섬아연석 억제제인 황산아연과 잔세이트의 상호 작용에 관한 연구

김민규,유광석 한국자원리싸이클링학회 2020 資源 리싸이클링 Vol.29 No.6

In this study, the depression behavior of zinc sulfate on the sphalerite with the addition of potassium butyl xanthate was investigated to clear the relationship between zinc sulfate and xanthate in depression of sphalerite. As a result of the experiment, it was confirmed that the depress effect of zinc sulfate on the sphalerite declined with the increase of its addition amount. From the results of SEM-EDS and FT-IR analysis, it was found out that the amorphous precipitate of metal xanthate (Zn-BX) was formed in sphalerite concentrate, when the solubility product of [Zn+ ]·[BX] in the pulp solution exceeded 3.71×10- 11 , which is the solubility of Zn-butyl xanthate. It is considered that the Zn-butyl xanthate had a negative effect on the depression of sphalerite. 섬아연석(Sphalerite, ZnS)을 대상으로 억제제 황산아연(zinc sulfate, ZnSO4)과 포수제인 포타슘 부틸 잔세이트(potassium butyl xanthate(KBX), C5H9KOS2)과의 상호 작용 및 이에 따른 섬아연석의 억제 거동을 규명하고자 섬아연석 부유 선별 실험을 진행했다. 실험결과, 억제제인 황산아연 첨가량이 일정 농도 이상에서는 KBX의 첨가로 섬아연석의 오히려 억제 효과가 떨어졌다. 할리몬드 튜브(Hallimond Tube) 부유선별 실험을 통해 얻어진 정광과 맥석을 대상으로 주사형 전자현미경/X선 분광분석(Scanning electron microscope/ energy dispersive spectroscopy, SEM-EDS: TM3000, Tabletop Microscope, HITACH)과 푸리에 변환 적외선분광법(Fourier-transform infrared spectroscopy, FT-IR: NICOLET 6700, Thermo SCIENTIFIC)로 분석한 결과 정광에서는 비정질의 Zn-butyl xanthate(Zn-BX) 가 생성되어 광물 입자에 흡착되어 있는 것을 확인 했다. 이러한 생성물은 용액 내 첨가된 황산아연의 용해에 따른 잔류 Zn 이온과 KBX 이온이 반응하여 생성되었다. 즉, 용액의 [Zn+ ]·[BX] 용해도 곱이 3.71×10- 11 이상에서 Zn-butyl xanthate이 생성되며, 이로 인해 섬아연석 억제에 부정적인 영향을 끼치는 것으로 나타났다.

무주 수왕광산에서 산출되는 섬아연석의 황동석 병변에 관한 연구

윤석태 한국지구과학회 2008 한국지구과학회지 Vol.29 No.7

The Soowang deposits occur in the quartz veins that were filled fissures in the middle Cretaceous porphyritic granite and/or the Precambrian Sobaegsan gneiss complex. Paragenetic studies suggest that the vein filling can be divided into four identifiable stages. Sphalerites were deposited by the cooling fluids at stages Ⅰ, Ⅱ, and Ⅲ. The results of microscopic observation and EPMA analysis suggest that the chalcopyrite dots and disease in sphalerite are replacement products by later hydrothermal solution at the early stage Ⅲ. The inferred processes of chalcopyrite disease are as follows : (1) Fe enrichment to the margins and along the cracks of the Fe-poor sphalerite by Fe-rich solution, (2) Formation of chalcopyrite dots in the Fe-enriched sphalerite formed at the stage Ⅱ, and Fe reduction of sphalerite near the chalcopyrite dots by Cu-bearing solution, (3) Formation of "chalcopyrite disease" penetrating the compositional zoning of sphalerite at the early stage Ⅲ. 수왕광상은 중생대 백악기 중기의 반상화강암이나 선캄브리아기의 소백산 편마암 복합체에 발달한 열극을 충진한 석영맥에서 산출된다. 광물 공생군에 대한 연구 결과 광화작용은 4차례에 걸쳐 일어났다. 섬아연석은 광화작용이 진행되는 동안 광화Ⅰ, Ⅱ, Ⅲ기에 각각 정출하였다. 현미경 관찰과 전자현미분석 결과 섬아연석에서 나타나는 황동석 점적과 황동석 병변은 광화 Ⅲ기 초에 열수용액의 교대작용에 의하여 생성되었을 것으로 생각된다. 황동석 병변의 생성 과정은 아래와 같다. (1) Fe가 풍부한 용액이 Fe가 결핍된 섬아연석의 가장자리나 틈을 통해 Fe 부화 (2) 광화Ⅱ기에 Fe가 결핍된 섬아연석에 황동석 점적을 형성하고 Cu를 함유한 용액에 의해 황동석 점적 주변의 섬아연석에 Fe 감소 (3) 광화Ⅲ기 초에 황동석 병변을 형성하였다.

