise mostly hedenbergitic pyroxene, garnet displaying oscillatory zonal texture composed of grossular and andradite, and a small amount of wollastonite, tremolite, and epidote, indicating reducing condition of formation. Ore minerals of skarn ore include sphalerite and galena with a small amount of pyrite, pyrrhotite, and chalcopyrite. In hydrothermal vein ore, arsenopyrite, sphalerite, chalcopyrite, and pyrite occur with a small amount of galena, native Bi, and stannite. Chemical compositions of sphalerite vary from 17.4 mole% FeS in average for dark grey sphalerite, 3.6 mole% for reddish brown sphalerite in skarn ore, and to 10.3 mole% FeS in hydrothermal vein ore. In comparison with representative metallic deposits in South Korea on the FeS-MnS-CdS diagram, skarn and hydrothermal vein ore plot close to the field of Pb-Zn deposits and Au-Ag deposits, respectively. Arsenic contents of arsenopyrite in hydrothermal vein ore decrease from 31.93~33.00 at.% in early stage to 29.58~30.21 at.% in middle stage, and their corresponding mineralizing temperature and sulfur fugacity are $441{\sim}490^{\circ}C$, $10^{-6}{\sim}10^{-4.5}atm$. and $330{\sim}364^{\circ}C$, <$10^{-8}atm$. respectively. Phase equilibrium temperatures calculated from Fe and Zn contents for coexisting sphalerite and stannite in hydrothermal vein are $236{\sim}254^{\circ}C$. Sulfur isotope compositions are 5.4~7.2‰ for skarn ore and 5.4~8.4‰ for hydrothermal vein ore, being similar or slightly higher to magmatic sulfur, suggesting that ore sulfur was mostly of magmatic origin with partial derivation from host rocks. However, much higher sulfur isotope equilibrium temperatures of $549^{\circ}C$와 $487^{\circ}C$, respectively for skarn ore and hydrothermal ore, than those estimated from phase equilibria imply that isotopic equilibrium has not been fully established.

• Transactions of the Korean hydrogen and new energy society
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• v.25 no.5
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• pp.482-490
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• 2014

Gaseous sulfur compound such as $H_2S$ or COS in coal- or biomass-derived hot syngas can be purified by solid sorbents at high temperatures. In this study, we investigated the physical properties and reactivity of solid regenerable desulfurization sorbents with 37.2, 41.9, and 46.5wt% ZnO to look into the ZnO content effect. The sorbents were produced by spray-drying method to apply to a fluidized-bed process. Sulfidation and regeneration reaction were carried out using a thermogravimetric analyzer. Sorbent prepared with 46.5wt% ZnO had physical properties suitable for a fluidized-bed process applications such as spherical shape, sufficient mechanical strength and density, high porosity and surface area. It showed high sulfur sorption capacity of 10.4wt% (ZnO utilization of 57%) at reaction temperatures of 500 and $650^{\circ}C$ for sulfidation and regeneration, respectively. However, the sulfur sorption capacity and ZnO utilization were significantly reduced and dimple shape appeared when the ZnO content decreased to 37.2 and 41.9wt%. Sulfur sorption capacity and regenerability were improved as reaction temperature increased within the experimental temperatures used in this work. The reaction temperature zones of $1500{\sim}550^{\circ}C$ and $650{\sim}700^{\circ}C$ are recommended for sulfidation and regeneration, respectively, to lead best reaction performances of the ZnO-based spray-dried sorbents developed in this work.

• Journal of Energy Engineering
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• v.11 no.3
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• pp.247-253
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• 2002

Natural manganese ore was selected as main active component for a non-zinc desulfurization sorbent used in the gas clean-up process of the integrated gasification combined cycle (IGCC) because of excellent H$_2$S removal efficiency and economical aspect . In this study, the regeneration characteristics of sorbent after desulfurization reaction were determined in a thermobalance reactor and a fixed bed reactor in the temperature range of 350~55$0^{\circ}C$. The mixed gases of oxygen and nitrogen are used as the regeneration reaction gases for manganese sorbent. According to Mn-S-O phase diagram, the manganese sorbent has a low regeneration efficiency in medium temperature due to formation of MnSO$_4$ and the regeneration temperature must be over 85$0^{\circ}C$. To improve that problem, ammonia and steam was added in regeneration mixed gases. Effect of new regeneration method was determined by XRD and difference of desulfurization through multicycle tests.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.880-883
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• 2009

