사용 후 태양광 셀로부터 Ultrasonic wave 활용 실리콘 및 유가금속 회수

이동헌 부경대학교 2022 국내석사

Due to the recent rapid industrial development, renewable energy is attracting attention due to the issue of resource depletion and environmental pollution. As interest in new and renewable energy increases, the use of representative eco-friendly energy solar energy is also increasing. As the usage of solar power increases, the amount of waste solar modules with a life expectancy of about 20 to 30 years is expected to increase. According to a report to the IEA, about 76 million tons of waste solar modules are expected to be generated by 2050. The solar module is composed of Si, Ag, Cu, Pb, and Al, of which Pb is expected to cause a lot of environmental pollution when the solar module is buried or incinerated after using it as a harmful component. In this regard, Europe has made it mandatory to collect and recycle waste solar panels since 2012, and in Korea, the EPR system has been implemented since 2023, designating solar modules as essential recycling items, and the need for solar module recycling technology is increasing. Particularly, although Pb included in solar cells among solar modules has a great influence on environmental pollution, technology for recovering solar cells is still insufficient. Conventionally, a stirring process based on acid leaching is used as a process for recycling solar cells. The stirring process makes it difficult to remove impurities from the surface of a photovoltaic cell, so it is judged that a method to remove impurities more finely is needed. This research recovered silicon from solar cells after use using an acid solution and ultrasonic cavitation effect and recovered valuable metals through precipitation, pH control, and reduction reaction from leachate after recovering silicon. Silicon recovery process was experimented with acid solution concentration, reaction temperature, reaction time, and ultrasonic strength as variables, and finally, the purity of silicon recovered was 99.58 % and the recovery rate was 99.94 %, and the purity of silver recovered was 99.72 % and 92.3 %. In addition, Cu and Pb were recovered together and the integrated purity was detected as 96.09 %, and the recovery rate was calculated as Cu 94.63 % and Pb 91.04 %.

폐태양광모듈내 구리리본전극으로부터 유가금속회수에 관한 연구

정우철 부경대학교 2016 국내석사

Photovoltaic solar cell is the energy that not produces pollutants and also not creates any noises and harmful gases, so it is different from fossil fuel, which is not harmful for the environment. Moreover, an energy resource is clean and unlimited. That's why photovoltaic industry is rapidly growing internationally as the life of general photovoltaic solar cell lasts more than 15 years. As photovoltaic industry is developing, the amount that spent photovoltaic solar cell produces is continually and accordingly increasing. As a result, accumulation amount is expected to reach around 130,000 ton in 2030. Although 90% of spent photovoltaic solar cell which all runs out is recyclable, most of them are shredded and grinded. It indicates that valued resources are wasting due to landfill and leaving alone. For these reasons, various investigations of spent photovoltaic solar cell have been conducted for valued resources's collection and recycling. However, investigations especially collecting Cu and Ag from spent photovoltaic solar cell have never tried internationally. This study is recovery of valuable metals such as Cu and Ag from photovoltaic ribbon of spent solar cell. First of all, to obtain copper ribbon and oxide scale, heat treatment by dry process was conducted. In addition, high purity of copper and silver was obtained from vacuum distillation and zone melting methods.