Sphalerite geochemistry of the Zn-Pb orebodies in the Taebaeksan metallogenic province, Korea

Lee, Jun Hee,Yoo, Bong Chul,Yang, Yun-Seok,Lee, Tong Ha,Seo, Jung Hun Elsevier 2019 Ore geology reviews Vol.107 No.-

<P><B>Abstract</B></P> <P>The Taebaeksan region, located in the northeastern part of South Korea, is an important metallogenic province which hosts numerous Zn-Pb-W-Mo-Fe-Cu (-Au-Ag) mineral systems. The Zn-Pb orebodies in the region (inclusive of skarn, carbonate replacement, and vein-breccia ore types) are hosted on the early Paleozoic carbonate sequences and they are associated with late Cretaceous to early Paleogene magmatic-hydrothermal activities. We collected Zn-Pb orebodies from 15 areas including non-metal deposits, such as high-Ca calcite marble, as well as exploration sites in the Taebaeksan metallogenic province. Thereafter, we studied the geochemistry of the sphalerite present in them to understand the regional Zn-Pb mineralization process and to establish an exploration strategy.</P> <P>The sphalerites collected from the region contained detectable amounts of Fe, Mn, Cd, Co, Cu, Ga, Ge, Mo, Ag, In, Sn, Sb, W, Tl, Pb, and Bi which were identified using microbeam techniques like EPMA and LA-ICP-MS. Sphalerites from economically significant Zn-Pb deposits characteristically have high Mn and low Cd content, while W (-Mo)-bearing deposits have remarkably high Cd content. Correlation trends between trace elements demonstrate the coupled substitution mechanisms such as 3 Zn<SUP>2+</SUP> ↔ 2 (Cu<SUP>+</SUP> or Ag<SUP>+</SUP>) + Sn<SUP>4+</SUP> and 2 Zn<SUP>2+</SUP> ↔ Cu<SUP>+</SUP> + In<SUP>3+</SUP>, occurring in the sphalerite. High-temperature ores such as skarn and vein-breccia are relatively enriched with Co and In, while Ga, Ag, and Sn tend to be concentrated in the relatively low-temperature ores, such as carbonate replacement type ores.</P> <P>Lead isotope compositions of the sphalerites show a well-defined, positive, linear trend with those of the local Cretaceous intrusions and the sedimentary sequence of the Taebaeksan region. Major economic Zn-Pb deposits show relatively more signatures of non-radiogenic Pb isotope closer to the intrusions, as compared to the minor and sub-economic Zn-Pb orebodies. The Pb isotope signature suggests that Cretaceous magmatic-hydrothermal fluids with a minimal degree of fluid-rock interactions are required for economic Zn-Pb mineralization in the Taebaeksan metallogenic province.</P> <P><B>Highlights</B></P> <P> <UL> <LI> The Zn-Pb orebodies in the Taebaeksan region were formed by magmatic-hydrothermal activities. </LI> <LI> Economic Zn-Pb mineralization is associated with minimal fluid-rock interaction. </LI> <LI> Trace elements in sphalerites show a temperature-dependent systematic trend. </LI> <LI> Geochemistry of the sphalerite provides insights regarding hidden Zn-Pb orebody. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

괴산 성도 연-아연 광상의 산출광물과 생성환경

안성열,신동복 대한자원환경지질학회 2017 자원환경지질 Vol. No.

