• Title/Summary/Keyword: Valuable Metals

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High-purity Lithium Carbonate Manufacturing Technology from the Secondary Battery Recycling Waste using D2EHPA + TBP Solvent (이차전지 폐액으로부터 D2EHPA + TBP solvent를 활용한 탄산리튬 제조기술)

  • Dipak Sen;Hee-Yul Yang;Se-Chul Hong
    • Resources Recycling
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    • v.32 no.1
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    • pp.21-32
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    • 2023
  • Because the application of lithium has gradually increased for the production of lithium ion batteries (LIBs), more research studies about recycling using solvent extraction (SX) should focus on Li+ recovery from the waste solution obtained after the removal of the valuable metals nickel, cobalt and manganese (NCM). The raffinate obtained after the removal of NCM metal contains lithium ions and other impurities such as Na ions. In this study, we optimized a selective SX system using di-(2-ethylhexyl) phosphoric acid (D2EHPA) as the extractant and tri-n-butyl phosphate (TBP) as a modifier in kerosene for the recovery of lithium from a waste solution containing lithium and a high concentration of sodium (Li+ = 0.5 ~ 1 wt%, Na+ = 3 ~6.5 wt%). The extraction of lithium was tested in different solvent compositions and the most effective extraction occurred in the solution composed of 20% D2EHPA + 20% TBP + and 60% kerosene. In this SX system with added NaOH for saponification, more than 95% lithium was selectively extracted in four extraction steps using an organic to aqueous ratio of 5:1 and an equilibrium pH of 4 ~ 4.5. Additionally, most of the Na+ (92% by weight) remained in the raffinate. The extracted lithium is stripped using 8 wt% HCl to yield pure lithium chloride with negligible Na content. The lithium chloride is subsequently treated with high purity ammonium bicarbonate to afford lithium carbonate powder. Finally the lithium carbonate is washed with an adequate amount of water to remove trace amounts of sodium resulting in highly pure lithium carbonate powder (purity > 99.2%).

Efficient Selective Recovery of Lithium from Waste LiFePO4 Cathode Materials using Low Concentration Sulfuric Solution and 2-step Leaching Method (저농도 황산 용액 및 2-스텝 침출 방법을 이용한 폐LiFePO4 양극재로부터 효율적인 리튬의 선택적 회수)

  • Dae-Weon Kim;Hee-Seon Kim
    • Clean Technology
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    • v.29 no.2
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    • pp.87-94
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    • 2023
  • The recovery of valuable metals from waste lithium-based secondary batteries is very important in terms of efficiently utilizing earth's limited number of resources. Currently, the cathode material of a LiFePO4 battery, a type of battery which is widely used in automobiles, contains approximately 5% lithium. After use, the lithium in these batteries can be used again as a raw material for new batteries through lithium recycling. In this study, low-concentration sulfuric acid, a commonly used type of inorganic acid, was used to selectively leach the lithium contained in a waste LiFePO4 cathode material powder. In addition, in order to compare and analyze the leaching efficiency and separation efficiency of each component, the optimalleaching conditions were derived by applying a two-step leaching process with pulp density being used as a variable during leaching. When leaching with pulp density as a variable, it was confirmed that at a pulp density of 200 g/L, the separation efficiency was approximately 200 times higher than at other pulp densities because the iron and phosphorus components were hardly leached at this pulp density. Accordingly, the pulp density of 200 g/L was used tooptimize the leaching conditions for the selective leaching and recovery of lithium.

Effects of Co-digestate application on the Soil Properties, Leachate and Growth Responses of Paddy Rice (통합혐기소화액의 시용이 벼 생육 및 논토양 환경에 미치는 영향)

  • Hong, Seung-Gil;Shin, Joung-Du;Kwon, Soon-Ik;Park, Woo-Kyun;Lee, Deog-Bae;Kim, Jeong-Gyu
    • Journal of the Korea Organic Resources Recycling Association
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    • v.18 no.4
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    • pp.31-37
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    • 2010
  • Livestock manures have a potential to be a valuable resource with an efficient treatment. In Korea, 42 million tons of livestock manure were generated in 2008, and 84 % of them were used for compost and liquid fertilizer production. Recently recycling of livestock manure for biogas production through anaerobic digestion is increasing, but its utilization in agriculture is still uncertified. In this study, there was applied co-digestate to the paddy for rice cultivation based on N supplement. Co-digestate was fertilizer fermented with pig slurry and food waste combined with the ratio of 70:30(v:v) in its volumetric basis. For assessing the safety of co-digestate, it was monitored the contents of co-digestate for seasonal variation, resulted in no potential harm to the soil and plant by heavy metals. The results showed that soil applied with co-digestate was increased in exchangeable potassium, copper and zinc mainly due to the high rate of pig slurry in co-digestate applied. Considering high salt content due to the combination with food waste, strict quality assurances are needed for safe application to arable land though it has valuable fertilizer nutrient. Leachate after treatment showed that the concentration of nitrate nitrogen washed out within two weeks. Considering the salt accumulation results in soil, it is highly recommended that the application rate of co-digestate should not exceed the crop fertilization rate based on N supplement. With these results, it was concluded that co-digestate could be used as an alternative fertilizer for chemical fertilizer. More study is needed for the long-term effects of co-digestate application on the soil and water environment.