폐 태양광 모듈 내 전지리본으로부터 유가금속 분리정제에 관한 연구

허세권 부경대학교 2018 국내석사

Due to the depletion of fossil fuels and the use of fuels because of the industrial development, the global warming issues have arisen. Therefore, the new renewable energy for solving the environmental issues and energy depletion are receiving much attention. In particular, the photovoltaic energy is the most promising and technically matured sector in the renewable energy sector. The importance of the recycling of photovoltaic modules is increasing and many studies are being conducted on the recovery of the valuable resources from the spent photovoltaic module and the recycling of them worldwide. However, there are not many studies conducted on the recovery of the valuable metals from the spent PV ribbon in the photovoltaic module. Therefore, the recovery and recycling of the valuable metals from the PV ribbon in the spent photovoltaic module is expected to make great contribution to the localization of the economic resources. This study is recovery of valuable metals such as copper, tin, and lead from photovoltaic ribbon in spent solar module by pyrometallurgy method. Photovoltaic ribbon in the spent solar module was oxidized at the surface therefore heat treatment was conducted at a high temperature in a reducing gas atmosphere. The Photovoltaic ribbon is coated with lead and tin alloy on the copper wire. In a high-temperature reducing atmosphere, lead and tin except copper are melted and separated copper by melting point difference. The melted and separated coating layer consists of copper, lead and tin. Under high temperature heat treatment conditions, lead is separated from the coating layer by vapor deposition method and separated into high purity lead and copper-tin alloy. As a result, Copper wire, high purity lead and Copper-tin alloy are successfully separated and recovered from the photovoltaic ribbon.

전기자동차용 리튬이온전지 양극활물질 (LiNiMnCoO₂)로부터 탄산리튬 및 유가금속 회수에 관한 연구

차태민 부경대학교 2019 국내박사

This study is about the recovery of carbon lithium and valuable material (Ni, Mn, Co) from the lithium-ion battery cathode active material for electric vehicles NCM (LiNiMnCoO2) and investigated the conditions of recovery of carbon lithium (Li2CO3) and valuable material by thermal reactions in lithium and valuable material in cathode active materia. To check the thermal behavior of NCM-type cathode active materia, a TGA (thermigravimetric analysis) analysis device was used and CO2 gas was supplied to simulate actual thermal reactions in an anode. cathode active materia was observed to vary in weight between 650 and 800°C, and it is believed that the increase in weight change was due to the super separation of carbon lithium and metal oxide CoO, MnO and NiO. Based on these results, Carbonation experiment was conducted in the temperature zone between 600 and 900°C, water penetration test for separating carbon lithium, and reduction heat treatment test for improving recovery rate of metal powder is as follows. 1. Carbonation test was conducted for phase separation from Li2CO3 and NiO, CoO, and MnO from NCM system acathode active material and confirmed that Li2CO3 and metal oxide NiO, MnO, and CoO are completely separated at 800 to 900°C. The temperature was maintained at 800°C for 2 hours and 2 hours. 2. To selectively recover carbon lithium from the electrolyte powder separated by Carbonation, water penetration was performed using the difference in solubility between carbon lithium and metal oxide. When the ratio of powder and distilled water was between 1:30 and 5 hours, the largest amount of carbon lithium was withdrawn and carbon lithium was recovered. In order to determine the amount of leachate Li from raw materials, the wet analysis method, Integrated Plasma (ICP), was used and approximately 89% lithium was recovered through water penetration. 3. The Monde process was used to selectively recover Ni from the remaining mixture (NiO, CoO, and MnO) after a water leak. Phase I of the process is a reduction phase, and hydrogen (H2) was supplied in the temperature zone (about 200°C) where only NiO can be reduced during the mixing powder. Stage II is the production of nickel carbonyl (Ni(CO)4(g)) so that the reduced Ni is easily separated from the mixture, and nickel carbonyl was produced by supplying CO gas to the mixture maintained at 80°C. Phase III was the final step in the selective recovery of Ni powder and (Ni(CO)4(g) was heat-dissolved at 180°C to obtain high purity Ni. The purity of the Ni powder recovered through the Mond process is approximately 97.99% and is sufficiently reusable for industrial use.