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-MnSCdS 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 441~490oC, 10-6~10-4.5 atm. and 330~364oC, <10-8 atm. respectively. Phase equilibrium temperatures calculated from Fe and Zn contents for coexisting sphalerite and stannite in hydrothermal vein are 236~254oC. 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 549oC 와 487oC, respectively for skarn ore and hydrothermal ore, than those estimated from phase equilibria imply that isotopic equilibrium has not been fully established. 성도 연-아연광상은 옥천층군 화전리층의 석회암을 교대한 스카른광체와 모암내 열극을 충진한 열수맥상광체로 구분된다. 스카른광물은 헤덴버자이트(hedenbergite) 계열의 휘석이 대부분이며, 그로슐라(grossular)와 안드라다이트(andradite)가 진동누대구조를 보이는 석류석, 그리고 소량의 규회석, 투각섬석, 녹염석 등이 산출되어 환원환경에서 정출된 것으로 보인다. 스카른광체에서는 섬아연석 및 방연석이 우세하고 황철석, 자류철석, 황동석이 소량 수반되며, 열수맥상광체에서는 유비철석, 섬아연석, 황동석 및 황철석과 더불어 방연석, 자연비스무스 및 황석석(stannite)이 소량수반된다. 스카른광체에서 암회색 섬아연석의 FeS 함량은 평균 17.4 mole%, 적갈색 섬아연석은 3.6 mole%이고, 열수맥상광체에서는 10.3 mole%를 나타낸다. 이들을 국내 주요 금속광상의 FeS-MnS-CdS 함량비와 비교한 결과 스카른광체는 연-아연, 열수맥상광체는 금-은 광상 영역에 도시된다. 열수맥상광체에서 산출되는 유비철석의 As 함량은 초기 31.93~33.00 at.%에서 중기 29.58~30.21 at.%로 가면서 점차 감소하며, 이에 따른 광화온도와 황분압은 초기441~490oC, 10-6~10-4.5 atm.와 중기 330~364oC, <10-8 atm.에 해당한다. 섬아연석과 공생하는 황석석의 Fe와 Zn 조성비를 이용한 광물상 평형온도는 236~254oC의 범위를 보인다. 스카른광체 황화광물의 황동위원소 조성은5.4~7.2‰, 열수맥상광체는 5.4~8.4‰로서 화성기원과 유사하거나 다소 높은 값을 나타내어 광상을 형성시킨 황이대체로 마그마에서 유래되었으나 일부 모암의 영향을 받았음을 시사한다. 그러나, 스카른광체와 열수맥상광체에서의황동위원소평형온도가 각각 549oC와 487oC로서 상평형온도 보다 현저히 높게 나타나고 있어서 이들이 동위원소적으로 충분한 평형을 이루지 못한 것으로 추정된다.

국전 Pb-Zn 스카른 광상의 산출상태

양창문 ( Chang Moon Yang ),최진범 ( Jin Beom Choi ) 한국광물학회 2010 광물과 암석 (J.Miner.Soc.Korea) Vol.23 No.4