Study on Preparation of High Purity Lithium Hydroxide Powder with 2-step Precipitation Process Using Lithium Carbonate Recovered from Waste LIB Battery (폐리튬이차전지에서 회수한 탄산리튬으로부터 2-step 침전공정을 이용한 고순도 수산화리튬 분말 제조 연구)

  • Joo, Soyeong;Kang, Yubin;Shim, Hyun-Woo;Byun, Suk-Hyun;Kim, Yong Hwan;Lee, Chan-Gi;Kim, Dae-Guen
    • Resources Recycling
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    • v.28 no.5
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    • pp.60-67
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    • 2019
  • A valuable metal recovery from waste resources such as spent rechargeable secondary batteries is of critical issues because of a sharp increase in the amount of waste resources. In this context, it is necessary to research not only recycling waste lithium-ion batteries (LIBs), but also reusing valuable metals (e.g., Li, Co, Ni, Mn etc.) recovered from waste LIBs. In particular, the lithium hydroxide ($LiOH{\cdot}xH_2O$), which is of precursors that can be prepared by the recovery of Li in waste LIBs, can be reused as a catalyst, a carbon dioxide absorbent, and again as a precursor for cathode materials of LIB. However, most studies of recycling the waste LIBs have been focused on the preparation of lithium carbonate with a recovery of Li. Herein, we show the preparation of high purity lithium hydroxide powder along with the precipitation process, and the systematic study to find an optimum condition is also carried out. The lithium carbonate, which is recovered from waste LIBs, was used as starting materials for synthesis of lithium hydroxide. The optimum precipitation conditions for the preparation of LiOH were found as follows: based on stirring, reaction temperature $90^{\circ}C$, reaction time 3 hr, precursor ratio 1:1. To synthesize uniform and high purity lithium hydroxide, 2-step precipitation process was additionally performed, and consequently, high purity $LiOH{\cdot}xH_2O$ powder was obtained.

Evaluation of the Removal Characteristics of Pollutants in Storm Runoff Depending on the Media Properties (여재 특성에 따른 강우 유출수 내 오염물질 제거특성 평가)

  • Kim, Tae-Gyun;Cho, Kang-Woo;Song, Kyung-Guen;Yoon, Min-Hyuk;Ahn, Kyu-Hong;Hong, Sung-Kwan
    • Journal of Korean Society of Environmental Engineers
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    • v.31 no.7
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    • pp.483-490
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    • 2009
  • The aims of this study were to evaluate the removal efficiency for various pollutants in urban storm runoff by a filtration device, and to determine design parameters depending on filter media properties. Appropriate selection of filter media will affect the size and life time of the filtration device. Sets of column tests were performed in order to evaluate the removal efficiency by perlite and a synthetic resin. An investigation of surface properties including CEC (cation exchange capacity) and zeta-potential suggested that the perlite had a superior adsorption capability for cationic pollutants. TCODcr and turbidity were analyzed to investigate the removal characteristic of particulate pollutant. In both columns, the particles in the collected storm runoff was almost completely capture with a small EBCT (empty bed contact time) of 2.5 minutes. Complete clogging at the EBCT of 2.5 minutes occurred after 630 minutes in the perlite column and 810 minutes in the resin column. The removal efficiency of TCODcr and turbidity at the EBCT of 2.5 minutes decreased to below 70% due to an wall effect. The removal efficiency for dissolved pollutant (SCODcr) was negligible due to the insufficient contact time for adsorption. The removal of heavy metals (Cu, Zn, Pb) was mostly ascribed to the filtration of particles containing metals, since the relationship between CEC and the removal efficiency was not apparent. The result of this study would be valuable for the application of filtration device to control of urban storm runoff.