양극 활물질 전구체(NCA)로부터 탄산리튬, 니켈 및 코발트 회수 연구

안세호 부경대학교 2019 국내석사

In recent years, lithium-ion batteries have been used as a main energy source for hybrid mobile phones as well as portable mobile power sources such as smart phones and netbooks due to their high output and high energy characteristics. LCO (LiCoO2), which is a layered structure with a stable capacity, has been widely used as a cathode material for lithium ion battery cells, but its price is unstable due to low capacity characteristics, environmental pollution and cobalt resource constraints. Therefore, NCA (LiNiCoAlO2) anode materials came up as an alternative for solving problems such as high cost and low capacity characteristics of LCO (LiCoO2). NCA (LiNiCoAlO2) has recently been in full swing for the electric vehicle battery market, and the demand for used output batteries has increased. Naturally, the demand for NCA, which is a middle- and high-output active material, has also increased. Studies on recycling of existing cathode active materials include leaching into hydrochloric acid (HCl) and nitric acid (HNO3), and recycling of these waste lithium secondary batteries selectively concentrates only electrode active materials for crushing, magnetic separation, classification, etc. After concentration, there is a method using sulfuric acid leaching method using hydrogen peroxide as a reducing agent, and treatment with mountain solution to recover lithium salt and cobalt salt. In the case of using organic acids, the study on the separation of valuable metals by citric acid (C6H8H8E8) and oxygen acid (C2H2SO4) was conducted. The use of such a wet process has the risk of causing costly processing and environmental problems of the byproducts generated during the process, so it is necessary to develop an environmentally friendly process. As a result, in this study, Carbonation through CO2 thermal reaction, water leaching, and CO gas thermal reaction were performed instead of the conventional wet processing. A method of separating and recovering Li2CO3, Co, and Ni from NCA (LiNiCoAlO2), a cathode active material of spent lithium ion batteries, was studied through an environmentally friendly and simple process. It is expected that it will contribute to localization of raw materials when applied to industry by environmentally friendly and simple metal recovery method.

희토류 산화물의 염소화 및 열환원 공정을 통한 희토류 금속 및 합금 제조

유주원 국립부경대학교 대학원 2025 국내석사

발전터빈 다이아프램 내외부링 링밀 소재 SUS410J1의 열처리 조건에 따른 특성 연구

곽현철 국립부경대학교 산업대학원 2025 국내석사

This paper is a study to evaluate the mechanical properties of ingot-cast alloy materials used as diaphragm materials for turbine components of power generation steam turbines. In this paper, the mechanical properties were confirmed using spark atomic emission spectroscopy, a universal testing machine, a Charpy impact tester, and a Brinell hardness tester. The material is a material (SUS410J1) manufactured by the ingot casting method according to the standards of Mitsubishi Hitachi Power Systems Co., Ltd. (e.g., 80G-10036). The mechanical properties were compared according to the tempering temperature. The JIS code was selected to identify the material properties by the inner surface, outer surface, and mean radius position of the material. According to the test results, the hardness was high in the order of 680℃ > 710℃ > 740℃. At room temperature, the tensile strength was high in the order of 680℃ > 710℃ > 740℃, the yield strength was high in the order of 680℃ > 710℃ > 740℃, the elongation was high in the order of 740℃ > 710℃ > 680℃, and the area shrinkage was high in the order of 740℃ > 710℃ > 680℃. In addition, when the inner diameter and outer diameter were compared, the inner diameter was higher than the outer diameter. The tempering temperature that satisfied the specifications for both the inner diameter and the outer diameter was 740℃.

황산리튬으로부터 침전 및 습식 전환법을 통한 수산화리튬 제조 연구

문정식 국립부경대학교 대학원 2024 국내석사

As the demand for High-Ni cathode materials increases rapidly, the importance of lithium hydroxide is emerging. Accordingly, it is necessary to study the efficient production method of lithium hydroxide monohydrate, which is an essential precursor for the production of lithium ion battery cathode materials. The purpose of this study is to explore the method of producing lithium hydroxide monohydrate from lithium sulfate monohydrate. First, lithium sulfate monohydrate was pyrolyzed and separated into lithium sulfate and water. After that, various precipitating agents (KOH, Ca(OH)2, Sr(OH)2, Ba(OH)2)) were used to compare and analyze the lithium hydroxide conversion rate of the lithium sulfate solution. As a result of the experiment, when Ba(OH)2 was used, the conversion rate was the highest at 95%. In consideration of the high conversion rate of Ba(OH)2, the optimization experiment was conducted with the lithium sulfate concentration, the reaction temperature, and the reaction ratio with the precipitating agent as variables, and a filtration process was performed to remove the precipitate. Finally, the conversion rate and lithium recovery rate of the lithium hydroxide solution were evaluated. The finally produced lithium hydroxide solution was dried at a temperature of 90°C or higher for 24 hours in a vacuum-Ar atmosphere to obtain 99.8% high-purity lithium hydroxide monohydrate.