국전 연-아연 광상은 백악기 말 유천층군의 정각산층 내에 협재된 석회암이 불국사 관입암류인 흑운모화강암에 의해 교대작용을 받아 형성된 스카른 광상이다. 정각산층은 주로 응회질 셰일로 구성되며 사암, 안산암질 응회암, 석회질암, 역암이 협재된다. 암색에 따라 하부, 중부, 상부로 나뉘며 석회질암은 하부에서 6∼8 m의 층후를 가지고 약 500 m 정도 연장을 보인다. 국전광상은 과거 갱내 채굴이 이루어진 죽갱 광체와 광산의 동쪽에 위치한 동부 광체로 구분된다. 주요 광석광물은 섬아연석과 방연석이며 황동석, 유비철석, 황철석, 자류철석 등이 수반되며, 스카른 광물로는 단사휘석과 석류석이 주로 산출되며 양기석, 녹니석, 엑시나이트, 방해석, 석영 등이 수반된다. 죽갱 광체의 경우 부광대를 이루는 중심부로부터 바깥쪽으로 대칭적으로 대상 분포하는 특징을 보여주는데, 중심부로부터 단사휘석(헤덴버자이트)대, 단사휘석-석류석(그로슐라)대, 석류석(안드라다이트)대, 호온펠스 변질대 순으로 분포한다. 단사휘석은 부광대에서 멀어질수록 Fe2+의 함량이 증가한다. 섬아연석은 부광대인 중심부를 포함하여 모든 대에서 산출되며 단사휘석과 마찬가지로 부광대에서 멀어질수록 섬아연석의 Fe2+ 함량이 증가한다. 이는 국전광상의 배태에는 단사휘석과 섬아연석의 공생이 밀접히 관련되어 있음을 지시한다. 따라서, 국전광상의 산출상태는 황철석의 함량이 비교적 적으며 품위가 높은 섬아연석이 단사휘석과 수반되어 부광대를 이루는 것으로 사료된다. The Gukjeon Pb-Zn mine was recognized as skarn deposits which replaced the limestone layer of the Jeongkansan Formation by intrusion of biotite granite in late Cretaceous. The Jeongkansan Formation is mainly composed of tuffaceous shale, and interlayers of sandstone, andesitic tuff, limestone, and conglomerate. The limestone layer is located in the lower part of the Jeongkansan Formation with 6∼8 m in thickness and about 500 m in length. The Gukjeon deposits are divided into the Jukgang ore bodies once mined underground and the eastern ore bodies. Main ores are sphalerite and galena, in association with small amounts of chalcopyrite, arsenopyrite, pyrite, and pyrrhotite, etc. Skarns mainly consist of clinopyroxenes and Ca-garnets, associated with actinolite, chlorite, axinite, and calcite, etc. The Jukgang ore bodies show symmetrical distribution of zoning outward, representing clinopyroxene (hedenbergite) zone, clinopyroxene-garnet (grossular) zone, garnet (andradite) zone, and alteration zone of hornfels. Fe2+ contents in clinopyroxenes increase with decreasing sphalerite grade. Sphalerite ores are found in all zones and Fe2+ contents in sphalerite increase in the same way as those in clinopyroxenes, implying that clinopyroxene and sphalerite are closely related each other. It is concluded that the Gukjeon ores occurred in the ore rich zone of high grade sphalerite with less pyrite in assoication with clinopyroxene.

Ferric methanesulfonate as an effective and environmentally sustainable lixiviant for Zn extraction from sphalerite (ZnS)

Fatemeh Nikkhou,Muhammet Kartal,Fang Xia 한국공업화학회 2021 Journal of Industrial and Engineering Chemistry Vol.96 No.-

Zinc is currently extracted from sphalerite (ZnS) by either sintering-smelting or roasting-leaching. Thesehigh-temperature processes produce environmentally hazardous sulfur dioxide gas. Hence, sustainablezinc extraction calls for direct leaching at low temperatures. Here, we show that ferric methanesulfonateis a high performing lixiviant for this purpose. Using 0.8 M ferric methanesulfonate, 99.3% Zn wasextracted from 106 150 mm sphalerite particles after leaching at 70 C for 96 h. Elemental sulfur, ratherthan sulfur dioxide, was produced as a by-product. When compared to common inorganic lixiviants suchas ferric sulfate or ferric chloride, ferric methanesulfonate demonstrates greater extraction efficiency andis less corrosive, less toxic, and does not release harmful gases. Mineralogical, microscopical, andcompositional characterization of reaction products confirmed the formation of a core–shell structureconsisting of a sphalerite core and a sulfur shell, and the manifestation of a coupled dissolutionreprecipitationmineral replacement mechanism. Efficient zinc extraction was facilitated by theinterconnected pores in sulfur, which provided pathways for mass transfer between the lixiviant andsphalerite core. The precipitation of anglesite (PbSO4), which in some instances caused surfacepassivation through the infilling of sulfur shells, suggests that Pb2+ concentration should be controlledwhen applying ferric methanesulfonate for Zn extraction.