Monitoring of Heavy Metals Migrated from Polylactide (PLA) Food Contact Materials in Korea (국내 유통 폴리락타이드(PLA) 식품용 기구 및 용기·포장의 중금속 이행량 모니터링)

  • Kim, Hyeonuk;Park, So-Yeon;Jo, Ye-Eun;Park, Yongchjun;Park, Se-Jong;Kim, Meehye
    • Journal of Food Hygiene and Safety
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    • v.33 no.2
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    • pp.102-109
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    • 2018
  • In the present study, a variety of polylactide (PLA) articles (n = 211) were tested for migration of lead (Pb), cadmium (Cd) and arsenic (As) into the food simulant (4% v/v acetic acid). Pb, Cd, and As were analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Migration tests were performed at $70^{\circ}C$ and $100^{\circ}C$ for 30 min. The amounts of Pb, Cd, and As increased at $100^{\circ}C$ for 30 min compared with levels at $70^{\circ}C$. However, the migration at both conditions was very low. The maximum level of Pb at $100^{\circ}C$ for 30 min corresponded to 1% of the migration limit. The estimated daily intakes (EDI) based on safety evaluation ranged from $2.5{\times}10^{-5}$ to $2.0{\times}10^{-3}{\mu}g/kg\;bw/day$ for Pb, Cd, and As. The EDI calculated from migration of Pb at $100^{\circ}C$ for 30 min in PLA was the maximum value, $2.0{\times}10^{-3}{\mu}g/kg\;bw/day$, which corresponded to 0.055% of provisional tolerable weekly intake (PTWI, $25{\mu}g/kg\;bw/week$). The data from this study represent a valuable source for science-based safety control and management of hazardous heavy metals migrating from polylactide food contact materials.

Characteristics of micronized blue ceramic pigments using electric arc furnace dust (제강분진을 활용한 청색 세라믹 안료의 미립화 거동에 관한 연구)

  • Kim, Hye-Jin;Han, Kyu-Sung;Hwang, Kwang-Taek;Nahm, Sahn;Kim, Jin-Ho
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.29 no.3
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    • pp.115-122
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    • 2019
  • Electric arc furnace dust (EAFD), which is a dust waste generated in the steel manufacturing process, contains heavy metals. Recently, researches of recycling a large amount of valuable metals such as zinc and iron in EAFD are being actively carried out. In this study, EAFD is used as a substitute for cobalt in blue ceramic pigments without any pretreatment. Then, the synthesized blue ceramic pigment using EAFD was micronized and formulated as a ceramic ink for inkjet printer. The particle size distribution, crystal structure and color characteristics during the micronization process were investigated for the development of ceramic ink. $Co_{0.75}Zn(EAFD)_{0.25}Al_2O_4$ ceramic pigments showed excellent blue coloric properties and monomodal distribution through micronization process. The average particle size of $Co_{0.75}Zn(EAFD)_{0.25}Al_2O_4$ ceramic pigments after 3 hours of milling was $0.271{\mu}m$, which is smaller than $0.303{\mu}m$, which is the average particle size of $CoAl_2O_4$ ceramic pigments without EAFD after 5 hours of milling. Especially, it was confirmed that $Co_{0.75}Zn(EAFD)_{0.25}Al_2O_4$ ceramic pigments showed a color difference (${\Delta}E{^*}_{ab}$) value of 5.67, which smaller than ${\Delta}E{^*}_{ab}$ value of $CoAl_2O_4$ during micronization. These results show that EAFD can be used as a raw material for a blue ceramic pigment by replacing expensive cobalt without any pretreatment.

Evaluation of Sprouted Barley as a Nutritive Feed Additive for Protaetia brevitarsis and Its Antibacterial Action against Serratia marcescens (흰점박이꽃무지 사료첨가제로서 새싹보리의 곤충병원성 세균에 대한 항균 효과에 관한 연구)

  • Song, Myung Ha;Kim, Nang-Hee;Park, Kwan-Ho;Kim, Eunsun;Kim, Yongsoon
    • Journal of Life Science
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    • v.31 no.5
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    • pp.475-480
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    • 2021
  • Interest in edible insects such as Protaetia brevitarsis has increased rapidly, and several insect producers use these insects in industrialized mass production. However, mass rearing of insects can cause insect diseases. Sprouted barley is a valuable source of nutrients and has antioxidant, antimicrobial, anti-inflammatory, and anti-cancer effects. This study was conducted to investigate the effect of sprouted barley as a feed additive for producing healthy P. brevitarsis larvae. P. brevitarsis larvae were fed feeds with or without sprouted barley, and their body weight and larval period wewe checked weekly. To confirm the antibacterial effects of sprouted barley, in vitro bioassays were performed by counting Serratia marcescens colonies, and in vivo bioassays were performed by determining the survival rate and body weights of the S. marcescens-infected larvae. Larvae fed different feeds were analyzed for their nutrient compositions (i.e., such as proximate composition, minerals, amino acids, and heavy metals). Larvae fed 5% and 10% sprouted barley had maximum weight increases of 19.2% and 23.1%, respectively. Both treatment groups had significantly shorter larval periods than those of the control group. Sprouted barley markedly inhibited the growth of entomopathogenic S. marcescens. Furthermore, larvae fed sprouted barley exhibited higher Cu, Zn, and K levels. Seventeen amino acids were present in larvae fed sprouted barley, of which, tyrosine and glutamic acid were predominant. No heavy metals were detected in any of the investigated groups. Therefore, sprouted barley may be a suitable feed additive for producing high-quality P. brevitarsis larvae.