석탄가스화복합발전(IGCC) 시스템에서 합성가스 중에 포함된 황화수소($H_2S$)는 후단의 가스 터빈과 같은 장치의 부식을 방지하고, 합성가스를 이용하는 연료전지 등의 연계 공정에서 요구하는 수준에 맞추어 정제되어야 한다. 본 연구에서는 $H_2S$ 정제공정 추가에 따른 IGCC 시스템의 효율저하를 최소화하기 위하여 고온고압에서 사용가능한 탈황제를 분무건조법을 이용하여 제조하고 제조된 탈황제에 대해 물성 및 황 흡수능 시험을 실시하였다. 형상, 내마모도, 평균입자크기, 충진밀도와 함께 제조된 탈황제가 적용되는 유동층 공정에 적합한 강도를 보유하는지 여부를 미국표준시험방법에 의하여 측정하였다. 황 흡수능은 열중량분석기를 반응기로 사용하여 모사 합성 가스 분위기에서 측정하였다. 분무건조 성형된 탈황제의 일부가 구형이 아닌 타원형 또는 도넛 형태를 나타내고 있어 형상 개선을 위한 제조방법 개선이 필요한 것으로 나타났다. 제조된 탈황제는 기공도가 65% 이상으로 macropore가 기공부피의 대부분을, mesopore가 비표면적의 대부분을 제공하고 있었다. 소성온도를 650 $^{\circ}C$에서 750 $^{\circ}C$로 증가시킴에 따라 대체로 강도가 감소하는 경향을 나타내었다. 열중량분석기로 측정된 황 흡수능은 약 10 wt%로 나타났다. 제조된 탈황제 중 일부는 유동층 공정에 적합한 물성을 보유하고 있었으며 반응성 또한 기존에 개발된 탈황제에 버금가는 성능을 나타내어 향후 공정 적용이 가능할 것으로 분석되었다.

• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.106.1-106.1
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• 2011

The Cu(In,Ga)Se2 (CIGS) thin film solar cells have been achieved until almost 20% efficiency by NREL. These solar cells include chemically deposited CdS as buffer layer between CIGS absorber layer and ZnO window layer. Although CIGS solar cells with CdS buffer layer show excellent performance, the short wavelength response of CIGS solar cell is limited by narrow CdS band gap of about 2.42 eV. Taking into consideration the environmental aspect, the toxic Cd element should be replaced by a different material. Among Cd-free candidate materials, the CIGS thin film solar cells with ZnS buffer layer seem to be promising with 17.2%(module by showa shell K.K.), 18.6%(small area by NREL). However, ZnS/CIGS solar cells still show lower performance than CdS/CIGS solar cells. There are several reported reasons to reduce the efficiency of ZnS/CIGS solar cells. Nakada reported ZnS thin film had many defects such as stacking faults, pin-holes, so that crytallinity of ZnS thin film is poor, compared to CdS thin film. Additionally, it was known that the hetero-interface between ZnS and CIGS layer made unfavorable band alignment. The unfavorable band alignment hinders electron transport at the heteo-interface. In this study, we focused on growing defect-free ZnS thin film and for favorable band alignment of ZnS/CIGS, bandgap of ZnS and CIGS, valece band structure of ZnS/CIGS were modified. Finally, we verified the photovoltaic properties of ZnS/CIGS solar cells.

• Applied Chemistry for Engineering
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• v.10 no.2
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• pp.183-189
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• 1999

Zinc-based sorbents for $H_2S$ removal were prepared. The reactivity of sorbents was investigated by the successive cycles of sulfidation-regeneration at $650^{\circ}C$ in a fixed bed reactor. The desulfurization sorbents were prepared with granulation method to produce a spherical pellet with good attrition resistance. The fresh and reacted sorbents were characterized by X-Ray Diffraction (XRD) and X-Ray Photoelectron Spectroscopy (XPS) and the characteristics of sorbents on calcination conditons were analysed by Mercury Porosimetery and BET. The reactivity of sorbents decreased as the number of sulfidation-regeneration cycle increased. It is due to the zinc loss and the increase of the diffusion resistance by sintering, cracking and spalling of sorbents at the high temperature.

• Journal of the Mineralogical Society of Korea
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• v.20 no.2 s.52
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• pp.115-124
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• 2007

Electrum-sulfide mineralization of the Youngbogari mine area occurred in two stages of massive quartz veins that fill the fractures along the fault/shear zones in the Precambrian gneiss. Ore mineralogy is simple, consisting of arsenopyrite $(31.4{\sim}33.4atom.%As)$, pyrite, sphalerite $(4.1{\sim}17.6mole%FeS)$, galena, chalcopyrite, argentite, and electrum. Electrum $(60.3{\sim}87.6atom.%Ag)$ is associated with galena, chalcopyrite and late sphalerite infilling the fractures in quartz and sulfides. Fluid inclusion data show that ore mineralization was formed from $H_2O-CO_2-CH_4-NaCl$ fluids $(X_{CO2+CH4}=0.0\;to\;0.2)$ with low salinities (0 to 10wt.% eq. NaCl) at temperatures between $200^{\circ}\;and\;370^{\circ}C$. Gold-silver mineralization occurred later than the base-metal sulfide deposition, at temperatures near $250^{\circ}C$ and was probably a result of cooling and decreasing sulfur fugacity caused by sulfide precipitation and/or $H_2S$ loss through fluid unmixing.