Density functional theory and experimental studies of Cu2+ activation on a cyanide-leached sphalerite surface

Tingsheng Qiu,Yuanqing He,Xianhui Qiu,Xiuli Yang 한국공업화학회 2017 Journal of Industrial and Engineering Chemistry Vol.45 No.-

Density functional theory calculations,flotation behavior, X-ray photoelectron spectroscopy, and infraredspectra were combined to reveal the Cu2+ activation mechanism on a cyanide (CN )-leached sphaleritesurface. Low CN adsorption enhanced the activation capability of Cu2+ on the sphalerite surface,whereas the hydrophilicity of the sphalerite increased with increasing CN coverage, which hindered Cu2+ adsorption. As the amount of chemically adsorbed Cu2+ on the sphalerite surface increased, Cu2+ beganto desorb CN , leading to the same result, which is consistent with the low CN coverage.

ZnS 형광체 분말의 결정결합에 따른 발광특성연구

박용규,성현호,조황신,양해석,이종찬,박대희 한국전기전자재료학회 2000 전기전자재료학회논문지 Vol.13 No.10

ZnS phosphors were sintered at vacuum atmosphere, Sintered under the temperature of 950$\^{C}$, ZnS phosphors were grown into the sphalerite structure and two emission peaks were observed at the positions of 460nm and 528nm of the emission spectra. Sintered over the temperature of 1050$\^{C}$, there were simultaneously the sphalerite and wurtize structure in the ZnS phosphors and three emission peaks were observed at the positions of 440nm and 515nm of emission spectra. The emission peaks of 460nm obsrved under the sphalerite structure and 440nm observed under the wurtize structure were due to the vacancy of Zn formed in the ZnS phosphors. The emission peaks of 528nm observed under the sphalerite structure and 515nm observed under the wurtize structure wre caused by the radiative transitions from the level of the vacancy of S formed in the ZnS phosphors to the valance band.

밀양 단장면 일대에 발달하는 아연-연 광화대의 산출특성

곽지영 ( Ji Young Kwak ),강창원 ( Chang Won Kang ),주수영 ( Soo Young Joo ),정재한 ( Jae Han Jeong ),최진범 ( Jin Beom Choi ) 한국광물학회 2015 광물과 암석 (J.Miner.Soc.Korea) Vol.28 No.3