Cation Exchange Capacities, Swelling, and Solubility of Clay Minerals in Acidic Solutions : A Literature Review

  • Park, Won Choon
    • Economic and Environmental Geology
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    • v.12 no.1
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    • pp.41-49
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    • 1979
  • A literature review is made on the physical and chemical characteristics of clay minerals in acidic solutions from the mineralogical and hydrometallurgical viewpoints. Some of the important characteristics of clays are their ability to cation exchange, swelling, and incongruent dissolution in acidic solutions. Various clay minerals can take up metallic ions from solution via cation exchange mechanism. Generally, cation exchange capacity increases in the following order : kaolinite, halloysite, illite, vermiculite, and montmorillonite. In acidic solutions, the cation uptake such as copper by clay minerals is strongly inhibited by hydrogen and aluminum ions and thus is not economically significant factor for recovery of metals such as uranium and copper. In acidic solutions, the cation uptake is substial. Swelling is minimal at lower pH, possibly due to lattice collapse. Swelling may be controllable with montmorillonite type clays by exchanging interlayer sodium with lithium and/or hydroxylated aluminum species. The effect of add on clay minerals are : 1. Division of aggregates into smaller plates with increase in surface area and porosity. 2. Clay-acid reactions occur in the following order: (i) $H^+$ replacement of interlayer cations, (ii) removal of octahedral cations, such as Al, Fe, and Mg, and (iii) removal of tetrahedral Al ions. Acid attack initiates, around the edges of the clay particles and continued inward, leaving hydrated silica gel residue around the edges. 3. Reaction rates of (ii) and (iii) are pseudo-1st order and proportional to acid concentration. Rate doubles for every temperature increment of $10^{\circ}C$. Implications in in-situ leaching of copper or uranium with acid are : 1. Over the life span of the operation for a year or more, clays attacked by acid will leave silica gel. If such gel covers the surface of valuable mineral surfaces being leached, recovery could be substantially delayed. 2. For a copper deposit containing 0.5% each of clay minerals and recoverable copper, the added cost due to clay-acid reaction is about 1.5c/lb of copper (or 0.93 lbs of $H_2SO_4/1b$ of copper). This acid consumption by clay may be a factor for economic evaluation of in-situ leaching of an oxide copper deposit.

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A Study on the Distributional Characteristics of Unminable Manganese Nodule Area from the Investigation of Seafloor Photographs (해저면 영상 관찰을 통한 망간단괴 채광 장애지역 분포 특성 연구)

  • Kim, Hyun-Sub;Jung, Mee-Sook;Park, Cheong-Kee;Ko, Young-Tak
    • Geophysics and Geophysical Exploration
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    • v.10 no.3
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    • pp.173-182
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    • 2007
  • It is well known that manganese nodules enriched with valuable metals are abundantly distributed in the abyssal plain area in the Clarion-Clipperton (C-C) fracture zone of the northeast Pacific. Previous studies using deep-sea camera (DSC) system reported different observations about the relation of seafloor topographic change and nodule abundance, and they were sometimes contradictory. Moreover, proper foundation on the estimation of DSC underwater position, was not introduced clearly. The variability of the mining condition of manganese nodule according to seafloor topography was examined in the Korea Deep Ocean Study (KODOS) area, located in the C-C zone. In this paper, it is suggested that the utilization of deep towing system such as DSC is very useful approach to whom are interested in analysing the distributional characteristics of manganese nodule filed and in selecting promising minable area. To this purpose, nodule abundance and detailed bathymetry were acquired using deep-sea camera system and multi-beam echo sounder, respectively on the seamount free abyssal hill area of southern part ($132^{\circ}10'W$, $9^{\circ}45'N$) in KODOS regime. Some reasonable assumptions were introduced to enhance the accuracy of estimated DSC sampling position. The accuracy in the result of estimated underwater position was verified indirectly through the comparison of measured abundances on the crossing point of neighboring DSC tracks. From the recorded seafloor images, not only nodules and sediments but cracks and cliffs could be also found frequently. The positions of these probable unminable area were calculated by use of the recorded time being encountered with them from the seafloor images of DSC. The results suggest that the unminable areas are mostly distributed on the slope sides and hill tops, where nodule collector can not travel over.