폐 태양광 셀로부터 고순도 유가금속 회수 연구

김현종 국립부경대학교 대학원 2024 국내석사

It is entering a carbon neutral society due to the recent surge in gas, coal, and oil prices, and the increase in population density and energy. Accordingly, competitiveness in new and renewable energy is increasing, and among them, the equalized power generation cost is the cheapest, and the solar market is expanding. In Korea, technology for recycling photovoltaic cells is insufficient, and research is being conducted on it worldwide, but it is in an insufficient situation. Therefore, this study aims to establish and optimize recycling technology by recovering high purity valuable metals from photovoltaic cells. In this study, the reactivity of each component of the photovoltaic cell to the leachate was confirmed through thermodynamic data collection, the material behavior of the photovoltaic cell to the leachate was confirmed during the equilibrium reaction according to stoichiometry, and the recovery process was optimized. As a result, about 6N of Si could be recovered, and almost all of Ag and Al could be recovered.

폐알루미늄 분진으로부터 용도별 합성 Zeolite 제조 연구

소은규 국립부경대학교 대학원 2024 국내석사

In this study, zeolite synthesis raw material was recovered as slag from waste aluminum dust using a dry melting process, and synthetic zeolite was manufactured using the recovered slag. The prepared zeolite was modified with various cations (Mg2+, Ca2+, K+) and then a comparative experiment on heavy metal removal rate was conducted. In addition, a comparison experiment of hard/soft water conversion ratio was conducted to evaluate the water hardness control performance of Na-Zeolite and K-Zeolite, which can be used to control water hardness. A comparative experiment was conducted according to the amount of carbon added for the dry melting process, and as a result of XRD analysis, it was confirmed that when 4g of carbon was added, the highest Al2O3 and SiO2 content and a single phase of mullite(Al6Si2O13) were formed. The zeolite synthesis process was conducted through comparative experiments depending on the concentration of NaOH, and as a result of XRD analysis, a 50wt.% NaOH solution in which Na-Zeolite was synthesized in the form of a single phase was derived as the optimal process condition. A comparative experiment was conducted on the heavy metal removal rates of the manufactured Na-Zeolite and Mg-Zeolite, Ca-Zeolite, and K-Zeolite converted through cation modification. Standard reagents for four heavy metals, Pb, Hg, Cr6+, and Cd, were prepared and heavy metal removal rate comparison experiments were conducted. The standard reagent was diluted with distilled water, and 5 g of zeolite was added to 50 ml of a 100 ppm concentration heavy metal solution and stirred at room temperature at a speed of 300 rpm for 30 minutes. After stirring, the concentration of heavy metals remaining in the solution was measured using ICP-OES analysis and the removal rate was calculated. In addition, a hard/soft water conversion rate evaluation experiment was conducted to confirm the water hardness control characteristics of Na-Zeolite and K-Zeolite prepared through Na-Zeolite cation modification. In order to confirm the hardness control characteristics of the prepared synthetic zeolite, a solution of 300ppm as CaCO3 or more was arbitrarily prepared and a hard/soft water conversion ratio comparison experiment was conducted. 5 g of K-Zeolite was added to 50 ml of prepared hard water and stirred for 30 minutes at room temperature at a speed of 300 rpm. After stirring was completed, the concentrations of Ca and Mg remaining in the solution were measured using ICP-OES analysis and the average value was calculated. As a result of the experiment, it was confirmed that Mg-Zeolite had the best heavy metal removal ability, and through the comparison test results of hard/soft water conversion rate, it was confirmed that K-Zeolite was more suitable for hard/soft water conversion than Na-Zeolite.