밀양시 단장면에서 대규모의 아연-연 광화대가 최근 새롭게 발견되었는데 정각산층 내에 협재되어 있는 석회암층을 모암으로 하는 스카른광상이다. 본 연구에서는 야외조사를 통한 광화대의 분포를 파악하고, 광석시료의 암석학적 특징 및 스카른광물과 광석광물의 조성 연구를 통해 이 지역에 발달된 광화대의 특성을 파악하였다. 단장면 일대에 발달하는 광화대는 국전리 광화대, 고례리 광화대 및 구천리 광화대로 크게 3개의 지역에서 산출이 확인되며, 광화대는 주로 약 200-300 m 고도에서는 섬아연석이 주 광석광물을 구성하며, 고도가 높아질수록 방연석의 함량이 많아진다. 광석은 주로 단사휘석대에 산출되며 암녹색 내지 암회색을 띠며 헤덴버자이트, 그로슐라, 양기석 및 녹염석 등의 스카른광물과 함께 수반되고, 액시나이트, 방해석 및 석영 등이 부성분광물로 산출된다. 광석광물로는 섬아연석과 방연석이 산출되는데 섬아연석은 내부에 황동석 및 방연석을 수반하거나 인접하게 산출하며, 단사휘석 및 녹염석과 함께 산출될 때 부광대를 형성한다. 섬아연석의 FeS의 함량은 1.53-23.07mole%로 넓은 범위를 보이며, 관계화성암으로 추정되는 흑운모화강암에서 멀어질수록 그 함량이 현저히 낮아진다. CdS의 값은 0.22-0.93 mole% 범위를 보이며, 국전리 지역에서 구천리 지역으로 갈수록 감소하는 경향을 보인다. 이와 같이 밀양 단장면 일대에 발달하는 아연-연 광화대는 국전리 지역에서부터 구천리지역에 이르기까지 광화유체가 지속적으로 진화하면서 섬아연석의 조성도 순차적으로 변하고 온도가 감소하였을 것으로 판단된다. New occurrences of large-scaled Zn-Pb deposits are recently found in the Danjang-myeon, Milyang. They are skarn-type deposits which replaced the intercalated limestone beds in the Jeonggaksan Formation. This study aims at characterizing occurrences, mineralogy, and chemistry of Zn-Pb ores and skarn minerals. Skarn orebodies are mainly found in 3 areas, named Gukjeon-ri, Gorye-ri, and Gucheon-ri orebodies, where sphalerite found as main ore mineral in 200-300 m in height and amount of galena increases as altitude does. Ores are dark grey to dark green in color and closely related with clinopyroxene zone. They occur with hedenbergite, grossular, actinolite, epidote, and small amounts of axinite, calcite, and quartz. Main ore mineral is sphalerite which includes tiny spotted grains of galena and chalcopyrite and becomes rich in grade in association with clinopyroxene and epidote. FeS contents in sphalerite show relatively wide range between 1.53 and 23.07 mole%, whose contents intend to increase towards biotite granite known as ore-related igneous rocks. CdS contents are in the range of 0.22-0.93 mole%, showing decrease tendency from southwest (Gukjeon-ri) to northeast (Gucheon-ri). Zn-Pb deposits developed in Danjang-myeon reveal decrease in temperature with increase of altitude, leading to gradual changes in compositions of ore and skarn minerals.

탄산염 혹은 황화물 풍부 조건의 하수 처리 과정을 모사한 환경에서 산화아연 (ZnO) 나노입자의 구조 변환 연구

이서연 ( Seoyeon Lee ),한준호 ( Junho Han ),노희명 ( Hee-Myong Ro ) 한국환경분석학회 2021 환경분석과 독성보건 Vol.24 No.2

Developmentofnanotechnologyhasledtotheextensiveapplicationofmetal-oxidenanoparticles(NPs)inindustry,anditcausetoxicityandarisktoecosystemsandhumanhealththroughunidentifiedpathways.Zincoxide(ZnO)isoneofthemostversatileNPs,whichcausesseveredirectandindirecttoxicityupontransformationbyenvironmentalfluctuations.Inthisstudy,thetransformationofZnONPswasexaminedinartificialsewage,whereinthesewagetreatmentprocesswassimulatedusingeithercarbonateorsulfide,underoxicandanoxicconditions.Dynamiclightscattering,transmissionelectronmicroscopy,X-raydiffraction(XRD),X-rayphotoelectronspectroscopy(XPS)wereemployedtoidentifythemorphologyandstructureoftheNPs.TheresultsindicatethatadecreasinginpHandionicstrengthcausestheaggregationofZnONPs,andthecarbonate-richconditionleadstothegrowthofasphericalcrystalintoarectangleform,withoutchangingthecrystalstructure.XRDandXPSanalysisrevealedthatZnONPstransformintothesmallerZnSNPs,sphalerite,undersulfide-richandanoxicconditions.ThisimpliesthatsewagetreatmentwouldcausethetransformationofZnONPsintoZnSNPs,whichhavehighercolloidalstabilityanddissolutionrate;therefore,thetransformationofNPsshouldbecarefullyexaminedandassessedforabetterunderstandingandsafeapplication.